Title of Invention

A METHOD AND APPARATUS FOR THE PREPARATION OF A POLYNUCLEATE METAL COMPOUND

Abstract The present invention discloses a method for the preparation of a polynucleate metal compound, comprising at least one metal in the +2 or the +3 valence state, wherein said polynucleate metal compound is formed by the aqueous reaction of a metal halide solution with at least one metal, wherein said metal halide solution comprises at least one metal in the +2 or +3 valence state, wherein said at least one metal is in the 0, +2 or +3 valence state, and if in the 0 valence state is capable of entering the +2 or +3 valence state wherein said metal halide solution is formed by the aqueous reaction between said metal(s) within said metal halide solution and a halide acid, and wherein said halide acid is formed by the reaction of a metal halide salt, comprising the corresponding halide of said halide acid, with a sulfoxy acid. The present invention also discloses a manufacturing apparatus for producing a polynucleate metal compound, said manufacturing apparatus comprising: one or more units defining a process flow path, wherein at least one or more units form said polynucleate metal compound from the aqueous reaction of a metal halide solution with at least one metal, wherein said metal halide solution comprises at least one metal in the +2 or +3 valence state, wherein said at least one metal comprises a metal(s) in the 0, +2 or +3 valence state, and if in the 0 valence state capable of entering the +2 or +3 valence state, wherein one or more units form said metal halide solution by reacting the metal(s) of said metal halide solution with a halide acid, wherein said halide acid formation comprises the reaction of a metal halide salt, comprising the corresponding halide of said halide acid, wherein said one or more units which form said halide acid by reacting a metal halide salt, comprising the corresponding halide of said halide acid, with a sulfoxy acid, are upstream of one or more units form said metal halide solution by reacting the metal(s) or said metal halide solution with a halide acid, as well as upstream of said one or more units forming said metal halide solution by reacting the metal(s) of said metal halide solution with a halide acid.
Full Text

PATENT SPECIFICATION
INVENTORS: RICHARD A. HAASE AND JOHN E. SMAARDYK
Related Application Data
This application claims priority based on U.S. Patent Application 11/041,329
filed January 24, 2005, U.S. Provisional Application 60/716,323 filed September 12,
2005 and U.S. Provisional Application 60/728,607 filed October 20, 2005.
BACKGROUND OF THE INVENTION
Field of the Invention
The instant invention relates to improved processes for the preparation of
polynucleate aluminum hydroxyl-halide complexes and of disinfectants. The instant
invention obtains simplified processes for the preparation of polynucleate aluminum
hydroxyl-chloride complexes, known as polynucleate aluminum compounds (PAC)
and aluminum chlorohydrate (ACH), with ACH normally used to define products
having basicities of over 50% and having a higher corresponding aluminum content.
All of these complexes have the general formulation Alx(OH)yClz.
The instant invention also obtains simplified processes for the preparation
of polynucleate metal hydroxy-halide complexes having the general formulation
Mx(OH)yHz, where H is a halogen, preferably CI, and M is at least one metal or
group of metals in either +2 or the +3 valence state and wherein, M is added to
the polynucleate aluminum hydroxy-halide metal complex in the form of the metal
halide acid solution, the base metal, the metal oxide or the metal hydroxide.
As defined in this instant invention, the term metal polymer (MP) is meant
to refer to any polynucleate aluminum or polynucleate metal(s) complex or
compound, including those which do not contain aluminum.

These MP are intended for use in liquid solids separations, such as in water
purification, sludge dewatering and paper production, as well as solids dewatering and
similar dewatering applications, being delivered in solution or in solid form. These MP
can be used in a variety of applications including water purification, antiperspirants,
corrosion control, and conductivity. The applications for these MP are only limited by
the inclusion metal(s) and the application mechanism of the associated product,
whether that product be in liquid, solid or dry form.
The instant invention obtains simplified processes for MP, wherein the halogen
raw material is in a salt form and is converted to an acid form via either acidification
with sulfuric acid (H2SO4) and/or sulfurous acid (H2SO3) or with electrolysis. The
instant invention obtains improved processes for the manufacture of disinfectants,
wherein the disinfectant contains an oxidative element or compound, and wherein
the energy of manufacture is obtained from the energy of formation from at least
one selected from a list consisting of: sulfur dioxide (SO2) from the burning of sulfur
(S) in air or O2, sulfur trioxide (SO3) from the oxidation of SO2, H2SO4 formation from
SO3, sulfurous acid (H2SO3) formation from SO2 with air or O2, halide acid formation
from the reaction of a metal halide with an acid based upon an oxidation state of
sulfur (a sulfoxy acid, preferably H2SO4 and/or H2SO3) and any combination therein.
The instant invention obtains improved processes for the manufacture of an acid and
a base, wherein said acid is based upon a halogen anion and wherein said base is
based upon the hydroxyl anion. The instant invention provides for an improved
process for the manufacture of gypsum, calcium sulfate di-hydrate, as well as
calcium sulfate V2 hydrate, calcium sulfite and calcium hydrogen sulfite, wherein
sulfur is a raw material for the manufacture of gypsum, and wherein said sulfur is
preferably a product of the purification of a hydrocarbon, such as oil.
The processes of the instant invention: use less expensive raw materials,
manage heat and chemical energy more efficiently, have lower transportation costs
and require less handling of hazardous chemicals thereby requiring significantly less
manufacturing cost.

Description of the Prior Art and Background
PAC - Since the 1970's it has been known in the art to prepare polynucleate (or
polynuclear) aluminum complexes, also known as aluminum polymers. The first
products that showed promise were poly aluminum sulfates. Processes for the
production of poly aluminum sulfates are disclosed and presented in U.S. Pat. Nos.
4,284,611 and 4,536,665 and Canadian Patent Nos. 1,203,364; 1,203,664;
1,203,665; and 1,123,306, while used as a reference in this instant invention. In
these patents, poly aluminum sulfate is produced by reacting sulfate solutions with
sodium carbonate or sodium hydroxide to form an insoluble aluminum hydroxide gel,
wherein soluble sodium sulfate is then removed.
U.S. Pat. No. 4,877,597 describes another process for the production of
poly aluminum sulfate, while used as a reference in this instant invention. This
process eliminated the initial step of producing an aluminum hydroxide gel by
reacting aluminum sulfate with sodium aluminate.
U.S. Pat. No. 3,544,476 discloses a process for the formation of a poly
aluminum chloral-sulfate, while used as a reference in this instant invention. It is
prepared by first producing an aluminum chloride/aluminum sulfate solution and
then basifying this solution with calcium carbonate of lime. The insoluble calcium
sulfate is removed.
U.S. Pat. Nos. 2,196,016; 2,392,153; 2,392,153; 2,392,531; 2,791,486;
3,909,439, and 4,082685 disclose processes for the production poly aluminum
chloride (low basicity ACH), while used as a reference in this instant invention.
These processes involve reacting aluminum oxy-hydrates or aluminum hydroxy-
hydrates with hydrochloric acid (HCI) under high temperature and pressure
conditions.
U.S. Pat. Nos. 4,362,643 and 4,417,996 disclose processes for the
production of poly aluminum-iron complexes, while used as a reference in this
instant invention. These processes involve reacting aluminum chloride/iron
chloride solution with aluminum hydroxide or aluminum oxy-hydrates, as well as
reacting a poly aluminum chloride with iron.
U.S. Pat. No. 4,131,545 discloses a process for the production of poly
aluminum sulfate compounds by reacting aluminum sulfate with phosphoric acid

and calcium sulfate, while used as a reference in this instant invention. In the
water industry, it is known at this time that PAC compounds containing sulfate are
known to out perform aluminum salts, iron salts, PAC and ACH in water
temperatures from approximately 34 to approximately 40° F (4 °C).
The most common PAC is ACH. ACH is the most common PAC due to its
higher aluminum content, which significantly increases the effectiveness of the
PAC in operating temperatures over 40° F (4 °C). U.S. Pat. Nos. 4,051,028 and
4,390,445 disclose processes for the formation of a poly aluminum
hydroxychloride (ACH), while used as a reference in this instant invention. It is
prepared by reacting aluminum chloride solution and aluminum hydroxide with
calcium carbonate or lime. Insoluble calcium carbonate is removed. U.S. Pat.
Nos. 4,034,067 and 5,182,094 disclose processes for the formation of a poly
aluminum hydroxychloride, while used as a reference in this instant invention. It
is prepared by reacting aluminum chloride solution with alumina or aluminum
hydroxide under conditions of high temperature and pressure.
U.S. Pat. No. 5,938,970 discloses a method of forming polynucleate bi-
metal hydroxide complexes (2 metals are used), while used as a reference in this
instant invention. This process describes the use of a trivalent metal in
combination with a divalent metal, wherein the trivalent metal is in an acid
solution and is reacted with the oxide or hydroxide form of the divalent metal.
WO 97/11029 (PCT/US96/13977) and U.S. Pat. No. 5,985,234 disclose a
method of forming polynucleate aluminum complexes, wherein sodium aluminate is
required to be reacted with either aluminum chloride or aluminum chlorosulfate,
while used as a reference in this instant invention; the reaction is carried out
under conditions of high shear agitation to minimize gel formation. The reaction is
to be carried out at a temperature of under 50 °C producing a milky suspension
which clears over time.
At this time, ACH is known to be prepared by four methods. The first method
is by reacting alumina and/or aluminum hydroxide with aluminum chloride solution
(ACS) in a single step process at elevated temperature or pressure or both. Alumina
is defined in the instant invention as any mixture comprising primarily aluminum oxy-
hydrates and/or aluminum hydroxy-hydrates as those occur in nature and as purified

from raw bauxite. Raw bauxite is purified by the Bayer process which utilizes the
amphoteric nature of aluminum, which allows aluminum to be soluble at high pH as
well as at low pH. Other metals do not exhibit this characteristic. Thereby aluminum
is purified from other metals at a pH of approximately greater than 10.0 and at high
enough operating temperature to flow the aluminum oxy- and hydroxy-hydrates.
The second method is by reacting HCI with an excess of alumina and/or aluminum
hydroxide at elevated pressure and/or temperature. The third process is by reacting
alumina and/or aluminum hydroxide with HCI and metal carbonates or metal oxides
at elevated temperature and/or pressure. The fourth method, which is disclosed in
U.S. Pat. No. 5,904,856, presents a method of acidifying cement in HCI or ACS. A
consequence of the second and the third process is large amounts of non-reacted
aluminum hydroxide material that have to be returned to the process, which makes
the process considerably more expensive. A consequence of the third process is a
frothing of the carbonates in the reaction vessel; further, these products do not dry
well should one desire a dry final aluminum polymer. The first and fourth processes
are very expensive requiring the transport of large quantities of ACS. The second,
third, and fourth processes are very expensive requiring the transportation of large
quantities of HCI. Depending upon the concentration, HCI is at least approximately
65 percent water and ACS is at least approximately 60 to 90 percent water, the
transportation of HCI or ACS requires the transportation and handling of large
quantities of water and is therefore not economical. A consequence of the fourth
process is the cost of first preparing the sintered cement containing Al2O3 and CIO. A
consequence of all these processes is a purity limitation of the bauxite, if bauxite is
used, as metal impurities in some forms of bauxite cannot be polymerized in the PAC
when the PAC is used for drinking water purification.
All of these PAC and MP patent(s) are incorporated herein as a reference.
All of these processes are limited with regard to the starting materials. Per any of
these processes, large amounts of HCI or ACS or other metal acid solution must be
handled. Per any of these processes, to prepare the ACS, HCI must be used. In
summary, all require transportation, storage, and handling of large quantities of
hazardous chemicals.

Further, the drinking water industry is placing restrictions on the amount of
soluble aluminum in the final water product. Industrial processes have for years
restricted aluminum salt coagulation to eliminate soluble aluminum in the final purified
water. PAC(s) do not produce soluble aluminum in the final water. MP's do not place
a soluble metal into the water. Due to requirements in both potable and industrial
water coagulation, a safer, simpler and more economical process is needed for the
manufacture of PAC(s) and MP(s).
Energy - None of these processes manage heat or chemical energy in an efficient
manner. All of these processes require adding heat to the PAC or MP reactor and
require heat in the preparation of alumina with no consideration given to the
exothermic nature of either HCI or ACS formation. All of these processes require
the preparation of HCI or delivery of HCI prior to ACS manufacture, while there
are significant amounts of potential chemical energy available in the conversion of
sodium chloride to HCI and in the conversion of aluminum to ACS utilizing HCI.
Finally, none of these processes investigate either the use of H2SO4 and/or H2SO3
for the preparation of HCI, the very exothermic production of H2SO4 and/or H2SO3
from S or the very exothermic formation of HCI from a metal chloride salt reacting
with H2SO4 and/or H2SO3, all of which present the ability to produce heat energy,
steam and electricity.
HCI - Other than the lost energy and the cost of purchase, HCI transportation has
many issues, which include increased cost and environmental concerns. HCI has to be
transported and suitable ventilation has to be arranged in order to eliminate the
release of Hydrogen Chloride gas, HCI(g). Further, aqueous chlorine (CI), or the
chloride ion, is produced from aqueous HCI. The chlorine (Cl2) production process is
an expensive one that requires drying and refrigeration prior to storage. The most
significant issue with Cl2 is storage. Cl2 is an extremely hazardous chemical to store;
therefore, storage of Cl2 is expensive. The hazardous nature of Cl2 has, in recent
years, caused many water purification facilities to reevaluate the usage of Cl2 versus
bleach or other disinfectants.

Upon contact with water, Cl2 forms both the chloride ion and the chlorite
ion. The chlorite ions are decomposed into chloride ions with temperature. The
addition of heat to large volumes of liquid is also very expensive. Moreover, HCI
must be stored and transported in polymer-lined containers where the releases of
HCI(g) vapors must be controlled. In summary, the production and transportation
of HCI and/or Cl2 is both expensive and hazardous.
ACS - ACS is formed by the reaction of HCI with aluminum hydroxide, alumina
(aluminum hydroxide and/or aluminum oxide in the dry or hydrate form) or
aluminum. While ACS can be prepared from bauxite, this is not preferred in most
applications because the acidification of aluminum in bauxite to ACS can also acidify
any other metal impurities that may be present in the raw bauxite. Formation of
ACS also releases HCI(g), which must be controlled. This is an expensive process.
Therefore, in summary, the current processes always provide complications leading
to increases in the cost of the final product, as well as many safety concerns which
must be managed.
Disinfectants - Further yet, in all applications of water purification, there are
efforts to eliminate the formation of chloro-organic compounds, which have been
found to be at least one of: toxic, carcinogenic, teratogenic and any combination
therein. The drinking water industry is limiting Cl2 and bleach disinfection,
investigating alternative disinfectants such as H2O2, O2, ozone (O3) and chlorine
dioxide (CIO2). The power industry has learned that those same chloro-organic
compounds prematurely contaminate demineralizer beds, thereby resulting in the
use of such alternative such as H2O2, O2, O3 and CIO2. The paper industry has
learned that those same chloro-organic compounds are found in both the final
paper product and in the plant wastewater, thereby requiring investigation of
alternatives such as H2O2, O2 and O3. The manufacture of O3 requires O2, which is
an expensive product formed by either separation of air or electrolysis of water.
Also, CIO2 is an extremely hazardous chemical to transport, thereby requiring on-
site generation from other Cl2 compounds, such as bleach (hypochlorite), chlorite
and chlorate. Previous work in the manufacture of chlorite and chlorate is

referenced herein in U.S. Patents 2,092,944; 2,092,945; 2,194,494; 2,323,180;
2,616,783; 2,833,624; 3,101,248; 3,450,493; 3,760,065; 3,760,065; 3,828,097;
3,997,462; 4,081,520; 4,086,329; 4,087,515; 4,421,730; 4,465,658; 4,473,540;
4,683,039; 5,091,166; 5,091,167; 5,116,595; 5,205,995; 5,366,714; 5,593,653;
5,597,544; 5,639,559; and 6,251,357; along with 2189289 from CA; 55-098965
from JP and 56-921O2 from JP. »
While there are many methods to prepare H2O2, there are two primary
chemical manufacturing processes: the hydroquinone (HQ) process and the sulfuric
acid/electrolysis (SAE) process. Historically, SAE was the preferred process until the
1960's and 1970's wherein industry converted to HQ due to the operating cost savings
of eliminating the electrical cost associated with SAE. However, by its nature, HQ has
a limitation of organic contamination, which is due to the use of an organic chemical
(hydroquinone) as a catalyst. Further, the discovery of chloro-organic toxicity has lead
industry to require more pure forms of H2O2. In H2O2 manufacturing, membranes
have been discussed as methods of H2O2 purification. U.S. Pat. Nos. 4,879,043 and
6,333,018 present the use of reverse osmosis membrane technology as a final
purification step in the production of H2O2 manufactured by HQ, while used as a
reference in this instant invention. U.S. Pat. Nos. 5,215,665; 5,262,058 and 5,906,738
present the use of reverse osmosis membrane technology in combination with cationic
resin technology as final purification steps in the production of H2O2 manufactured by
HQ, while used as a reference in this instant invention. U.S. Pat. Nos. 5,851,042 and
6,113,798 present the use of converting contaminant particles by reacting said
particles with micro-ligands, then separating said reaction products with membranes as
a final purification step in the production of H2O2 manufactured by HQ, while used as a
reference in this instant invention. U.S. Pat. No. 5,800,796 presents an
electrochemical reactor wherein O2 and H2 are reacted across a conductive membrane
containing reducing catalysts forming H2O2, while used as a reference in this instant
invention. This novel process eliminates HQ while simplifying the process H2O2
production. However, the potential for contamination of H2O2 with heavy metals from
the reducing catalyst is significant. Heavy metals contamination eliminates the
potential use of H2O2 in either the production of micro-circuitry or water purification. In
addition, the potential safety issues from the reaction of very explosive O2 and/or H2 in

an electrolytic environment preclude the potential use of this process at the end-use
site. U.S. Publication 20040126313 teaches the use of membrane technology in
combination with SAE; however, a source of electricity is not presented. None of these
references present SAE with a source of electricity. All of these H2O2 patents are
incorporated herein as a reference.
While there are many methods to prepare O2, the separation of air into its
component gases is performed by three methods: cryogenic distillation, membrane
separation and pressure swing adsorption (PSA, which includes vacuum).
Conventional cryogenic distillation processes that separate air into O2, Argon (Ar) and
nitrogen (N2) are commonly based on a dual pressure cycle. Air is first compressed
and is subsequently cooled, wherein cooling is accomplished by one of four methods:
1 - vaporization of a liquid, 2 - the Joule Thompson effect; 3 - counter-current heat
exchange with previously cooled warming product streams or with externally cooled
warming product streams, and 4 - the expansion of a gas in an engine doing external
work. The cooled and compressed air is usually introduced into two fractioning zones.
The first fractioning zone is thermally linked with a second fractioning zone which is at
a lower pressure. The two zones are thermally linked such that a condenser of the
first zone reboils the second zone. Air undergoes a partial distillation in the first zone
producing a substantially pure N2 fraction and a liquid fraction that is enriched in O2.
The enriched O2 fraction is an intermediate feed to the second fractioning zone. The
substantially pure N2 from the first fractioning zone is used as reflux at the top of the
second fractioning zone. In the second fractioning zone, separation is completed
producing substantially pure O2 from the bottom of the zone and substantially pure N2
from the top. When Ar is produced or removed a third fractioning zone is employed.
The feed to this third zone is a vapor fraction enriched in Ar which is withdrawn from
an intermediate point in the second fractioning zone. The pressure of this third zone is
of the same order as that of the second zone. In the third fractioning zone, the feed is
rectified into an Ar rich stream which is withdrawn from the top, and a liquid stream
which is withdrawn from the bottom of the third fractioning zone and introduced to the
second fractioning zone at an intermediate point. Reflux for the third fractioning zone
is provided by a condenser which is located at the top. In this condenser, Ar enriched
vapor is condensed by heat exchange from another stream, which is typically the

enriched O2 fraction from the first fractioning zone. The enriched O2 stream then
enters the second fractioning zone in a partially vaporized state at an intermediate
point above the point where the feed to the third fractioning zone is withdrawn.
The distillation of air, a ternary mixture into N2, O2 and Ar may be viewed as
two binary distillations. One binary distillation is the separation of the high boiling
point O2 from the intermediate boiling point Ar. The other binary distillation is the
separation of the intermediate boiling point Ar from the low boiling point N2. Of these
two binary distillations, the former is more difficult, requiring more reflux and/or
theoretical trays than the latter. Ar-O2 separation is the primary function of the third
fractioning zone and the bottom section of the second fractioning zone below the point
where the feed to the third zone is withdrawn. N2-Ar separation is the primary
function of the upper section of the second fractioning zone above the point where the
feed to the third fractioning zone is withdrawn. The ease of distillation is a function of
pressure. Both binary distillations become more difficult at higher pressure. This fact
dictates that for the conventional arrangement, the optimal operating pressure of the
second and third fractioning zones is at or near the minimal pressure of one
atmosphere. For the conventional arrangement, product recoveries decrease
substantially as the operating pressure is increased above one atmosphere mainly due
to the increasing difficulty of the Ar-O2 separation. There are other considerations,
however, which make elevated pressure processing attractive. Distillation column
diameters and heat exchanger cross sectional areas can be decreased due to increased
vapor density. Elevated pressure products can provide substantial compression
equipment capital cost savings. In some cases, integration of the air separation
process with a power generating gas turbine is desired. In these cases, elevated
pressure operation of the air separation process is required. The air feed to the first
fractioning zone is at an elevated pressure of approximately 10 to 20 atmospheres
absolute. This causes the operating pressure of the second and third fractioning zones
to be approximately 3 to 6 atmospheres absolute. Operation of the conventional
arrangement at these pressures results in very poor product recoveries due to the
previously described effect of pressure on the ease of separation. Previous work to
cryogenically separate air into its components can be referenced in U.S. Pat. Nos.
5,386,692; 5,4O2,647; 5,438,835; 5,440,884; 5,456,083; 5,463,871; 5,582,035;

5,582,036; 5,596,886; 5,765,396; 5,896,755; 5,934,104; 6,173,584; 6,2O2,441;
6,263,700; 6,347,534; 6,536,234; 6,564,581; 5,341,646; 5,245,832; 6,048,509;
6,082,136; 6,499,312; 6,298,668; and 6,333,445, while used as a reference in this
instant invention. All of these patents are incorporated herein as a reference.
It is also well known in the chemical industry to separate air with membranes.
Two general types of membranes are known in the art: organic polymer membranes
and inorganic membranes. These membrane air separation processes are improved
by setting up an electric potential across a membrane that has been designed to be
electrically conductive. Previous work performed to separate air into its components
with membranes can be referenced in U.S. Pat. Nos. 6,523,529; 6,761,155;
6,277,483; 5,820,654; 6,293,084; 6,360,524; 6,551,386; 6,562,104; 6,361,583;
6,565,626; 6,572,678; 6,572,679; 6,579,341; 6,592,650; 6,372,010; 5,599,383;
5,820,654; 5,820,655; 5,837,125; 6,117,210; 5,599,383; 5,9O2,370; 6,117,210;
6,139,810; 6,403,041; and 6,767,663, while used as a reference in this instant
invention. All of these membrane patents are herein incorporated as reference.
While these patents present many innovations in membrane technology, none
present use of a membrane wherein the energy of air separation is obtained from
the formation energy of at least one selected from a list consisting of: SO2 from the
burning of S in air or O2, SO3 from the oxidation of SO2, H2SO4 formation from S03,
H2SO3 formation from SO2, halide acid formation and any combination therein.
It is also well known to separate air into O2 and N2 with PSA (herein to include
vacuum swing adsorption). Previous work performed to separate air into its
components with PSA can be referenced in U.S. Pat. Nos. 6,572,838; 6,761,754;
6,780,806; 3,793,931; 4,481,018; 4,544,378; 5,464,467; 5,810,909; 5,868, 818;
5,885,331; 6,350,298; 6,171, 370; 6,423,121; 6,649,556; 6,652,626; 4,013, 429;
4,264,340; 4,329,158; 4,685,939; 5,137,548; 5,152,813; 5,258,058; 5,268,012;
5,354,360; 5,413,625; 5,417,957; 5,419,891; 5,454, 857; 5,672,195; 6,004,378;
6,357,601; 6,321,915; 6,315,884; 6,298,664; 6,497,098; 6,510,693; and 6,516,787,
while used as a reference in this instant invention. All of these PSA patents are
herein incorporated as reference. While these patents present many innovations in
PSA technology, none teach wherein the energy of manufacture is obtained from the
formation energy of at least one selected from a list comprising: SO2 from the burning

of S in air or O2, SO3 from the oxidation of SO2, H2SO4 formation from SO3, H2SO3
formation from SO2, halide acid formation and any combination therein.
An additional method for the manufacture of O2 is the electrolysis of water
(H2O). Previous work in the electrolysis of H2O can be referenced in U.S. Pat. Nos.
6,723,220; 5,585,882; 6,572,759; 6,551,735; 6,471,834; 6,361,893; 6,338,786; and
6,336,430, while used as a reference in this instant invention. All of these
electrolysis patents are herein incorporated as reference. While these patents
present many innovations in electrolysis technology, none present wherein the
energy of manufacture is obtained from the energy of formation from at least one
selected from a list comprising: SO2 from the burning of S in air or O2, SO3 from the
oxidation of SO2, H2SO4 formation from SO3, H2SO3 formation from SO2, halide acid
formation and any combination therein.
It is well known in the art of methods and processes to manufacture oxides
of halogens to form said halogen oxide from a metal/halogen salt via electrolysis.
While the most common metal is sodium, calcium is often used. While the most
common halogen is chlorine, bromine, fluorine and iodine are often used. Previous
work in the production of halogen oxide manufacture can be referenced in U.S. Pat.
Nos. 5,342,601; 5,376,350; 5,409,680; 5,419,818; 5,423,958; 5,458,858;
5,480,516; 5,523,072; 5,565,182; 5,599,518; 5,618,440; 5,681,446; 5,779,876;
5,851,374; 5,858,322; 5,916,505; 5,972,196; 6,004,439; 6,203,688; 6,306,281;
6,436,435; 6,740,223; 6,761,872; 6,805,787; and 6,814,877, while used as a
reference in this instant invention. All of these patents in the preparation of an
oxide form of a halogen are herein incorporated as reference. While these patents
present many innovations in the production of halogen oxides, none present
wherein the energy of manufacture is obtained from the energy of formation from
at least one selected from a list comprising: SO2 from the burning of S in air or O2,
SO3 from the oxidation of SO2, H2SO4 formation from SO3, H2SO3 formation from
SO2, halide acid formation and any combination therein.
Acid Manufacture (Sulfuric, Sulfurous and Hydrochloric) - HCI is known in
the art to be produced by 2 processes, the Electrolysis Unit (EU) process and the
Sulfuric Acid Process (SAP). The raw materials for EU production of HCI include

sodium chloride, water, and electricity. The raw materials for SAP production of
HCI include sodium chloride, H2SO4 and water.
Sulfuric acid has many forms and equivalents, all of which are based upon
the sulfoxy (SxOy) anion moiety, wherein X can vary from 1 to 2 and Y can vary
from 2 to 8. Examples would be sulfurous acid, sulfuric acid, oleum and persulfuric
acid. As defined in this instant invention a sulfoxy acid is any proton donating acid
containing a sulfoxy moiety. H2SO4 and H2SO3 are manufactured primarily by two
competing processes, the condensation process and the contact process. In both
cases in a sulfuric acid plant, which will be herein after referred to as the sulfuric
acid reactor (SAR), S is combusted in air and/or O2 to produce SO2. SO2 is then
converted into SO3 in the contact process with the use of a catalyst, usually V2O5, in
the presence of excess air at a temperature of about 400 - 450 °F (204 - 233 °C).
In either process, SO3 can be slowly converted into H2SO4 by contact of said SO3
with H2O. In the condensation process, the combusted SO2 is contacted with H2O
quickly forming H2SO3 and slowly forming H2SO4. In the contact process, said SO3
is contacted with H2SO4 forming H2S2O7 (oleum); oleum is then contacted with H2O
forming 100 percent H2SO4. Often the oleum step is bypassed by directly reacting
said SO3 with H2SO4 and H2O, thereby forming H2SO4. It is difficult to obtain 100
percent H2SO4with the condensation process.
Bleach Manufacture - Bleach, a group IA or group IIA metal in solution with a
hypohalite, is currently manufactured by two processes, electrolysis and acid/base
blending. In electrolysis, a salt solution comprising a group IA or group IIA metal
halide is placed in an electrolysis cell, wherein the salt is separated into the
corresponding halide acid and the corresponding group IA or group IIA hydroxide,
and wherein said halide acid and said group IA or group IIA hydroxide is allowed to
mix, therein forming the corresponding group IA or group IIA metal in solution with
the hypohalite while releasing hydrogen gas. In acid/base blending, a cold dilute
solution of a group IA or group IIA metal hydroxide is mixed with either a halogen
acid in aqueous form or with a halogen acid gas, wherein is formed the
corresponding group IA or group IIA metal in solution with the hypohalite while
releasing hydrogen gas. In all situations, concentration of the group IA or group

IIA metal hypohalite in solution may be increased by adding an excess of a base,
preferably the group IA or group IIA hydroxide until a concentration of about 15
percent of the group IA or group IIA metal hypohalite is obtained.
Under current manufacturing practices, the group IA or group IIA metal
hydroxide used in the formation of a bleach is formed by the electrolysis of the
corresponding group IA or group IIA salt in water. Therefore, the manufacture of
any bleach is currently constrained by the cost and/or availability of electricity to
perform electrolysis.
Previous work in the manufacture of a group IA or group IIA hydroxide are
referenced herein in U.S. Patents 3,976,556; 4,O25,405; 4,100,050; 4101,395;
4,187,350; 4,221,644; 4,240,883; 4,295,944; 4,486,276; 4,586,994; 4,969,981;
6,488,833; along with A 1 067 215 from EP; 1120481 from EP; 55-89486 from JP;
1-234585 from JP; and 10-11O287 from JP.
Gypsum Manufacture - Gypsum, calcium sulfate di-hydrate, is a widely used
product being the major component in the manufacture of wall-board or sheetrock.
Gypsum is currently manufactured by three competing processes: the mining of
calcium sulfate di-hydrate, the hydration of mined calcium sulfate and the
scrubbing of waste sulfoxy acid gases by an oxide of calcium, usually calcium oxide
and/or calcium hydroxide. In all cases, the purity of manufactured gypsum is an
issue. In the case of mined calcium sulfate and calcium sulfate di-hydrate,
contaminants from the earth are an issue. And, in the case of scrubbing waste
sulfoxy acid gases, impurities in the gas stream are often also oxidized and left in
the gypsum product.
Previous work performed to purify a sulfoxy acid gas, thereby forming gypsum
are herein referenced in U.S Patents 3,976,747; 4,312,280; 4,590,049; 4,782,772;
4,867,955; 4,915,920; 4,931,264; 5,006,323; 5,345,884; 5,538,703; 5,544,596;
5,551,357; 5,795,548; 5,814,288; 6,290,921; 6,309,996 and 6,912,962, along
with foreign patents 40 39 213 from DE, 40 23 030 from DE, 2 107 207 from GB
and 99/5822/6 from WO.

Transportation of Hazardous Chemicals and Sulfur Management
As population density increases, the transportation of hazardous chemicals,
including acids and disinfectants, leads to an increased incidence of spills while
the consequences of spills become more serious. While solutions of halide acids,
hypohalites and halites are safer disinfectants for transportation, handling, and
storage, the cost of manufacture of these disinfectants has limited their use. A
more economical process is required for the manufacture of O2, CIO2, halide acids,
hypohalites, and halates. In addition, while the US EPA required removal of sulfur
from hydrocarbon fuels has limited atmospheric releases of oxides of sulfur from
combustion exhaust, said removal is creating an abundance of sulfur, such that
the refining industry is in need of a way to dispose of said abundance of sulfur.
SUMMARY OF THE INVENTION
A primary object of the instant invention is to devise an effective, efficient,
and economically feasible process for producing polynucleate aluminum and/or
polynucleate metal complexes.
Another object of the instant invention is to devise an effective, efficient,
and economically feasible process for producing polynucleate aluminum and/or
polynucleate metal complexes without the transportation and handling of
hazardous materials.
Still another object of the instant invention is to devise an effective,
efficient, and economically feasible process for producing polynucleate complexes
that contain metals in addition to and/or instead of aluminum.
Still yet another object of the instant invention is to devise an effective,
efficient, and economically feasible process for producing disinfectants and/or
oxidants, preferably those utilized in the water treatment and the paper industries,
specifically: O2, O3, H2O2, NaOH, H2O2, hypohalites, halites, halates, halogen oxides
and halide acids.
Still further yet another object of the instant invention is to devise an
effective, efficient, and economically feasible process for producing HCI and
H2SO4, as well as metal sulfites, metal bisulfites and metal sulfates.

Still further yet another object of the instant invention is to devise an effective,
efficient, and economically feasible process for using the energy of formation from at
least one selected from a list consisting of: SO2 from sulfur and air or oxygen, SO3
from SO2 and air or oxygen with a catalyst, H2SO4 from oleum and water, H2SO4 from
H2SO3, H2SO4 and water, and any combination therein to make steam, wherein said
steam is used to generate electricity to manufacture by electrolysis at least one
selected from a list consisting of: O2 and H2 from H2O, O3 from O2, H2O2 from water
using H2SO4 as a catalyst, a metal hydroxide and a hydrogen halide from said metal
halide, a hypohalite, a halite, a halate, a halogen oxide, and any combination therein.
Still further yet also another object of the instant invention is to devise an
effective, efficient, and economically feasible process for using the energy of
formation from at least one selected from a list consisting of: SO2 from sulfur and
air or oxygen, SO3 from SO2 and air or oxygen with a catalyst, H2SO4 from oleum
and water, H2SO4 from H2SO3, H2SO4 and water, and any combination therein to
make steam, wherein said steam is used to generate mechanical energy to
manufacture at least one selected from a list consisting of: O2 and H2 from H2O.
Still further also yet another object of the instant invention is to devise an
effective, efficient, and economically feasible process for the chemical
manufacture of bleach, wherein the group IA or group IIA metal hydroxide is
manufactured without the need of electrolysis.
Still also further yet another object of the instant invention is to devise an
effective, efficient, and economically feasible process for the chemical
manufacture of gypsum, wherein the purity of the gypsum is increased.
And, still also further yet another object of the instant invention is to devise
an effective, efficient, and economically feasible process for the chemical
manufacture of gypsum, wherein the sulfur incorporated in said gypsum is from
the removal of said sulfur from a hydrocarbon.

Brief Description of the Accompaying Drawings
A better understanding of the instant invention can be obtained when the
following preferred embodiments are considered in conjunction with the following
drawings, in which:

Figure 1 illustrates a legend for Figures 2 through 10.
Figure 2 illustrates in block diagram form a general description of a
preferred embodiment of the proposed methods and processes to manufacture
disinfectants with electrolysis, wherein the energy for electrolysis is obtained from
the formation of at least one selected from a list consisting of: SO2, SO3, H2SO3,
oleum, H2SO4 and any combination therein.
Figure 3 illustrates in block diagram form a general description of a
preferred embodiment of the above methods and processes in combination with a
process for halogen acid reaction (HAR), wherein a sulfoxy acid, preferably, H2SO4
and/or H2SO3, is reacted with a metal halide salt to form the corresponding halide
acid, along with the corresponding metal sulfoxy salt, most preferably the metal
sulfate, sulfite or bisufite.
Figure 4 illustrates in block diagram form a general description of a
preferred embodiment of the methods and process in Figures 1 and 2 in
combination with the manufacture of a PAC and/or an MP.
Figure 5 illustrates in block diagram form a general description of a preferred
embodiment, wherein the H2 produced in electrolysis is recycled as an energy source
for electrolysis to improve the economics of electrolysis.
Figure 6 illustrates in block diagram form a general description of a
preferred embodiment comprising a steam turbine, wherein air separation,
preferably cryogenic distillation, is used to produce O2 and electrolysis is used to
turn said O2 into O3.
Figure 7 illustrates in block diagram form a general description of a
preferred embodiment comprising a steam engine, wherein air separation,
preferably cryogenic distillation, is used to produce O2 and electrolysis obtains
electricity via a steam turbine/generator to turn said O2 into O3.
Figure 8 illustrates in block diagram form a general description of a
preferred embodiment, wherein the H2 produced in electrolysis is recycled as an
energy source for electrolysis to improve the economics of electrolysis.
Figure 9 illustrates in block diagram form a general description of a preferred
embodiment, wherein air separation, preferably, cryogenic distillation is used to

produce O2 and electrolysis obtains electricity via a steam turbine/generator to
turn said O2 into O3.
Figures 10 and 11 illustrate in block diagram form a general description of a
preferred embodiment of the proposed methods and processes to manufacture the
halide acid and the metal sulfoxy salt from a sulfoxy acid and a metal halide salt,
wherein said manufacture is to occur in an extruder and/or auger type of reactor,
wherein the screw in said reactor transfers said metal halide salt into reaction with
said sulfoxy acid, wherein said halide acid is removed from at least one vented
portion of said extruder and/or auger, wherein said extruder and/or auger transfers
said metal sulfoxy salt from said extruder and/or auger at an end opposite of the
entry of said metal halide salt. Figure 10 illustrates a metal hydroxide to pH adjust
said metal sulfoxy salt, thereby creating said metal sulfoxy salt from any excess said
sulfoxy acid while releasing water in at least one vented portion of said extruder
and/or auger reactor. As Figure 10 illustrates two vents, one for said halide acid and
one for said water vapor, it is an embodiment to have one vent, two vents, or more
vents. It is preferred that a heated water jacket be placed on said extruder and/or
auger. It is most preferred that said water jacket flow co-current to said reaction of
said metal halide salt with said sulfoxy acid. It is preferred that said extruder and/or
auger and said water loop be as is known in the art of such equipment.
Figure 12 illustrates in block diagram form a general description of a
preferred embodiment, wherein sulfur, alumina, a metal halide salt and water are used
to produce a polynucleate metal compound, a metal halide solution, a metal halite, a
metal hypohalite, a metal hydroxide, and calcium sulfate dehydrate.
DESCRIPTION OF THE PREFERRED EMBODIMENTS



Reactions which are most preferred comprise at least one selected from a list
consisting of number: 1, 2, 4, 6, 7, 8, 10, 11, 12, 14, 15, 16, 17, 19, 25, 26, and
any combination therein. Reactions required to remove calcium and thereby

increase product purity are 11 and 12. Reaction 26 is preferred for on-site
manufacture of chlorine dioxide. Alumina is herein estimated at about 2/3
aluminum oxide and 1/3 aluminum hydroxide; however, Alumina can be any
concentration of the base aluminum metal with any concentration of aluminum
oxide and any concentration of aluminum hydroxide. It is preferred to use at
least one metal other than aluminum.
Sulfoxy Acid Formation - SAR
Significant economies of manufacture can be obtained by the preparation of a
sulfoxy acid. A sulfoxy acid is defined herein as any acid comprising an SOx moiety;
further the sulfoxy moiety is herein defined as any SOx moiety. It is most preferred
that the sulfoxy acid in this instant invention be H2SO4. While the market for H2SO4
and H2SO3 is very competitive, the formation of H2SO4 and/or H2SO3 from S, air and
H2O or S, O2 and H2O is very exothermic. There are two processes known to
manufacture H2SO4 and H2SO3, the sulfuric acid condensation (SAC) and the sulfuric
acid contact process (SACP), both are herein referred to as SAR, and are an
embodiment in this instant invention, with the SACP preferred. The SACP produces
H2SO4 and/or H2SO3 from S, H2O and air or O2 (with one stage of reaction requiring a
catalyst, preferably vanadium oxide, V2O5). Every mole of about anhydrous H2SO4
produced from S, H2O, and air or O2 also produces approximately 126 kcal of energy.
This valuable energy is preferably used to produce steam for at least one selected
from a list comprising: the purification of bauxite, heating of the metal polymer reactor
(MPR, which can used to manufacture PAC(s) as well as MP(s)), heating of an HAR
and/or HAR product distillation, reducing the H2O content of by-product metal sulfate,
sulfite or bisulfite salts with air evaporative dehydration, electricity generation to
operate the EU and any combination therein. The SACP is summarized by:

(Contact of SO3 with H2SO4 to form oleum can be eliminated; however, SO3 +
H2O → H2SO4 is a slow reaction.)

Sulfurous acid, H2SO3, is formed by reacting SO2, from the first reaction,
with H2O.
It is preferred to obtain sodium sulfite by reacting SO2, from the first reaction in
an aqueous solution of sodium hydroxide; a metal sulfite is formed by reacting SO2, from
the first reaction in an aqueous solution of said metal hydroxide or by reacting a metal
sulfite with H2SO3.
It is preferred to obtain sodium bisulfite by the reaction of SO2, from the
first reaction, in an aqueous solution of sodium carbonate; and a metal bisulfite is
formed by the reaction of SO2, from the first reaction, in an aqueous solution of
said metal carbonate.
In addition to the electrical and steam energy economics of H2SO4 and/or
H2SO3 production, on-site production of H2SO4 and/or H2SO3 eliminates the
transportation and storage of H2SO4 and/or H2SO3. As discussed previously, H2SO4
and/or H2SO3 are hazardous chemicals that must be stored in the appropriate
tankage, wherein the vapors must be controlled. Therefore, it is preferred that
H2SO4 and/or H2SO3 produced for the HAR have minimal volume storage. It is a
most preferred embodiment to produce H2SO4 and/or H2SO3 from the SACP and
then react said "hot" H2SO4 and/or H2SO3 with a metal halide in the HAR, thereby
utilizing the H2SO4 and/or H2SO3 energy to distill the halide acid and/or dry the HAR
produced metal sulfoxy salt.
It is preferred that said SACP be of design, construction and operation as is
known in the art.
Halogen Acid Reactor - HAR
In the HAR, at least one of the about anhydrous salt and brine is reacted with a
sulfoxy acid, preferably H2SO4 and/or H2SO3, and most preferably H2SO4, to form the
associated halide acid, which in the case of sodium chloride is HCI, and the associated
byproduct metal sulfoxy salt, which in the case of sodium chloride is a sodium sulfoxy
salt, wherein said sulfoxy moiety in said metal sulfoxy salt is preferably at least one
selected from a list consisting of: sulfate, bisulfate, sulfite, bisulfite and any
combination therein. It is most preferred that said metal comprise sodium; it is
preferred that said metal comprise a group IA or group IIA metal, while it is an

embodiment that the metal comprise at least one selected from a group consisting of:
ammonium, a Group IA metal, a Group IIA metal, a Group IIIB metal, a Group VIII
metal, a Group IB metal, a Group IIB metal, a Group IIIA metal, sodium, calcium,
potassium, magnesium, aluminum, copper and any combination therein.
The boiling point of about anhydrous H2SO4, Na2SO4 and NaCI at atmospheric
pressure is approximately 340, N.B. and 1413, ° C (644, N.B. and 2575 ° F)
respectively, while the boiling point of about anhydrous HCI at atmospheric pressure
is approximately -85 °C (185 °F), leaving separation of the byproduct metal salt from
the halide acid rather easily performed. Distillation, or separation, of the resulting
anhydrous and/or aqueous halide acid solution permits the capability of directly
controlling the aqueous halide acid concentration by concentration of the salt in the
brine and/or by addition of water to said halide acid, which is preferably performed
via an eductor and/or a compressor, wherein said eductor moves said halide acid via
a stream of water and said compressor moves and/or pressurizes said halide acid. It
is a preferred embodiment that said eductor move said halide acid via a stream of
aqueous halide acid. It is a preferred embodiment that said compressor move said
halide acid via a stream of about anhydrous halide acid. It is an embodiment that
said compressor move said halide acid via a stream of aqueous halide acid.
An embodiment is to perform in the HAR reaction of a metal halide salt with a
sulfoxy acid, preferably H2SO4, as said sulfoxy acid contains heat (measured as
temperature) from the SAR process. A preferred embodiment is to perform the
reaction of a metal halide salt in the HAR with a sulfoxy acid, preferably H2SO4 and/or
H2SO3, as said sulfoxy acid contains heat from said SAR process at a temperature of
between about 0 and about 600 ° C, thereby providing said heat to create hot water
and/or steam energy via heat transfer from the HAR via a water jacket on the HAR. A
most preferred embodiment to perform in the HAR reaction of a metal halide salt with
sulfoxy acid, preferably H2SO4, as said sulfoxy acid contains at least partially the heat
from formation of at least one selected from a list consisting of: SO2, SO3, oleum,
H2SO4, H2SO3 and any combination therein, wherein the temperature of said reaction
in said HAR is controlled by a water and/or steam jacket between about 0 and 600 °C.
It is preferred that said temperature in said HAR be between about 100 and 300 ° F
(38 - 149 ° C) to form a bi-sulfate or a bi-sulfite salt in said HAR. It is preferred that

said temperature in said HAR be between about 300 and about 600 °F to form a
sulfate or a sulfite salt in said HAR. A most preferred embodiment is to utilize said
water and/or steam energy from the jacket of said HAR to heat at least one selected
from a list consisting of: the formation of a metal hypohalite, the formation of a
polynucleate metal compound, dry a metal sulfoxy salt to at least one of its anhydrous,
hydrate, di-hydrate state, and any combination therein.
It is an embodiment to perform about anhydrous and/or aqueous halide acid
distillation and/or separation from sulfoxy acid and/or metal sulfoxy salt under the
pressure condition of at least one of: atmospheric, positive gage, vacuum and any
combination therein. It is preferred that the time/temperature relationship of said
halide acid or halide acid solution be managed to decompose any halite ions to
halide ions (approximately 60 °C (142 °F) is required). The resulting byproduct, a
sulfoxy salt, preferably of the sulfate, bisulfate, sulfite and/or bisulfite moiety may
be purified by reacting with any metal hydroxide or caustic to a desired pH, thereby
purifying said byproduct metal sulfoxy salt while creating heat to the reaction of
said metal halide salt with said sulfoxy acid. It is most preferred that said
byproduct metal sulfoxy salt be pH adjusted with NaOH. It is preferred that said
byproduct metal sulfoxy salt be pH adjusted with a metal hydroxide, wherein the
metal in said metal hydroxide corresponds to the metal in said byproduct metal
sulfoxy salt. It is most preferred to dehydrate said byproduct metal sulfoxy salt to
a powder for sale. It is preferred to sell said byproduct metal sulfoxy salt as a
hydrate. It is preferred to sell said byproduct metal sulfoxy salt as a cake. It is an
embodiment to sell the byproduct metal sulfoxy salt in solution.
While the reaction to form said sulfoxy acid is exothermic, as depicted in
reaction 1, the reaction to form said metal sulfate or sulfite salt is endothermic, as
depicted by reaction 3; similar energies are required for the reaction of any metal
halide salt with a sulfoxy acid, preferably sulfuric acid, to form a metal sulfate salt. It is
therefore preferred to manufacture a metal bi-sulfate or bi-sulfite salt as is depicted in
reaction number 4, thereby reducing the required energy for formation of a halide
acid, while still providing a metal bi-sulfate salt, albeit in a form containing hydrogen.
It is an embodiment to recover at least a portion of the energy of formation
of said metal sulfoxy salt and water from the reaction of a metal hydroxide with a

sulfoxy acid, wherein said energy is used to heat said reaction of said metal halide
with said sulfoxy acid, as depicted in reactions 13 and 14. It is a preferred
embodiment to use H2 generated in an electrolysis unit (EU), as described herein,
or use H2 generated in the formation of a metal hypohalite, as described herein, to
heat said reaction of said metal halide salt with said sulfoxy acid to form the
desired metal sulfoxy salt in said HAR. It is a preferred embodiment to use natural
gas to heat said reaction of said metal halide salt with said sulfoxy acid to form the
desired metal sulfoxy salt in said HAR.
As depicted in Figure 10, it is an embodiment that said HAR comprise a
mixing/reaction section, which is preferably of an extruder/auger-type design. It is
preferred that said HAR comprise at least one auger and/or extruder, wherein said
metal halide salt is added to one end of said auger and/or extruder, wherein said
sulfoxy acid is reacted with said metal halide salt, wherein the resultant halide acid is
allowed to leave said auger and/or extruder from at least one vent. It is most
preferred that said HAR comprise at least one auger and/or extruder, wherein said
metal halide salt is added to one end of said auger and/or extruder, wherein said
sulfoxy acid reacts with said metal sulfoxy salt, wherein the resultant halide acid is
allowed to leave said auger and/or extruder from at least one vent, and wherein a
metal hydroxide or a metal oxide is added to said auger and/or extruder in order to
react said metal hydroxide or metal oxide with any remaining sulfoxy acid in said
auger and/or extruder, such that a metal sulfoxy salt is formed with water. It is most
preferred that said HAR comprise at least one auger and/or extruder, wherein said
metal halide salt is added to one end of said auger and/or extruder, wherein said
sulfoxy acid reacts with said metal halide salt, wherein the resultant halide acid is
allowed to leave said auger and/or extruder from at least one vent, wherein a metal
hydroxide or a metal oxide is added to said auger and/or extruder in order to react
said metal hydroxide or metal oxide with any remaining sulfoxy acid in said auger
and/or extruder to form a metal sulfoxy salt and water, wherein said water is allowed
to leave said auger and/or extruder via at least one vent. To dry said metal sulfoxy
salt, it is preferred that said auger and/or extruder have an operating temperature of
at least approximately 140 ° F (60 ° C) or greater after the addition of any metal
hydroxide. To dry said metal sulfoxy salt, it is most preferred that said auger and/or

extruder have an operating temperature of at least approximately 212 °F (100 °C) or
greater after the addition of any metal hydroxide. To maintain a reaction
temperature in said auger and/or extruder it is preferred that said auger and/or
extruder comprise a water jacket.
It is most preferred that said metal halide salt be added to said HAR in
about anhydrous form. It is preferred that said metal halide salt be added to said
HAR in aqueous form.
EU
It is preferred to prepare at least one disinfectant or oxidant, wherein said
disinfectant or oxidant is formed by electrolysis, wherein the electricity for said
electrolysis is created in a generator turned by a steam turbine, wherein said
steam turbine is turned by steam energy, and wherein the steam energy to turn
said steam turbine is obtained from the energy of formation of at least one
selected from a list consisting of: SO2 from S and air, SO2 from S and O2, SO3 from
SO2 and air, SO3 from SO2 and O2, said H2SO3 from SO2 and H2O; said H2SO4 from
SO3 and H2O; oleum from H2SO4 and SO3, said H2SO4 from oleum and H2O, and any
combination therein.
It is preferred to produce in an EU at least one selected from a list consisting
of: a metal hypohalite from a metal halide salt solution, a metal halite from a metal
halide salt, a metal halate from a metal halide salt, a halide acid from a metal halide
salt, O2 from H2O, O3 from O2, H2 from H2O, H2O2 from H2SO4 via H2S2O8 and H2O,
any combination therein, wherein at least a portion of the electrical energy in the EU
is created by a generator, and wherein the generator is turned by a steam turbine,
wherein the steam turbine is turned by steam energy obtained from the energy of
formation of at least one selected from a list consisting of: SO2 from S and air, SO2
from S and O2, SO3 from SO2 and air, SO3 from SO2 and O2, said H2SO3 from SO2 and
H2O; said H2SO4 from SO3 and H2O; oleum from H2SO4 and SO3, said H2SO4 from
oleum and H2O and any combination therein.
It is preferred to react said SO2 with at least one selected from a list
consisting of: a metal hydroxide to from a metal sulfite, a metal carbonate to form a

metal bi-sulfite, a metal halate and H2SO4 to form the corresponding halogen
dioxide, and any combination therein.
It is preferred to use at least a portion of said H2 in at least one of a:
combustion engine to turn a generator to generate electricity, fuel cell to generate
electricity, and heat the reaction between a metal halide salt with a sulfoxy acid.
It is preferred to use at least a portion of said electricity generated by said H2 via
a combustion engine or a fuel cell to perform electrolysis in said EU.
It is most preferred that the halogen of said halide, hypohalite, halite or halate
comprises chlorine or bromine. It is an embodiment that said metal halide solution
comprises a waste catalyst or waste brine. It is an embodiment to use at least a
portion of said H2 to heat an HAR to form a metal sulfoxy salt.
If the EU is used to produce a halide acid, the halide acid from the EU is
preferably heated: immediately after the EU, within the EU, during AHS formation,
during Metal Acid Solution (MAS) formation or a combination therein so that the halite
ions are decomposed into halide ions while utilizing the enthalpy from at least one
selected from: electrolysis, AHS formation,. MAS formation and any combination therein
to minimize heating expense.
It is most preferred to produce in the EU a chlorine moiety comprising at
least one selected from a list consisting of: chlorine gas, hydrochloric acid,
hypochlorite, chlorite and chlorate, and any combination therein, wherein at least a
portion of the electrical energy for the EU is obtained from steam energy, wherein
said steam energy is obtained from the energy of formation of at least one selected
from a list consisting of: SO2 from S and air, SO2 from S and O2/ SO3 from SO2 and
air, SO3 from SO2 and O2, said H2SO3 from SO2 and H2O; said H2SO4 from SO3 and
H2O; oleum from H2SO4 and SO3, said H2SO4 from oleum and H2O and any
combination therein.
It is preferred that halide acid production, from either the EU or the HAR be
employed for the production of the associated halide or halogen gas, halide acid,
hypohalite, halite or halate. It is preferred that a waste brine used in the EU.
Metal hydroxides, while a potential by-product of the EU, are a preferred
material to be used in at least one selected from a list consisting of: the
preparation of alumina, the production of a hypohalite, the production of a halite,

the production of a halate, the production of a halogen dioxide, the scrubbing of
a halide acid gas released from any of the processes in the instant invention, pH
control applications that include those in the water treatment industry and pH
polishing of the by-product metal sulfoxy, preferably sulfate, bisulfate, sulfite or
bisulfite, salt formed in the HAR.
An embodiment is to utilize any metal halide salt in the EU, wherein the
associated acid product is the associated halide acid and the associated caustic
product is the associated metal hydroxide. Of all the available metals to be
incorporated in the metal halides to be used in the EU and the HAR, it is preferred
that said metal comprise at least one selected from a list consisting of: sodium,
potassium, magnesium, and any combination therein.
A most preferred embodiment is to use any metal halide salt in the EU,
wherein the associated product is an oxidation product of the halide, such as a
halide, hypohalite, halite or halate, wherein said halide, hypohalite, halite or halate
can comprise any halogen from the periodic table. A preferred embodiment is to
manufacture a halogen dioxide, wherein the EU forms at least one selected from a
list consisting of: metal halite, metal halate, halide acid, and any combination therein,
wherein said halogen dioxide is formed via at least one of said manufactured: metal
halite, metal halate, halide acid, SO2, H2SO4 and any combination therein. A most
preferred embodiment is to manufacture CIO2, wherein the EU forms a metal chlorite
and/or chlorate and wherein CIO2 is formed via said manufactured chlorite and/or
chlorate. A most preferred embodiment is to manufacture CIO2, wherein the EU
forms a chlorite and/or a chlorate, and wherein CIO2 is formed via said manufactured
chlorite and/or chlorate with said HCI manufactured by the HAR, as said formation of
CIO2, as well as chlorate and/or chlorite. A most preferred embodiment is to
manufacture CIO2, wherein the EU forms a chlorite and/or a chlorate along with a
hypochlorite, and wherein CIO2 is formed with at least one of said manufactured
chlorite, chlorate and hypochlorite with said HCI manufactured by the HAR. A most
preferred embodiment is to manufacture a halogen dioxide in the EU, wherein the EU
is used to form a metal chlorite and/or chlorate, wherein a halide acid is formed by
the HAR, and wherein said halogen dioxide is formed via at least one of said EU
manufactured halite, halate and hypohalite with said halide acid manufactured by the

HAR. A most preferred embodiment is to manufacture a metal halate in the EU,
along with SO2 and H2SO4 in the SAP, wherein said SO2 and H2SO4 are reacted to
form the corresponding halogen dioxide. A most preferred embodiment is to react
said halogen dioxide with a metal hydroxide and hydrogen peroxide to manufacture
a metal halate, as is known in the art.
It is preferred to manufacture in the EU a halide acid, wherein at least a portion
of said halide acid is used to form at least one selected from a list consisting of the
corresponding: hypohalite, halite, halate, available oxide form of said halide, said
halide in the form of a dioxide, and any combination therein.
It is most preferred that the EU comprise a diaphragm construction, as is
known in the art.
It is preferred that the metal(s) in said metal halide salt used in said EU
comprises at least one selected from a list consisting of: ammonium, a Group IA
metal, a Group IIA metal, a Group IIIB metal, a Group VIII metal, a Group IB
metal, a Group IIB metal, a Group IIIA metal, sodium, calcium, potassium,
magnesium, aluminum, copper and any combination therein. It is most preferred
that the metal(s) used in said EU comprise sodium.
O2 and O3
O2 is preferably produced via at least one selected from a list comprising:
cryogenic distillation of air, membrane separation of air, PSA separation of air and
any combination therein; all of these process and process combinations therein are
herein each referred to as an air separation process (ASP).
It is preferred to prepare O2, wherein the formation of at least one selected
from a list consisting of: SO2 from S and air, SO2 from S and O2, SO3 from SO2 and
air, SO3 from SO2 and O2, said H2SO3 from SO2 and H2O; said H2SO4 from SO3 and
H2O; oleum from H2SO4 and SO3, said H2SO4 from oleum and H2O, and any
combination therein, wherein the energy of said formation(s) is used to generate
steam, and wherein said steam is used to perform at least one selected from a list
consisting of: turn a steam turbine to generate electricity, wherein said electricity
is used in the electrolysis of H2O to H2 and said O2, turn a steam turbine to

generate electricity, wherein said electricity is used to power an ASP, turn a steam
engine, wherein said steam engine powers an ASP, and any combination therein.
It is preferred that said ASP be as is known in the art. It is preferred that
at least a portion of said electricity be used to power an electrolysis unit to
convert O2 into O3.
It is preferred that said H2 is at least partially used in at least one of a:
combustion engine to turn a generator to generate electricity, fuel cell to generate
electricity, and heat the reaction between a metal halide salt with a sulfoxy acid.
H2O2
H2O2 can be produced utilizing H2SO4 as the catalyst. In this reaction,
H2O2 is formed in a two stage process, wherein the first stage H2S2O8 and H2 are
formed by electrolysis from H2SO4. In the second stage, the H2S2O8 from the first
stage is reacted with H2O to form H2O2 and H2SO4. The H2 gas can be vented,
stored or used as an energy source; the H2SO4 can be recycled for additional
production of H2S2O8 and H2. The use of H2O2 in water treatment and other
applications has been limited due to its explosive nature creating expense in both
transportation and in storage; H2O2 is a much more hazardous chemical than is
H2SO4 and/or H2SO3 to store and transport. It is most preferred to produce H2O2
utilizing H2SO4 from said SACP. It is preferred to produce H2O2 and H2 wherein,
at least a portion of the electricity for electrolysis of H2O to H2O2 is obtained from
the energy of formation of at least one selected from a list comprising: SO2 from S
and air, SO2 from S and O2, SO3 from SO2 and air, SO3 from SO2 and O2, said H2SO3
from SO2 and H2O; said H2SO4 from SO3 and H2O; oleum from H2SO4 and SO3, said
H2SO4 from oleum and H2O, and any combination therein. It is preferred to recycle
at least a portion of the H2 from H2O2 electrolysis manufacture wherein, at least a
portion of the electrical energy for the electrolysis of H2O to H2O2 is obtained from
the energy of combustion and/or of fuel cell conversion of said H2.
Halogen Dioxide and Metal Halite Formation
It is preferred to form a metal halate in the EU from an aqueous solution of
the corresponding metal halide, wherein the energy of electrolysis (energy of

formation) for said metal halate is at least partially created by a generator, wherein
said generator is turned by stream energy, and wherein said steam energy is
obtained from the energy of formation of at least one selected from a list consisting
of: SO2 from S and air, SO2 from S and O2, SO3 from SO2 and air, SO3 from SO2 and
O2, said H2SO3 from SO2 and H2O; said H2SO4 from SO3 and H2O; oleum from
H2SO4 and SO3, said H2SO4 from oleum and H2O and any combination therein.
It is an embodiment to formation a halogen dioxide with said metal halate
formed in the EU, wherein said halate is further reacted to form said halogen dioxide
from said metal halate, wherein the energy of electrolysis (energy of formation) for
said metal halate is at least partially created by a generator, wherein said generator
is turned by stream energy, and wherein said steam energy is obtained from the
energy of formation of at least one selected from a list consisting of: SO2 from S and
air, SO2 from S and O2, SO3 from SO2 and air, SO3 from SO2 and O2, said H2SO3
from SO2 and H2O; said H2SO4 from SO3 and H2O; oleum from H2SO4 and SO3; said
H2SO4 from oleum and H2O and any combination therein.
It is an embodiment to form the available oxide form of a halogen, including
a halogen dioxide, wherein said formation is performed with at least one selected
from a list consisting of said corresponding: halide acid, hypohalite, halide acid,
halite, halate and any combination therein, wherein at least one of said halide acid,
hypohalite, halide acid, halite and halate is formed in an EU, wherein the electricity
of electrolysis for the EU is at least partially created by a generator, wherein said
generator is turned by stream energy, and wherein said steam energy is obtained
from the energy of formation of at least one selected from a list consisting of: SO2
from S and air, SO2 from S and O2, SO3 from SO2 and air, SO3 from SO2 and O2,
said H2SO3 from SO2 and H2O; said H2SO4 from SO3 and H2O; oleum from H2SO4
and SO3, said H2SO4 from oleum and H2O and any combination therein.
It is an embodiment to react said metal halate to form the corresponding
halogen dioxide. It is preferred to react said metal halate to form the corresponding
halogen dioxide according to at least one of reactions 18, 19, 20 or 21 to form the
corresponding halogen dioxide, as is known in the art. It is most preferred to react
said metal halate to form the corresponding halogen dioxide according to reaction 19.

It is most preferred to perform reaction 19, wherein at least one of said H2SO4
can be a sulfoxy acid in general, wherein said sulfoxy acid and said SO2 is obtained
from an SAR, wherein the electrical energy of electrolysis to form said metal halate is
obtained from steam energy, and wherein said steam energy is obtained from the
energy of formation of at least one selected from a list consisting of: said SO2 from S
and air, said SO2 from S and O2, SO3 from SO2 and air, SO3 from SO2 and O2, H2SO3
from SO2 and H2O; said H2SO4 from SO3 and H2O; oleum from H2SO4 and SO3, said
H2SO4 from oleum and H2O and any combination therein.
It is preferred to perform reaction 21, wherein said H2SO4, which can be a
sulfoxy acid in general, is obtained from an SAR; it is most preferred that said H2O2 is
at least partially obtained by the electrolysis of H2SO4 via H2S208 and H2O, wherein
the electrical energy of electrolysis to form said metal halate is obtained from steam
energy, and wherein said steam energy is obtained from the energy of formation of
at least one selected from a list consisting of: said SO2 from S and air, said SO2 from
S and O2, SO3 from SO2 and air, SO3 from SO2 and O2, H2SO3 from SO2 and H2O; said
H2SO4 from SO3 and H2O; oleum from H2SO4 and SO3, said H2SO4 from oleum and
H2O and any combination therein.
It is preferred to use at least a portion of said steam energy to at least partially
perform at least one selected from a list consisting of: refine bauxite to alumina, heat
said aqueous reaction of a metal halide solution with at least one metal, evaporate H2O
from a metal sulfoxy salt, degrade a halite to a halide, heat S, turn a steam turbine
which turns a generator to create electricity, heat the reaction of a metal hydroxide
and a halide acid to form a metal hypohalite, and any combination therein.
It is preferred then to react said halogen dioxide to form a metal halite, as is
known in the art. It is most preferred then to react said halogen dioxide according to
reaction 25 to form the corresponding metal halite. It is most preferred then to react
said halogen dioxide according to reaction 25 to form the corresponding metal halite,
wherein said H2O2 is formed by the electrolysis of water, wherein the electrical
energy of electrolysis to form said H2O2 is obtained from steam energy, and wherein
said steam energy is obtained from the energy of formation of at least one selected
from a list consisting of: said SO2 from S and air, said SO2 from S and O2, SO3 from
SO2 and air, SO3 from SO2 and O2, H2SO3 from SO2 and H2O; said H2SO4 from SO3

and H2O; oleum from H2SO4 and SO3, said H2SO4 from oleum and H2O and any
combination therein. It is most preferred to then react said halogen dioxide
according to reaction 25 to form the corresponding metal halite, wherein said NaOH
can be any metal hydroxide, yet is most preferably sodium hydroxide, wherein said
metal hydroxide is formed by at least one of: electrolysis of the corresponding metal
halide and the reaction of a metal sulfoxy salt with a moiety of calcium, wherein said
moiety of calcium is preferably calcium oxide or calcium hydroxide, wherein said
metal sulfoxy salt is obtain from an HAR (as presented herein), and wherein the
reaction within said HAR to form said metal sulfoxy salt comprises a reaction
between the corresponding metal halide with the corresponding sulfoxy acid. It is
most preferred that said halogen comprise chlorine and said halate comprise
chlorate. It is most preferred that said metal comprise sodium.
Once transported to the location of use, it is an embodiment to then form a
halogen dioxide from said metal halite, as is known in the art. Once transported to
the location of use, it is preferred to then form a halogen dioxide from said metal
halite according to reaction 26. Once transported to the location of use, it is most
preferred to then form a halogen dioxide from said metal halite according to reaction
26, wherein said HCI can be any halogen acid, yet is most preferably hydrochloric
acid, wherein said halogen acid is manufactured by at least one of: the formation of
said halogen acid by electrolysis of the corresponding metal halide salt, wherein the
electrical energy of electrolysis to form said H2O2 is obtained from steam energy, and
wherein said steam energy is obtained from the energy of formation of at least one
selected from a list consisting of: said SO2 from S and air, said SO2 from S and O2,
SO3 from SO2 and air, SO3 from SO2 and O2, H2SO3 from SO2 and H2O; said H2SO4
from SO3 and H2O; oleum from H2SO4 and SO3, said H2SO4 from oleum and H2O and
any combination therein; and the formation of said halide acid in an HAR from the
reaction of the corresponding metal halide salt with a sulfoxy acid.
In the formation of said metal halite, it is an embodiment of the instant
invention to react chloride ions, preferably having a concentration of from about 1 M
to about 5 M, with chlorate ions, preferably having a concentration of from about 0.1
M to about 7 M, in an aqueous acid reaction medium having an acid normality of
from about 0.05 N to about 5 N. As sodium chloride precipitates in the system, it

may be separated by means of a filter or recycled in a solution or slurry to the EU. A
gaseous product mixture comprising a halogen dioxide, preferably chlorine dioxide,
may be absorbed in any suitable aqueous medium. However, it is beneficial for the
absorption medium to preferably absorb chlorine dioxide and less preferably chlorine.
An example of such a medium is dilute hydrochloric acid. A suitable reagent able to
destroy traces of chlorine, such as, for example hydrogen peroxide, may optionally
be added to the absorption medium, if desired.
In order to transfer the absorbed chlorine dioxide from the absorption
medium to the chlorite formation reactor, any suitable gas stripping method may
be employed. The stripping of chlorine dioxide may be carried out with an inert
gas or gas mixture, such as air or nitrogen. If air is used in the chlorine dioxide
stripping, it is preferred to purify the air from traces of carbon dioxide, by using,
for example, a caustic scrubber. Hydrogen peroxide can optionally be added to
the system prior to effecting the stripping step.
It is preferred to transfer the gaseous product mixture formed in the chlorine
dioxide generator directly to the chlorite formation reactor without the intermediate
step of chlorine dioxide absorption and stripping. Instead of absorption/stripping, gas
transfer membranes can be employed, as in known in the art, thereby allowing the
transfer of chlorine dioxide in the absence of any air addition.
It is an embodiment to modify the halogen dioxide generator by addition of a
supplementary reducing agent, such as hydrogen peroxide, as is known in the art.
It is also an embodiment to improve the performance of the halogen-
dioxide generator by using any suitable catalytically-active agent containing
elements, such as silver, manganese, palladium, chromium, vanadium or a
combination thereof.
While it is known in the art to use the chloride ion as an inexpensive
reducing agent, the reaction of the chloride ion with the chlorate ion necessarily
results in the formation of some chlorine, e.g.:

which may negatively affect purity of the final halite, preferably chlorite, product
while increasing use of hydrogen peroxide. It is therefore, a preferred

embodiment to generate said halogen dioxide, preferably chlorine dioxide, by
reaction 26.
Reaction 26 can be carried out in a very broad acid normality range of from
about 2 N to about 14 N, preferably from about 6 N to about 12 N. The optimum
chlorate ion concentration is dependent on acid normality in the reaction medium and
can vary from about 0.1 M to saturation, preferably from about 0.5 M to about 3.5 M.
Operation at higher acidities is typically associated with a lower chlorate concentration
in the reaction medium. The gaseous product mixture comprising chlorine dioxide and
water vapor can be used directly in the chlorite formation reactor without the
intermediate step of recovery of chlorine dioxide solution, i.e., by omitting the
absorption and stripping stages.
Such an operation leads to significant cost savings due to the elimination of
certain parts of the conventional chlorine dioxide generating system, such as
condenser, absorption tower and stripping tower.
The co-produced oxygen gas can be used along with the water vapor for the
dilution of gaseous chlorine dioxide to safe concentration levels. By adjusting the
chlorine dioxide to water vapor ratio to meet the requirements of the chlorite
formation reactor, the water balance of the overall system is improved. The relative
ratio of chlorine dioxide and water vapor in the gaseous mixture entering the chlorite
formation reactor affects the concentration of metal halite, preferably group IA or
group IIA metal chlorite, in the final product aqueous solution. Therefore, there may
still be a need to condense at least some of the water vapor.
It is preferred to integrate the halogen dioxide, preferably chlorine dioxide,
generator with a methanol based chlorine dioxide generating system, as is known
in the art, wherein the acidic, sulfate and/or bisulfate containing effluent or slurry
formed in the hydrogen peroxide based generator is cascaded to the methanol
based generator. This integration eliminates the requirement for the filtration step
following the hydrogen peroxide based generator.
The above described cascade of two chlorine dioxide generators offers
several advantages which are difficult to accomplish in conventional generators.
For example, it is possible to add a small amount of sodium chloride, typically
about 0.5 to about 1.0 wt. % based on the chlorate, to the hydrogen peroxide

based generator preferably operating at acid normalities above 5N. Such an
addition of chloride may have little or no impact on the chlorine dioxide purity
resulting from the hydrogen peroxide based process, while such addition may be
beneficial with regard to the production rate and efficiency. The presence of
hydrogen peroxide should effectively prevent chlorine from being generated in the
chlorine dioxide generating process.
It is an embodiment to recover the metal sulfate and/or bisulfate, preferably
sodium sulfate and/or sodium bisulfate, following the hydrogen peroxide-based
generator by reaction with a moiety of calcium, preferably CaOH to form the
corresponding metal hydroxide, preferably sodium hydroxide, and calcium sulfate,
calcium sulfate ½ hydrate and calcium sulfate di-hydrate (gypsum).
It is an embodiment to recover the metal sulfate and/or bisulfate, most
preferably sodium sulfate and/or sodium bisulfate, following the conversion of the
halogen dioxide to a metal halate by reacting said metal sulfate and/or bisulfate with
a moiety of calcium, preferably CaOH, to form the corresponding metal hydroxide,
most preferably at least one of sodium, and calcium sulfate, calcium sulfate ½
hydrate and calcium sulfate di-hydrate (gypsum). I is preferred that the metal(s) in
said metal sulfate and/or bisulfate comprise a group IA or group IIA metal.
Any possible chloride input to the peroxide-based process may ultimately
exit the system with the chlorine dioxide produced in the methanol-based chlorine
dioxide generator. However, the impact on the product purity should not be
significant, especially when the production capacity of the latter process is much
higher than that of the peroxide-based process.
The combination of two halogen dioxide, preferably chlorine dioxide,
generators permits all or part of the halogen dioxide containing condensate
originating from the peroxide-based process to be forwarded to the chlorine
dioxide absorption system associated with the methanol-based process. This
embodiment is particularly beneficial since the need to remove the chlorine
dioxide from the condensate is eliminated.
Any suitable catalyst can be added to the peroxide-based chlorine dioxide
generating process, if desired. It is understood that the chlorate ions required for
the chlorine dioxide generation can be supplied not only by a group IA or IIA metal

chlorate, preferably sodium chlorate, but also by chloric acid or mixtures thereof
with said group IA or IIA metal chlorate. While the most preferred acid used in the
process of the instant invention is sulfuric acid, any other strong mineral acid, such
as perchloric acid, chloric acid, nitric acid, phosphoric acid, hydrochloric acid or the
mixtures thereof can be employed.
While any suitable reactor design can be used in the halogen dioxide
formation step, a packed tower reactor is most preferred, wherein the halogen
dioxide leaves the top of the tower after reacting with an aqueous phase of the metal
halate, along with the other required reactants, as required by the method
employed. It is an embodiment to form the halogen dioxide in a stirred vessel while
capturing the halogen dioxide gas above; however, such a scenario without a packed
tower may lead to loss of reactants and/or halide ions with the halogen dioxide.
While any suitable reactor design can be used in the chlorite formation step, a
packed tower reactor is most preferred, wherein the chlorite solution is recirculated
and enters the reactor from the top. Hydrogen peroxide is added to the recirculation
loop at a point prior to solution entry to the reactor. Sodium hydroxide and,
optionally, dilution water is added at the bottom of the recirculation loop. The
addition point of chlorine dioxide diluted with at least one inert gas, such as air,
water vapor and nitrogen, is at the bottom of the reactor. The gas is passed counter-
currently to the chlorite solution.
The pH of the reaction medium is maintained generally in the range of
about 11.8 to about 13.0, preferably about 12.0 to about 12.6. The hydrogen
peroxide excess is maintained using a potentiometric (ORP) measurement. The
ORP values, which are pH dependent, are generally maintained in the range of
between about -30 to about -200 mV vs. Ag/AgCI, preferably about -40 to about -
90mV vs. Ag/AgCI.
Halide Acid - Metal Hydroxide - Metal Sulfoxy Salt Formation
In the instant invention, both the halide acid and its associated metal
hydroxide or metal oxide may be produced from the metal halide salt by electrolysis
in the aforementioned EU. While sodium chloride is preferred, any metal halide salt
may be used to form the associated halide acid and the associated metal hydroxide,

preferably in solution. However, the halide acid is more economically formed by the
reaction of the metal halide salt with a sulfoxy acid, preferably H2SO4, according to
the SAP in an HAR. This reaction produces the halide acid, along with the
corresponding metal salt, wherein the anion for said salt is a sulfoxy molecule,
preferably at least one selected from a list consisting of a: sulfite, bisulfite, sulfate,
bisulfate and any combination therein.
A preferred embodiment utilizes about anhydrous or aqueous sodium chloride
in the EU as a metal halide salt, wherein the associated acid product is HCI and the
associated caustic product is sodium hydroxide (NaOH). A more economical and
most preferred process embodiment utilizes about anhydrous sodium chloride as a
metal halide salt in said HAR, wherein the associated acid product is HCI, preferably
HCI(g), and the associated byproduct salt is sodium in combination with at least one
selected from a list consisting of a: sulfate, bisulfate, sulfite, bisulfite and any
combination therein.
A preferred process embodiment utilizes about anhydrous or aqueous
calcium chloride as the metal halide salt in an EU, wherein the associated acid
product is HCI and the associated caustic product is calcium hydroxide. A more
economical and most preferred process embodiment utilizes about anhydrous
calcium chloride as a metal halide salt in said HAR, wherein the associated acid
product is HCI and the associated byproduct salt is calcium in combination with at
least one selected from a list consisting of a: sulfate, bisulfate, sulfite, bisulfite
and any combination therein.
A preferred process embodiment utilizes about anhydrous or aqueous
potassium chloride as a metal halide in the EU, wherein the associated acid
product is HCI and the associated caustic product is potassium hydroxide. A more
economical and most preferred process embodiment utilizes about anhydrous
potassium chloride as a metal halide in said HAR, wherein the associated acid
product is HCI and the associated byproduct salt is potassium in combination with
at least one selected from a list consisting of: sulfate, bisulfate, sulfite, bisulfite
and any combination therein.
A preferred process embodiment utilizes about anhydrous or aqueous
magnesium chloride as a metal halide in the EU, wherein the associated acid

product is HCI and the associated caustic product is magnesium hydroxide. A
more economical and most preferred process embodiment utilizes about
anhydrous magnesium chloride as a metal halide in said HAR, wherein the
associated acid product is HCI and the associated byproduct salt is magnesium in
combination with at least one selected from a list consisting of: sulfate, bisulfate,
sulfite, bisulfite and any combination therein.
As can be readily seen herein, the metal halide salt in the EU or in the HAR
can easily be any metal in combination with any halide. It is preferred that the metal
comprise at least one selected from a list comprising: Group IA metal, Group IIA
metal, Group IIIB metal, Group VIII metal, Group IB metal, Group IIB metal, Group
IIA metal and any combination therein. It is most preferred that the metal comprise
at least one selected from a list consisting of: sodium, calcium, potassium,
magnesium, aluminum, copper and any combination therein.
Bleach, Metal Hydroxide and Gypsum Formation
In the instant invention, it is preferred to utilize at least a portion of the
generated electricity obtained from a generator turned by a steam turbine, wherein
said steam turbine is turned by steam energy, and wherein said steam energy is
obtained from the formation of at least one selected from a list consisting of: SO2
from S and air, SO2 from S and O2, SO3 from SO2 and air, SO3 from SO2 and O2/ said
H2SO3 from SO2 and H2O; said H2SO4 from SO3 and H2O; oleum from H2SO4 and SO3,
said H2SO4 from oleum and H2O, and any combination therein in an electrolysis unit
to form at least one selected from a list consisting of: a metal halate from an
anhydrous or hydrous metal halide salt, a metal hypohalite from an anhydrous or
hydrous metal halide salt, a metal halite from an anhydrous or hydrous metal halide
salt, oxygen from water, hydrogen from water, hydrogen peroxide from the
electrolysis of H2SO4 to H2S2O8 followed by the reaction of said H2S2O8 with H2O, a
metal hydroxide from an anhydrous or hydrous metal halide salt, a halogen acid from
an anhydrous or hydrous metal halide salt and any combination therein.
It is preferred to manufacture a group IA or group IIA metal hypohalite by the
reaction of a group IA or group IIA metal hydroxide with a halide acid, wherein said
halide acid is manufactured in an HAR from the reaction of a metal halide salt with a

sulfoxy acid, thereby forming the corresponding group IA or group IIA metal sulfoxy
salt along with the corresponding halide acid, and wherein said group IA or group IIA
metal sulfoxy salt is then reacted with a group IA or group IIA metal hydroxide to
form said group IA or group IIA metal hydroxide along with the corresponding group
IIA sulfoxy salt in either an aqueous or hydrated form. It is most preferred that the
unit forming said group IA or group IIA metal hypohalite by the reaction of a group
IA or group IIA metal hydroxide with a halide acid, bleach reactor, comprise at least
one selected form a list consisting of: continuous stirred tank reaction, batch stirred
tank reaction, plug flow reaction and any combination therein.
It is preferred to manufacture a group IA or group IIA metal hypohalite by the
reaction of a group IA or group IIA metal hydroxide with a halogen acid, wherein said
halogen acid is manufactured in an electrolysis unit, wherein the electrical energy for
electrolysis in said electrolysis unit is generated by the energy of formation of at least
one selected from a list consisting of: SO2 from S and air, SO2 from S and O2, SO3 from
SO2 and air, SO3 from SO2 and O2, said H2SO3 from SO2 and H2O; said H2SO4 from SO3
and H2O; oleum from H2SO4 and SO3, said H2SO4 from oleum and H2O, and any
combination therein, wherein a group IA or group IIA metal sulfoxy salt is formed in
an HAR from the reaction of a group IA or group IIA metal halide salt with a sulfoxy
acid, and wherein said group IA or group IIA metal sulfoxy salt is then reacted in an
aqueous phase with a group II metal hydroxide to form said group IA or group IIA
metal hydroxide along with the corresponding group IIA metal sulfoxy salt.
It is preferred to prepare (manufacture) a group IA or group IIA metal
hydroxide in aqueous solution, wherein a group IA or group IIA metal sulfoxy salt is
reacted with group IIA metal hydroxide, thereby creating a mixture comprising a
group IA or group IIA metal hydroxide, water and a group IIA metal sulfoxy salt,
wherein said group IIA metal sulfoxy salt comprises at least one selected from a list
consisting of: sulfate, sulfate V2 hydrate, sulfate di-hydrate, sulfite, hydrogen sulfite,
sulfite di-hydrate and any combination therein, and wherein said mixture is
separated, thereby forming an aqueous solution comprising said group IA or group
IIA metal hydroxide, and a moist solid phase comprising said group IIA metal sulfoxy
salt, said group IA or group IIA metal hydroxide and water.

It is preferred to perform a separation of the aforementioned group IA or
group IIA metal hydroxide in aqueous solution from said group IIA sulfoxy salt in
order to react said group IA or group IIA metal hydroxide aqueous solution with
said halogen acid to form said group IA or group IIA metal hypohalite aqueous
solution. It has been found that due to the specific gravity difference between an
aqueous solution of a group IA or group IIA metal hydroxide and a calcium sulfoxy
salt (or any group IIA metal sulfoxy salt) in combination with the inherent
insolubility of a calcium sulfoxy salt (or any group IIA metal sulfoxy salt) with the
inherent solubility of a group IA or group IIA metal hydroxide (again sodium is the
most preferred metal), it is preferred to perform said separation by gravity
settling. It is preferred that said gravity settling be enhanced by a vibration-type
device placed upon and/or within the vessel of separation, thereby facilitating said
separation of said group IIA moiety in the form of at least one selected from a list
consisting of: sulfoxy, sulfoxy hydrate, sulfoxy di-hydrate and any combination
therein. It is most preferred that the solids phase (containing water, e.g. moist
solids) from said separation comprise at least one selected from a list consisting
of: calcium sulfate, calcium sulfate ½ hydrate, calcium sulfate di-hydrate, calcium
sulfite, calcium hydrogen sulfite, calcium sulfite di-hydrate and any combination
therein. It is preferred that said solid phase from said separation be about 25 to
85 percent solids. It is most preferred that said solid phase from said separation
be about 60 to 90 percent solids. It is most preferred that said separation vessel
comprise near the bottom portion of said separation vessel at least a portion of a
conical shape, wherein the pointed portion of said conical shape point down such
that said separated solid phase pass through an opening in said pointed portion of
said conical shape. While said conical shape can be of circular construction,
thereby having no corners, it is an embodiment said conical shape be of a
construction which comprises at least three comers. It is preferred that said
conical shape have between three and ten comers or locations wherein a side of
said conical shape meets another section of said conical shape. While said
vibration-type device may enhance the liquid/solids separation of said group IA or
group IIA metal hydroxide aqueous solution from said solid phase, it is preferred

that said vibration-type device have the ability to limit or minimize bridging of the
solid phase in the bottom of the conical section of said separation vessel.
It is most preferred to separate an aqueous solution of a group IA or group IIA
metal hydroxide from said a group IIA sulfoxy salt, such that an aqueous solution is
obtained comprising said group IA or group IIA metal and said hydroxide, and a moist
solid phase is obtained comprising said solid, said metal, said hydroxide and water.
It is most preferred that said separation vessel, as described previously herein
be performed a number of times, wherein a subsequent separation vessel have
added to it the moist solids phase from a previous separation vessel, and wherein
within or prior to said subsequent separation vessel water is added to the separated
moist solids from said previous separation vessel, such that the concentration is
lowered of said group IA or group IIA metal hydroxide in aqueous solution. It is
preferred that the water concentration within the first separation vessel be controlled
by the addition of water to at least one selected from a list consisting of: water to a
lime slaker, water to calcium hydroxide, water to said first separation vessel, water to
a group IIA metal other than calcium, and any combination therein.
It is preferred to perform a water dilution of a moist solid phase from a
separation thereby creating a mixture comprising said group IA or group IIA metal,
water, a hydroxide and a solid, wherein said solid comprises a group IIA metal with
at least one selected form a of list consisting of: sulfate, sulfate ½ hydrate, sulfate
di-hydrate, sulfite, hydrogen sulfite, sulfite di-hydrate and any combination therein,
wherein the concentration of said group IA or group IIA metal hydroxide in said
mixture is less than previous, and wherein said aqueous solution is separated from
said solid, such that an aqueous solution is obtained comprising a group IA or group
IIA metal hydroxide, and a moist solid phase is obtained comprising said solid, said
group IA or group IIA metal hydroxide and water.
It is most preferred that the solids phase from a separation vessel be
transferred to a subsequent separation vessel. It is an embodiment that said
transfer comprise at least one selected from a list consisting of: a screw, an
auger, a conveyor, a pneumatic system, and any combination therein, or other
conveying device as is known in the art of solids transfer.

It is most preferred that the solids phase from the last separation vessel, final
separated moist solids, be transferred to a dryer so as to remove any remaining water
from said solids. It is preferred to pH adjust said final separated solids with an acid
prior to said transfer to said dryer. It is preferred that said acid for said pH adjustment
of said final separated solids comprise a sulfoxy type acid. It is most preferred that
said sulfoxy type acid comprise sulfuric acid.
It is preferred that said group IIA metal hydroxide is formed by the reaction
with water of: said group IIA metal or said group IIA metal oxide, in what is
otherwise known as a slaker unit. It is preferred that said group IA or group IIA
metal comprises a group IA metal. It is most referred that said group IA metal
comprise sodium and said halogen comprise chlorine. It is most preferred that said
group IIA metal comprise calcium, such that said group IIA oxide comprises
calcium oxide, said group IIA metal hydroxide comprises calcium hydroxide and
said group IIA metal sulfoxy salt comprises calcium sulfoxy salt. It is most
preferred that said sulfoxy moiety comprise sulfate.
It has been learned by this instant invention that should the aqueous phase in
said last separation vessel be about less than 10% of a group IA metal hydroxide
that the final separated solids will be about 90 to 98 percent of at least one selected
from a list consisting of: a calcium sulfoxy salt, a calcium sulfoxy salt hydrate, a
calcium sulfoxy salt dehydrate and any combination therein, herein referred to as
gypsum product. (Again, calcium can be replaced with a group IIA metal.)
As the solubility of calcium hydroxide in water is about less than 2,000 mg/L,
depending upon temperature, there may be situations wherein it is preferred to
remove soluble calcium, or any group IIA metal, from a group IA metal hydroxide
or a group IA metal hypohalite. It is a preferred embodiment to purify a group IA
metal hydroxide or group IA metal hypohalite of calcium, or any group IIA metal,
by adding to an aqueous solution of said group IA metal hydroxide or group IA
metal hypohalite a from of carbonate or of carbon dioxide, which forms carbonate
upon contact with water. Said carbonate, it is found by the instant invention, will
then form calcium carbonate, or a group IIA carbonate, within said group IA metal
hydroxide solution or said group IA metal hypohalite solution. Calcium carbonate,
or group IIA metal carbonates, being soluble at only about 20 mg/L or less, will

then form a precipitate leaving about less than 20 mg/L of calcium in solution with
said group IA metal hydroxide. Said calcium carbonate is then preferably
separated from said group IA metal hydroxide solution or group IA metal
hypohalite by at least one selected form a list consisting of: an additional
separation vessel, as described herein; filtration; gravity settling; clarification; and
any combination therein. It is preferred that said calcium carbonate be dried
separately or with said gypsum product.
POLYNUCLEATE ALUMINUM COMPOUNDS (PAC), PMC, AND MP(s)
Polynucleate aluminum compounds (PAC) and polynucleate metal
compounds (PMC), whether or not containing aluminum, are both referred to as
metal polymers (MP(s)). MP(s) as used herein refer to polynucleate metal
compositions such as aluminum chlorohydrate, aluminum hydroxychloride,
aluminum hydroxyhalide, polyaluminum hydroxysulfate and polyaluminum
hydroxychlorosulfate, polyaluminum hydroxyhalosulfate polyaluminum hydroxy
sulfate calcium chloride, polyaluminum hydroxy sulfate calcium halide,
polyaluminum hydroxychlorosulfate calcium chloride, polyaluminum
hydroxychlorosulfate calcium halide, polyaluminum hydroxyphosphate chloride,
polyaluminum hydroxyphosphate halide, polyaluminum hydroxy "metal" chloride
and/or sulfate and/or phosphate, polyaluminum "multi-metal" hydroxy chloride
and/or sulfate and/or phosphate, polyaluminum hydroxy "metal" halide and/or
sulfate and/or phosphate, polyaluminum "multi-metal" hydroxy halide and/or
sulfate and/or phosphate and the like, wherein the "metal" is any metal that exists
in the +2 or + 3 valence state.
It has been shown possible by means of the instant invention to obtain the
above-mentioned MP(s), whereby the raw materials can simply be: a metal halide salt;
along with a metal in said MP in the form of at least one selected from a list consisting
of: the base metal, hydroxide form, oxide form and any combination therein, as well as
comprising a sulfoxy acid, preferably H2SO4 and/or H2SO3. Moreover, recycled metal is
a possibility, as compared to a refined metal oxide and/or hydroxide. Metals, other
than aluminum, can be used if prepared or capable of entering their +2 or +3 valence
state in their respective acid, oxide or hydroxide form. And, as a recycling measure,

waste catalyst streams or waste brine streams from refineries and/or chemical plants
containing aluminum halide or other metal halides can be used to manufacture MP.
It is a preferred embodiment to prepare a polynucleate aluminum compound,
comprising at least one metal in the +2 or the +3 valence state, wherein said
polynucleate metal compound is formed by the aqueous reaction of a metal halide
solution with at least one metal, wherein said metal halide solution comprises at least
one metal in the +2 or +3 valence state, wherein said at least one metal is in the 0,
+2 or +3 valence state, and if in the 0 valence state is capable of entering the +2 or
+3 valence state, wherein said metal halide solution is formed by the aqueous
reaction between said metal(s) within said metal halide solution and a halide acid,
and wherein said halide acid is formed by the reaction of a metal halide salt,
comprising the corresponding halide of said halide acid, with a sulfoxy acid.
It is preferred that the metal(s) in said metal halide solution or said at least one
metal comprise at least one selected from a group consisting of: ammonium, a Group
IA metal, a Group HA metal, a Group IIIB metal, a Group VIII metal, a Group IB
metal, a Group IIB metal, a Group IIIA metal, sodium, calcium, potassium,
magnesium, aluminum, copper and any combination therein. It is preferred that said
metal in said metal halide solution comprise a group IA or IIA metal; it is most
preferred that said metal in said metal halide salt comprise sodium. It is most
preferred that said sulfoxy acid comprise H2SO4. It is preferred that the sulfoxy acid is
formed by the sulfuric acid contact process. It is preferred that the reaction of a metal
halide salt with a sulfoxy acid be performed in an HAR producing a metal sulfoxy salt
comprising a moiety of at least one selected from a list consisting of: sulfate, bisulfate,
sulfite, bisulfite and any combination therein.
It is preferred that at least one of: the metal in the metal halide solution is
aluminum and said at least one metal is aluminum, the metal in said metal halide
solution is aluminum and the at least one metal is at least one metal other than
aluminum, the metal in the metal halide solution is a metal other than aluminum and
the at least one metal is aluminum, and the metal in the metal halide solution and
the at least one metal is a metal other than aluminum.
It is preferred that the halide in the polynucleate metal compound comprise at
least one of chlorine and bromihe. It is preferred that said polynucleate metal

compound comprises at least one selected from a list consisting of: sulfate, phosphate,
carbonate, silicate, nitrate and any combination therein.
MP formation is to be performed in a metal polymerization reactor (MPR). Said
MPR can comprise at least one selected from a list consisting of a: continuous stirred
tank reactor (CSTR), a batch stirred tank reactor, a pipe reactor (otherwise known as a
plug flow reactor, PFR), and any combination therein, as known in the art. (If a CSTR,
rather long residence times may be required.) It is most preferred that said MPR have
high shear mixing, as the instant invention has found high shear conditions during
aqueous formation of MP(s) to minimize waste-product, gel, formation and maximize
final product, MP formation. It is preferred that reactor mixing energy create a shear
situation of approximately greater than 30 sec-1. It is most preferred that reactor
mixing energy create a shear situation of approximately greater than 45 sec-1. High
shear is defined in this instant invention as a mixing energy of approximately greater
than 30 sec-1. However, as is known in the art of mixing and agitation, a high shear
mixing scenario can be obtained by many means, including a centrifugal pump,
homogenizer, reactor agitator or any physical system which combines the aqueous
reactants in a situation of high kinetic energy contact, thereby creating a situation of
high Reynolds Number of about greater than about 1,000 and preferably greater than
about 2,000. It is a preferred embodiment to manufacture said MP by batch in a
stirred tank reactor. It is most preferred to manufacture said MP in a plug flow or pipe
reactor. It has further been found in the instant invention that high shear mixing
energies lengthen the shelf life of the MP by as much as 100 to 500 percent. It is
theorized that this increase is obtained due to a minimization on an atomic scale, of gel
and thereby a minimization of available sites for gel to begin formation over time.
A final MP product is prepared having a metal content, preferably comprising
aluminum, of approximately 3-12 percent. A solid MP can be obtained by drying,
wherein a product containing approximately 12 - 24 percent of aluminum is
obtainable, whereby spray drying or rolling can be used as the drying method. A
product containing aluminum and another metal(s) can be obtained, wherein the
combined aluminum/other metal(s) concentration is less than or equal to
approximately 12 percent if in solution or approximately equal to or less than 24
percent if dried. A product containing at least one metal other than aluminum can be

obtained, wherein the metal(s) concentration is less than or equal to approximately
12 percent if in solution or approximately equal to or less than 24 percent if dried.
There is no need to use an excess of aluminum or metal in the MPR, as with
high shear mixing, the reaction has demonstrated near complete incorporation of
aluminum. As is known in the art, a higher molar relationship can easily be
increased by adding CaO, CaCO3 or Ca(OH)2 whereby a molar relationship of 1.8 -
1.9 can be obtained without increasing the reaction time to any considerable
extent. In the case that one should want a further increase in the molar
relationship OH:AI or OH:metal up to 2.5, metallic aluminum or metallic metal is to
be added in the stoichiometric amount.
It is preferred to manufacture an MP containing the sulfoxy moiety by
incorporating a sulfoxy acid into the MPR under a situation of high shear mixing.
It is a preferred embodiment there is no vehicular transportation of at least one
selected fro a list consisting of said: halide acid, metal halide solution, sulfoxy acid, and
any combination therein.
It is preferred to manufacture said MP, as described herein along with
obtaining steam from the formation of at least one selected from a list consisting
of: SO2 from S and air, SO2 from S and O2, SO3 from SO2 and air, SO3 from SO2
and O2, said H2SO3 from SO2 and H2O; said H2SO4 from SO3 and H2O; oleum from
H2SO4 and SO3, said H2SO4 from oleum and H2O, and any combination therein. It
is further an embodiment to create electricity from the energy of said steam as
described previously in this instant invention.
MAS (ACS Formation)
It is an embodiment to react at least one metal other than aluminum into
the MP; said metal(s) are to be preferably acidified prior to addition to the MPR.
When any metal other than aluminum is reacted in the MP, said metal(s) needs
to: form either a +2 or +3 valence state in said MAS, be prepared in their
respective oxide or hydroxide form in either the +2 or +3 valence state prior to
addition to the MPR or be capable of entering a +2 or +3 valence state in the
MPR. While more than one metal other than aluminum can be entered into the
MP and an MP can be manufactured with at least one metal other than aluminum,

wherein no aluminum is used, in the instant invention it is preferred to maximize
the use of aluminum and minimize the use of other metals due to the availability
and cost of bauxite, alumina and aluminum. For particular applications, it may be
preferred to choose a metal for that particular application; examples would
include zirconium for antiperspirants, copper for algae control in water systems,
tin as a sacrificial metal in corrosion control applications and gold, copper or silver
for conductivity applications. MAS is, therefore, defined herein as at least one
metal in halide acid solution wherein said metal(s) are in the +2 or +3 valence
state in concert with at least one halogen in anionic form.
MAS is formed from the aqueous reaction of a halide acid with a metal, metal
salt, metal oxide or metal hydroxide, wherein said reaction with a metal, metal oxide
and metal hydroxide is preferred. Aluminum halide solution (AHS) is formed from the
reaction of the halide acid with at least one selected from a list consisting of: bauxite,
an aluminum salt, aluminum, aluminum oxide and aluminum hydroxide. The
formation of MAS or AHS can occur in any vessel with agitation, such as a CSTR or a
PFR. A vent scrubber is preferably to be placed on said reactor or downstream of said
reactor to control emissions of hydrogen chloride gas (HCI(g)), or other halogen gas if
a halogen acid other than HCI is used. A portion of the enthalpy from AHS or MAS
manufacture can be utilized to decompose halite ions and/or provide heat to said MPR.
AHS and/or MAS containing up to 5 percent aluminum can easily be prepared. AHS
and MAS are easily prepared with the appropriate halide acid reacting with the chosen
metal, metal salt, metal oxide or metal hydroxide.
Alumina
The purification of bauxite to alumina creates alumina for the preparation of
aluminum halide solution (AHS), wherein ACS can be formed by reacting alumina
with HCI. Purified bauxite, alumina, may also be required for MP production, in the
MPR, if the raw bauxite contains any other heavy metal impurities and the resultant
MP is to be used in drinking water purification or another application where heavy
metal purity is an issue.
It is preferred to provide steam to a portion of the metal hydroxide solution in
order to perform the "Bayer" Refining Process (BRP), which can preferably proceed

adjacent to the EU, thereby utilizing the enthalpy of electrolysis to minimize steam
required in the BRP. While the BRP is most preferably used to purify bauxite, an
alternate preferred method would be to utilize recycled aluminum metal, where the
metal is purified in the BRP alone or with bauxite. If recycled aluminum is used, a
portion of the halide acid production can be used to assist in the purification of the
recycled aluminum or converting the aluminum to the associated aluminum halide
acid, which is preferably ACS. A side stream of the hydroxide solution is preferably
available to the MPR to assist in managing either the reactor pH or final MP basicity, as
needed. Portions of the metal hydroxide solution are preferably sent to the haiide acid
gas scrubbing system to pH-neutralize the liquid effluent and/or to the by-product
metal stream to pH balance the final by-product metal sulfate, sulfite or bisulfite salt.
Aluminum is provided for the MP or AHS with at least one selected from a list
comprising: bauxite, alumina, aluminum hydroxide, aluminum metal and any
combination therein. The aluminum metal can be refined or recycled. Should bauxite
be used and NaOH or MOH from the EU be provided to refine the bauxite, the waste
minerals from bauxite refining have many market uses, such as soils stabilization. It is
most preferred to use alumina, aluminum or purified recycled aluminum in the
preparation of AHS and MP because the acidification of bauxite, aluminum, aluminum
oxides and aluminum hydroxides to AHS can also acidify any other metal impurities
that may be present in recycled aluminum or bauxite, thereby allowing said metal
impurities to react within the AHS and/or the final MP. In cases wherein heavy metal
contamination is not an issue and/or the bauxite is pure enough from other earthen
contaminants, both AHS and MP can be formed utilizing the raw bauxite. Any metal
oxides that do not enter the MP complex can be used for soil stabilization.
Energy
The instant invention manages hazardous materials, heat energy, chemical
energy, electrical energy, as well as investments in equipment and raw materials more
effectively than previous processes, which focused primarily on formation of the
polynucleate aluminum compounds and/or disinfectants. In contrast, the instant
invention focuses on the processes of MP production and disinfectant production,
incorporating methods to manage materials and energy not taught previously. Due to

this management, the cost of manufacture of MP(s) and ACS, or any aluminum halide
Solution (AHS) or metal halide solution (MAS), is much less than that previously. Due
to this management, the cost of manufacture of a disinfectant and/or an oxidant is
much less than that previously.
The metal acid reactor (MAR) used to form AHS and/or MAS is also preferably
placed near or adjacent to the EU and/or the HAR and preferably adjacent to the
MPR so that the enthalpy of reaction to from MAS or AHS can be utilized in the MPR.
It is preferred that the MPR and he MAR be the same equipment, e.g. the same
vessel, such that in that same vessel: a) an aqueous solution of said halide acid is
formed from the reaction of said halide acid in water, b) said metal halide solution is
formed by the reaction of said metal(s) in said halide acid, and c) said polynucleate
aluminum compound is formed by the reaction of said at least one metal(s) in said
metal halide solution.
The MPR is preferably adjacent or near the EU and/or the BRP so that the
enthalpy of alumina formation can be utilized in the formation of MP(s). It is
preferred that a vent scrubber be placed on the reactor to control halide acid gas
emissions. The MPR may be equipped to operate at elevated temperature, pressure
or both to form MP(s). It is preferred that the MPR be operated at approximately
100 - 150 °C (212 - 3O2 °F); however, depending on the final product composition,
the MPR can be operated between approximately 30 - 200 °C (86 - 381 °F). While
higher temperatures allow for an increase in the reaction rate constant for MP
formation, increases in MPR operating temperature require a corresponding increase
in the operating pressure to maintain reactants in an aqueous solution (H2O, Al, OH,
CI, etc.) Reactor pressure can be 1 to 7 atmospheres absolute, wherein 1 to 4
atmospheres is preferred.
Heat energy, enthalpy or temperature of matter, may be obtained from: SAR
or SCAP; sulfoxy salt formation; calcium hydroxide formation; the electrolysis unit;
formation of a calcium sulfoxy salt; pH adjustment; halogen dioxide formation; metal
halate formation; metal halide acid formation, and halide acid formation. Energy will
be required for bauxite purification to alumina, if bauxite is used and needs to be
purified. Energy will be required for MP formation in the MPR. Energy will be
required for recycled aluminum purification, if employed. Depending on production

rates and the type of raw materials utilized, energy can be easily transferred from
one reaction vessel to another (via heat transfer of water and/or steam, vessel water
jacketing and vessel steam jacketing, or in the form of the product itself) so that
there is maximal efficiency in the use of enthalpy from chemical reactions and usage
as hot water and/or steam energy. For example, if larger quantities of AHS or MAS
were required than could be used to provide heat for halite decomposition or to heat
the MPR for MP production or to heat the Bayer Process for bauxite purification. For
example, waste steam or low pressure steam can be used to heat sulfur to a molten
state for ease of handling in and to the SACP.
It is preferred that the energy from the formation of at least one selected
from a list consisting of: SAR; bisulfate or bisulfite formation; calcium hydroxide
formation; the electrolysis unit; formation of a calcium sulfoxy salt, pH
adjustment, halogen dioxide formation, metal halate formation, metal AHS or MAS
formation, halide acid formation, and any combination therein is used to heat
water and/or steam. It is preferred that the heated water and/or steam is at least
partially used to heat at least one selected from a list consisting of: the aqueous
reaction of a metal halide solution with- a metal to form a polynucleate metal
compound, the reaction of a metal hydroxide with a halide acid to form a metal
hypohalite, heating and/or drying of a calcium sulfoxy salt, heating and/or drying
of a group IA or a group IIA sulfoxy salt, and any combination therein.
It is most preferred to manufacture at least one of: MP(s), AHS(s), hypohalites,
halites, halates and halogen oxides without vehicular transportation of hazardous
materials, which would include at least one selected from a list comprising: metal acid
solution, halide acid solution, sulfuric acid and caustic.
Construction Materials
It is preferred that said metal sulfoxy salt and/or said gypsum product be
used in wall-board, sheetrock, manufacture. It is most preferred that said metal
sulfoxy salt and/or gypsum product comprise or be blended with at least one
selected from a list consisting of: sodium sulfate, lime, hydrated lime, calcium
sulfate, magnesium sulfate, aluminum sulfate, silicone sulfate, sodium carbonate,
calcium carbonate, magnesium carbonate, aluminum carbonate, silicone carbonate,

silica, silicates, sand, wax, glass, glass fiber, paper, adhesive, cement and any
combination thereof to form a wall-board product. It is preferred that said sulfoxy
salt, gypsum product or wallboard product be used in the manufacture of
construction materials. It is most preferred that said construction materials
comprise a wall-board or sheet-rock type product.
It is an embodiment that said gypsum product is used in soil stabilization.
Manufacturing Process Flow Paths
A preferred embodiment of the instant invention is to form within a
manufacturing plant, manufacturing process systems and flow paths.
It is a preferred embodiment to form at least one process flow path,
wherein at least one of water and steam obtain by heat transfer via heat transfer
equipment from at least a portion of the energy of formation of at least one
selected from a list comprising: SO2 from S and air, SO2 from S and O2, SO3 from
5O2 and air, SO3 from SO2 and O2, said H2SO3 from SO2 and H2O; said H2SO4 from
SO3 and H2O; oleum from H2SO4 and SO3, said H2SO4 from oleum and H2O, and
any combination therein.
It is a preferred embodiment to form at least one process flow path,
wherein steam and/or hot water energy is obtained by heat transfer from at least
a portion of the energy of formation of a halide acid and a metal sulfoxy salt from
the reaction of a sulfoxy acid with a metal halide salt.
It is a preferred embodiment to form at least one process flow path,
wherein steam and/or hot water energy is obtained by heat transfer from at least
a portion of the energy of formation of a calcium hydroxide from the reaction of
water and at least one of calcium and calcium oxide.
It is a preferred embodiment to form at least one process flow path,
wherein steam and/or hot water energy is obtained by heat transfer from at least
a portion of the energy of formation of a calcium sulfoxy salt from the reaction of
a calcium hydroxide with a metal sulfoxy salt. It is most preferred that said metal
comprise sodium.
It is a preferred embodiment to form at least one process flow path, wherein
steam and/or hot water energy is obtained by heat transfer from at least a portion of

the energy of formation of a metal sulfoxy salt from the reaction of a metal
hydroxide with a sulfoxy acid. It is most preferred that said metal comprise sodium.
It is a preferred embodiment to form at least one process flow path, wherein
steam and/or hot water energy is obtained by heat transfer from at least a portion
of the energy of formation of a metal halide solution from the reaction of at least
one metal with a halide acid. It is most preferred that said metal comprise sodium.
It is most preferred that said halide comprise chlorine.
It is a preferred embodiment to form at least one process flow path, wherein
steam and/or hot water energy is obtained by heat transfer from at least a portion of
the energy of formation of a halogen dioxide from the reaction of a metal halate with a
sulfoxy acid and sulfur dioxide. It is most preferred that said metal comprise sodium.
It is most preferred that said halide comprise chlorine.
It is a preferred embodiment to form at least one process flow path, wherein
steam and/or hot water energy is obtained by heat transfer from at least a portion of
the energy of formation of a halogen dioxide from the reaction of a metal halate with
a sulfoxy acid and hydrogen peroxide. It is most preferred that said metal comprise
sodium. It is most preferred that said halide comprise chlorine.
It is a preferred embodiment to form at least one process flow path, wherein
steam and/or hot water energy is obtained by heat transfer from at least a portion of
the energy of formation of a metal halate from the reaction of a halogen dioxide with
a hydrogen peroxide and a metal hydroxide. It is most preferred that said metal
comprise sodium. It is most preferred that said halide comprise chlorine.
It is a preferred embodiment that at least one MPR, at least one unit
reacting a halide acid with a metal, and at least one HAR, form a process flow
path, wherein said at least one unit reacting a halide acid with a metal is
upstream of said at least one MPR, wherein said at least one HAR is upstream of
said at least one unit reacting a halide acid with a metal, wherein a polynucleate
metal compound is formed in said at least one MPR by reacting at least one metal
with a metal halide solution formed in said at least one unit reacting a halide acid
with a metal, and wherein said halide acid is formed in said at least one HAR by
reacting a metal halide salt with a sulfoxy acid.

It is a preferred embodiment that at least one MPR, at least one unit
reacting a halide acid with a metal, at least one SAR, and at least one HAR, form
a process flow path, wherein said at least one unit reacting a halide acid with a
metal is upstream of said at least one MPR, wherein said at least one HAR is
upstream of said at least one unit reacting a halide acid with a metal, wherein
said SAR is upstream of said HAR, wherein a polynucleate metal compound is
formed in said at least one MPR by reacting at least one metal with a metal halide
solution formed in said at least one unit reacting a halide acid with a metal,
wherein said halide acid is formed in said at least one HAR, and wherein said
halide acid is formed by reacting a metal halide salt with a sulfoxy acid formed in
said at least one SAR.
It is a preferred embodiment to manufacture a polynucleate metal
compound, wherein there is no vehicular transportation of at least one selected from
a group consisting of said: halide acid, metal halide solution, sulfoxy acid, and any
combination therein.
It is a preferred embodiment that at least one MPR, at least one unit reacting
a halide acid with a metal, at least one SAR, at least one HAR, and at least one EU
form a process flow path, wherein said at least one unit reacting a halide acid with a
metal is upstream of said at least one MPR, wherein said at least one HAR is
upstream of said at least one unit reacting a halide acid with a metal, wherein said
SAR is upstream of said HAR, wherein said at least one EU is upstream of said at
least one unit reacting a halide acid with a metal, wherein a polynucleate metal
compound is formed in said at least one MPR by reacting at least one metal with a
metal halide solution formed in said at least one unit reacting a halide acid with a
metal, wherein said halide acid is formed in at least one of said at least one HAR and
at least one EU, and wherein said HAR said halide acid is formed by reacting a metal
halide salt with a sulfoxy acid formed in said at least one SAR.
It is preferred to form a process flow path, wherein a unit or units comprising
an MPR (which includes both polynucleate aluminum manufacture and polynucleate
metal manufacture) is downstream of at least one metal acid reaction (MAR) unit
manufacturing ACS and/or MAS. It is preferred that said MAR is downstream of at least
one unit forming a halide acid, wherein said unit(s) forming said halide acid can be at

least one of an EU and an HAR. It is preferred to form a process flow path, wherein at
least one MPR is downstream of at least one MAR, wherein said MAR forms ACS
and/or MAS and is downstream of at least one unit forming a halide acid, wherein said
unit(s) forming said halide acid can be at least one of an EU and an HAR, wherein the
sulfoxy acid, preferably H2SO4, for said HAR is manufactured in a unit or units
comprising an SACP and the electricity for said EU is created in a generator driven by a
steam turbine, wherein steam energy turns said steam turbine, and wherein said
steam energy is obtained from the formation of at least one selected from a list
comprising: SO2 from S and air, SO2 from S and O2, SO3 from SO2 and air, SO3 from
SO2 and O2, said H2SO3 from SO2 and H2O; said H2SO4 from SO3 and H2O; oleum from
H2SO4 and SO3, said H2SO4 from oleum and H2O, and any combination therein.
It is preferred for the MPR and MAR unit(s) to be one and the same, such
that: a first reaction forms a halide acid from the reaction of a halide acid gas in
water or addition of an aqueous halide acid to the reactor, a second reaction forms
an MAS (preferably ACS) by the addition of at least one metal (preferably comprising
alumina) to said halide acid and a third reaction forms an polynucleate metal
compound (preferably comprising AlxCIY(OH)z) from the addition of at least one
metal (preferably comprising alumina) to said reactor.
It is a preferred embodiment to form a process flow path, wherein at least one
unit forms a disinfectant and/or an oxidant in an EU, wherein the electricity for
electrolysis in said EU is obtained from a generator driven by a steam turbine, wherein
the steam energy used to turn said steam turbine is obtained from heating at least one
of water and steam by heat transfer from at least a portion of the energy of formation
of at least one selected from a list comprising: SO2 from S and air, SO2 from S and
O2, SO3 from SO2 and air, SO3 from SO2 and O2, said H2SO3 from SO2 and H2O; said
H2SO4 from SO3 and H2O; oleum from H2SO4 and SO3, said H2SO4 from oleum and
H2O, and any combination therein.
It is a preferred embodiment that an EU and an HAR form a process flow path,
wherein at least one disinfectant is formed in said EU and at least one halide acid and
a metal sulfoxy salt is formed in an HAR, wherein said halide acid(s) can be used to
further form an additional disinfectant in at least one unit downstream of said EU by
reacting said halide acid formed in said HAR with a disinfectant formed in said EU; it is

most preferred that said disinfectant formed in said EU is a metal halate and that the
disinfectant formed with the reaction of said metal halate with said halogen acid be the
corresponding halogen dioxide, preferably chlorine dioxide. It is preferred that said
metal comprise a group IA or group IIA metal. It is most preferred that said metal
comprise sodium. It is most preferred that said halogen comprise chlorine.
It is a preferred embodiment that at least one EU, at least one SAR, at least
one HAR, at least one gypsum unit, at least one slaker, at least one separator, at least
one dryer, at least one halogen dioxide generator, at least one metal halite unit, and at
least one bleach unit, form a process flow path, wherein said at least one EU is
upstream of said at least one halogen dioxide generator, wherein said at least one
halogen dioxide generator is upstream of said at least one metal halite unit, wherein
said at least one gypsum unit is downstream of said at least metal halite unit and said
at least one halogen dioxide generator, wherein said at least one separator is
downstream of said at least one gypsum unit, wherein said at least one slaker is
upstream of said at least one gypsum unit, wherein said at least one dryer is
downstream of said at least one separator, wherein said separator is upstream of said
at least one metal halite unit and said at least one bleach unit, wherein said at least
one bleach unit is downstream of said at least one HAR and downstream of said at
least one EU and downstream of said at least one separator, wherein said at least one
HAR is downstream of said at least one SAR, wherein said at least one SAR is
upstream of said halogen dioxide generator, wherein said at least one SAR produces
energy to be used in the generation of electricity for said at least one EU, wherein the
electricity for electrolysis in said EU(s) is obtained from a generator driven by a steam
turbine, wherein the steam used to turn said steam turbine to create said electricity is
obtained from heat transfer from at least a portion of the energy of formation of at
least one selected from a list comprising: SO2 from S and air, SO2 from S and O2, SO3
from SO2 and air, SO3 from SO2 and O2, said H2SO3 from SO2 and H2O; said H2SO4
from SO3 and H2O; oleum from H2SO4 and SO3, said H2SO4 from oleum and H2O, and
any combination therein, wherein a halogen dioxide is formed in said halogen dioxide
generator by the reaction of a metal halate from said at least one EU in combination
with a sulfoxy acid formed in said at least one SAR and in combination with at least
one of SO2 formed in said at least one SAR and H2O2 formed in said at least one EU,

wherein a group IA or group IIA metal halite is formed by the reaction of said halogen
dioxide with H2O2 formed in said at least one EU and with a group IA or group IIA
metal hydroxide from at least one of said at least one separator and said at least one
EU, wherein a mixture of a calcium sulfoxy salt and said metal hydroxide is formed in
said at least one gypsum unit by reacting a metal sulfoxy salt from at least one of said
at least one halogen dioxide generator, said at least one metal halite unit and said at
least one HAR, wherein a dry product comprising an anhydrous calcium sulfoxy salt or
a hydrated calcium sulfoxy salt is obtained from said at least one dryer by drying a
calcium sulfoxy salt formed in said at least one gypsum unit, wherein a calcium
hydroxide is formed in said at least one slaker by the reaction of water with at least
one of calcium and calcium oxide, wherein a metal hypohalite is formed in said at least
one bleach unit by reacting a halide acid from at least one of said at least one HAR and
said at least one EU with a metal hydroxide from at least one of said at least one EU
and said at least one separator, and wherein a halide acid and a metal sulfoxy salt is
formed in said at least one HAR from the reaction of a metal halide salt with a sulfoxy
acid formed in said at least one SAR. It is preferred that metal comprise a group IA or
group IIA metal. It is most preferred that said metal comprise sodium. It is most
preferred that said halogen comprise chlorine.
It is a preferred embodiment that at least one EU, at least one SAR, at least s
one HAR, and at least one dryer, form a process flow path, wherein said at least one
EU is downstream of said at least one SAR, wherein said at least one HAR is
downstream of said at least one SAR, wherein said dryer is downstream of said at
least one HAR, wherein said at least one SAR produces energy to be used in the
generation of electricity for said at least one EU, wherein the electricity for
electrolysis in said EU(s) is obtained from a generator driven by a steam turbine,
wherein the steam used to turn said steam turbine to create said electricity is
obtained from heat transfer from at least a portion of the energy of formation of at
least one selected from a list comprising: SO2 from S and air, SO2 from S and O2,
SO3 from SO2 and air, SO3 from SO2 and O2, said H2SO3 from SO2 and H2O; said
H2SO4 from SO3 and H2O; oleum from H2SO4 and SO3, said H2SO4 from oleum and
H2O, and any combination therein, wherein at least one of a halogen gas, halide acid
and metal hydroxide, metal hypohalite, metal halate, and metal halite is formed in

said at least one EU, wherein a halide acid and a metal sulfoxy salt is formed in said
at least one HAR by reacting a metal halide salt with a sulfoxy acid formed in said at
least one SAR, and wherein a dry anhydrous metal sulfoxy salt or a hydrated metal
sulfoxy salt is formed in said dryer by heat energy from said steam. It is preferred
that metal comprise a group IA or group IIA metal. It is most preferred that said
metal comprise sodium. It is most preferred that said halogen comprise chlorine.
It is a preferred embodiment that at least one SAR, at least one HAR, and at
least one dryer, form a process flow path, wherein said HAR is downstream of said at
least one SAR, wherein said dryer is downstream of said at least one HAR, wherein
electricity is obtained from a generator driven by a steam turbine, wherein the steam
used to turn said steam turbine to create said electricity is obtained from heat
transfer from at least a portion of the energy of formation of at least one selected
from a list comprising: SO2 from S and air, SO2 from S and O2, SO3 from SO2 and air,
SO3 from SO2 and O2, said H2SO3 from SO2 and H2O; said H2SO4 from SO3 and H2O;
oleum from H2SO4 and SO3, said H2SO4 from oleum and H2O, and any combination
therein, wherein a halide acid and a metal sulfoxy salt is formed in said at least one
HAR from the reaction of a metal halide salt with a sulfoxy acid formed in said at
least one SAR, and wherein a dry anhydrous metal sulfoxy salt or a hydrated metal
sulfoxy salt is formed in said dryer by heat energy from said steam. It is preferred
that metal comprise a group IA or group IIA metal. It is most preferred that said
metal comprise sodium. It is most preferred that said halogen comprise chlorine.
It is a preferred embodiment that at least one EU, at least one SAR, at least
one gypsum unit, at least one slaker, at least one separator, at least one dryer, at least
one halogen dioxide generator, at least one metal halite unit, and at least one bleach
unit, form a process flow path, wherein said at least one EU is upstream of said at
least one halogen dioxide generator, wherein said at least one halogen dioxide
generator is upstream of said at least one metal halite unit, wherein said at least one
gypsum unit is downstream of said at least metal halite unit and said at least one
halogen dioxide generator, wherein said at least one separator is downstream of said
at least one gypsum unit, wherein said at least one slaker is upstream of said at least
one gypsum unit, wherein said at least one dryer is downstream of said at least one
separator, wherein said separator is upstream of said at least one metal halite unit and

said at least one bleach unit, wherein said at least one bleach unit is downstream of
said at least one EU and downstream of said at least one separator, wherein said at
least one SAR is upstream of said halogen dioxide generator, wherein said at least one
SAR produces energy to be used in the generation of electricity for said at least one
EU, wherein the electricity for electrolysis in said EU(s) is obtained from a generator
driven by a steam turbine, wherein the steam used to turn said steam turbine to
create said electricity is obtained from heat transfer from at least a portion of the
energy of formation of at least one selected from a list comprising: SO2 from S and
air, SO2 from S and O2, SO3 from SO2 and air, SO3 from SO2 and O2, said H2SO3 from
SO2 and H2O; said H2SO4 from SO3 and H2O; oleum from H2SO4 and SO3, said H2SO4
from oleum and H2O, and any combination therein, wherein a halogen dioxide is
formed in said halogen dioxide generator by the reaction of a metal halate from said at
least one EU in combination with a sulfoxy acid formed in said at least one SAR and in
combination with at least one of SO2 formed in said at least one SAR and H2O2 formed
in said at least one EU, wherein a group IA or group IIA metal halite is formed by the
reaction of said halogen dioxide with H2O2 formed in said at least one EU and with a
group IA or group IIA metal hydroxide from at least one of said at least one separator
and said at least one EU, wherein a mixture of a calcium sulfoxy salt and said metal
hydroxide is formed in said at least one gypsum unit by reacting a metal sulfoxy salt
from at least one of said at least one halogen dioxide generator, said at least one
metal halite unit and said at least one HAR with a calcium hydroxide formed in said at
least one slaker, wherein a dry product comprising an anhydrous calcium sulfoxy salt
or a hydrated calcium sulfoxy salt is obtained from said at least one dryer by drying a
calcium sulfoxy salt formed in said gypsum unit, wherein a calcium hydroxide is formed
in said at least one slaker by the reaction of water with at least one of calcium and
calcium oxide, wherein a metal hypohalite is formed in said at least one bleach unit by
reacting a halide acid from said at least one EU with a metal hydroxide from at least
one of said at least one EU and said at least one separator, and wherein a sulfoxy acid
formed in said at least one SAR. It is preferred that metal comprise a group IA or
group IIA metal. It is most preferred that said metal comprise sodium. It is most
preferred that said halogen comprise chlorine.

It is a preferred embodiment that at least one EU, at least one SAR, at least
one HAR, at least one gypsum unit, at least one separator, at least one dryer, at least
one halogen dioxide generator, at least one metal halite unit, and at least one bleach
unit, form a process flow path, wherein said at least one EU is upstream of said at
least one halogen dioxide generator, wherein said at least one halogen dioxide
generator is upstream of said at least one metal halite unit, wherein said at least one
gypsum unit is downstream of said at least metal halite unit and said at least one
halogen dioxide generator, wherein said at least one separator is downstream of said
at least one gypsum unit, wherein said at least one dryer is downstream of said at
least one separator, wherein said separator is upstream of said at least one metal
halite unit and said at least one bleach unit, wherein said at least one bleach unit is
downstream of said at least one HAR and downstream of said at least one EU and
downstream of said at least one separator, wherein said HAR is downstream of said at
least one SAR, wherein said at least one SAR is upstream of said halogen dioxide
generator, wherein said at least one SAR produces energy to be used in the generation
of electricity for said at least one EU, wherein the electricity for electrolysis in said
EU(s) is obtained from a generator driven by a steam turbine, wherein the steam used
to turn said steam turbine to create said electricity is obtained from heat transfer from
at least a portion of the energy of formation of at least one selected from a list
comprising: SO2 from S and air, SO2 from S and O2, SO3 from SO2 and air, SO3 from
SO2 and O2, said H2SO3 from SO2 and H2O; said H2SO4 from SO3 and H2O; oleum from
H2SO4 and SO3, said H2SO4 from oleum and H2O, and any combination therein,
wherein a halogen dioxide is formed in said halogen dioxide generator by the reaction
of a metal halate from said at least one EU in combination with a sulfoxy acid formed
in said at least one SAR and in combination with at least one of SO2 formed in said at
least one SAR and H2O2 formed in said at least one EU, wherein said group IA or group
IIA metal halite is formed in said at least one metal halite unit by the reaction of said
halogen dioxide with H2O2 formed in said at least one EU and with a metal hydroxide
from at least one of said at least one separator and said at least one EU, wherein a
mixture of a calcium sulfoxy salt and said metal hydroxide is formed in said at least
gypsum one unit by reacting a metal sulfoxy salt from at least one of said at least one
halogen dioxide generator, said at least one metal halite unit and said at least one HAR

with calcium hydroxide, wherein a dry product comprising an anhydrous calcium
sulfoxy salt or a hydrated calcium sulfoxy salt is obtained from said at least one dryer
by drying a calcium sulfoxy salt formed in said gypsum unit, wherein a metal
hypohalite is formed in said at least one bleach unit by reacting a halide acid from at
least one of said at least one HAR and said at least one EU with a metal hydroxide
from at least one of said at least one EU and said at least one separator, and wherein
a halide acid and a metal sulfoxy salt is formed in said HAR from the reaction of a
metal halide salt with a sulfoxy acid formed in said at least one SAR. It is preferred
that metal comprise a group IA or group IIA metal. It is most preferred that said
metal comprise sodium. It is most preferred that said halogen comprise chlorine.
It is a preferred embodiment that at least one EU, at least one SAR, at least
one gypsum unit, at least one separator, at least one dryer, at least one halogen
dioxide generator, at least one metal halite unit, and at least one bleach unit, form a
process flow path, wherein said at least one EU is upstream of said at least one
halogen dioxide generator, wherein said at least one halogen dioxide generator is
upstream of said at least one metal halite unit, wherein said at least one gypsum unit
is downstream of said at least one metal halite unit and said at least one halogen
dioxide generator, wherein said at least one separator is downstream of said at least
gypsum one unit, wherein said at least one dryer is downstream of said at least one
separator, wherein said separator is upstream of said at least one metal halite unit and
said at least one bleach unit, wherein said at least one bleach unit is downstream of
said at least one EU and downstream of said at least one separator, wherein said at
least one SAR is upstream of said generator forming a halogen dioxide, wherein said at
least one SAR produces energy to be used in the generation of electricity for said at
least one EU, wherein the electricity for electrolysis in said EU(s) is obtained from a
generator driven by a steam turbine, wherein the steam used to turn said steam
turbine to create said electricity is obtained from heat transfer from at least a portion
of the energy of formation of at least one selected from a list comprising: SO2 from S
and air, SO2 from S and O2, SO3 from SO2 and air, SO3 from SO2 and O2, said H2SO3
from SO2 and H2O; said H2SO4 from SO3 and H2O; oleum from H2SO4 and SO3, said
H2SO4 from oleum and H2O, and any combination therein, wherein a halogen dioxide is
formed in said halogen dioxide generator by the reaction of a metal halate from said at

least one EU in combination with a sulfoxy acid formed in said at least one SAR and in
combination with at least one of SO2 formed in said at least one SAR and H2O2 formed
in said at least one EU, wherein said group IA or group IIA metal halite is formed by
the reaction of said halogen dioxide with H2O2 formed in said at least one EU and with
a group IA or group IIA metal hydroxide from at least one of said at least one
separator and said at least one EU, wherein a mixture of a calcium sulfoxy salt and
said metal hydroxide is formed in said at least one gypsum unit by reacting a metal
sulfoxy salt from at least one of said at least one halogen dioxide generator and said at
least one metal halite unit, wherein a dry product comprising an anhydrous calcium
sulfoxy salt or a hydrated calcium sulfoxy salt is obtained from said at least one dryer
by drying a calcium sulfoxy salt formed in said gypsum unit, wherein a metal
hypohalite is formed in said at least one bleach unit by reacting a halide acid from at
least one of said at least one HAR and said at least one EU with a metal hydroxide
from at least one of said at least one EU and said at least one separator, and wherein
a sulfoxy acid is formed in said at least one SAR. It is preferred that metal comprise a
group IA or group IIA metal. It is most preferred that said metal comprise sodium. It
is most preferred that said halogen comprise chlorine.
It is a preferred embodiment that at least one SAR, at least one HAR, at least
one gypsum unit, at least one slaker, at least one separator, at least one dryer, and at
least one bleach unit, form a process flow path, wherein said at least one separator is
downstream of said at least one gypsum unit, wherein said at least one slaker is
upstream of said at least one gypsum unit, wherein said at least one dryer is
downstream of said at least one separator, wherein said separator is upstream of said
at least one bleach unit, wherein said at least one bleach unit is downstream of said at
least one HAR and downstream of said at least one separator, wherein said at least
one HAR is downstream of said at least one SAR, wherein said at least one SAR
produces energy to be used in the generation of electricity for said at least one EU,
wherein the electricity for electrolysis in said EU(s) is obtained from a generator driven
by a steam turbine, wherein the steam used to turn said steam turbine to create said
electricity is obtained from heat transfer from at least a portion of the energy of
formation of at least one selected from a list comprising: SO2 from S and air, SO2 from
S and O2, SO3 from SO2 and air, SO3 from SO2 and O2, said H2SO3 from SO2 and H2O;

said H2SO4 from SO3 and H2O; oleum from H2SO4 and SO3, said H2SO4 from oleum and
H2O, and any combination therein, wherein a mixture of a calcium sulfoxy salt and said
metal hydroxide is formed in said at least one gypsum unit by reacting a metal sulfoxy
salt from at least one of said HAR, wherein a dry product comprising an anhydrous
calcium sulfoxy salt or a hydrated calcium sulfoxy salt is obtained from said at least
one dryer by drying a calcium sulfoxy salt formed in said at least one gypsum unit,
wherein a calcium hydroxide is formed in said at least one slaker by the reaction of
water with at least one of calcium and calcium oxide, wherein a metal hypohalite is
formed in said at least one bleach unit by reacting a halide acid from said at least one
HAR with a metal hydroxide from said at least one separator, and wherein a halide
acid and a metal sulfoxy salt is formed in said at least one HAR from the reaction of a
metal halide salt with a sulfoxy acid formed in said at least one SAR. It is preferred
that metal comprise a group IA or group IIA metal. It is most preferred that said
metal comprise sodium. It is most preferred that said halogen comprise chlorine.
It is a preferred embodiment that at least one EU, at least one SAR, at least j
one HAR, at least one gypsum unit, at least one slaker, at least one separator, at least
one dryer, at least one halogen dioxide generator, and at least one bleach unit, form a
process flow path, wherein said at least one EU is upstream of said at least one
halogen dioxide generator, wherein said at least one gypsum unit is downstream of
said at least one halogen dioxide generator, wherein said at least one separator is
downstream of said at least one gypsum unit, wherein said at least one slaker is
upstream of said at least one gypsum unit, wherein said at least one dryer is
downstream of said at least one separator, wherein said separator is upstream of said
at least one bleach unit, wherein said at least one bleach unit is downstream of said at
least one HAR and downstream of said at least one EU and downstream of said at
least one separator, wherein said at least one HAR is downstream of said at least one
SAR, wherein said at least one SAR is upstream of said halogen dioxide generator,
wherein said at least one SAR produces energy to be used in the generation of
electricity for said at least one EU, wherein the electricity for electrolysis in said EU(s) is
obtained from a generator driven by a steam turbine, wherein the steam used to turn
said steam turbine to create said electricity is obtained from heat transfer from at least
a portion of the energy of formation of at least one selected from a list comprising:

SO2 from S and air, SO2 from S and O2, SO3 from SO2 and air, SO3 from SO2 and O2,
said H2SO3 from SO2 and H2O; said H2SO4 from SO3 and H2O; oleum from H2SO4 and
SO3, said H2SO4 from oleum and H2O, and any combination therein, wherein a halogen
dioxide is formed in said halogen dioxide generator by the reaction of a metal halate
from said at least one EU in combination with a sulfoxy acid formed in said at least one
SAR and in combination with at least one of SO2 formed in said at least one SAR and
H2O2 formed in said at least one EU, wherein a mixture of a calcium sulfoxy salt and
said metal hydroxide is formed in said at least one gypsum unit by reacting a metal
sulfoxy salt from at least one of said at least one halogen dioxide generator, said at
least one metal halite unit and said at least one HAR, wherein a dry product
comprising an anhydrous calcium sulfoxy salt or a hydrated calcium sulfoxy salt is
obtained from said at least one dryer by drying a calcium sulfoxy salt formed in said at
least one gypsum unit, wherein a calcium hydroxide is formed in said at least one
slaker by the reaction of water with at least one of calcium and calcium oxide, wherein
a metal hypohalite is formed in said at least one bleach unit by reacting a halide acid
from at least one of said at least one HAR and said at least one EU with a metal
hydroxide from at least one of said at least one EU and said at least one separator,
and wherein a halide acid and a metal sulfoxy salt is formed in said at least one HAR
from the reaction of a metal halide salt with a sulfoxy acid formed in said at least one
SAR. It is preferred that metal comprise a group IA or group IIA metal. It is most
preferred that said metal comprise sodium. It is most preferred that said halogen
comprise chlorine.
It is a preferred embodiment to form a process flow path, wherein at least one
unit performs ASP, thereby producing O2 and N2, wherein said ASP is powered by
electricity and/or torque, wherein said electricity and/or torque is produced from
steam, and wherein said steam is converted heat energy from at least a portion of the
energy of formation of at least one selected from a list comprising: SO2 from S and
air, SO2 from S and O2, SO3 from SO2 and air, SO3 from SO2 and O2, said H2SO3 from
SO2 and H2O; said H2SO4 from SO3 and H2O; oleum from H2SO4 and SO3, said H2SO4
from oleum and H2O, and any combination therein.
It is a preferred embodiment that at least one SAR, at least one HAR, at least
one gypsum unit, at least one slaker, at least one separator, at least one dryer, and at

least one bleach unit, form a process flow path, wherein said at least one separator is
downstream of said at least one gypsum unit, wherein said at least one slaker is
upstream of said at least one gypsum unit, wherein said at least one dryer is
downstream of said at least one separator, wherein said separator is upstream said at
least one bleach unit, wherein said at least one bleach unit is downstream of said at
least one HAR and downstream of said at least one separator, wherein said at least
one HAR is downstream of said at least one SAR, wherein said at least one SAR
produces energy to be used in the generation of electricity for said at least one EU,
wherein the electricity for electrolysis in said EU(s) is obtained from a generator driven
by a steam turbine, wherein the steam used to turn said steam turbine to create said
electricity is obtained from heat transfer from at least a portion of the energy of
formation of at least one selected from a list comprising: SO2 from S and air, SO2 from
S and O2, SO3 from SO2 and air, SO3 from SO2 and O2, said H2SO3 from SO2 and H2O;
said H2SO4 from SO3 and H2O; oleum from H2SO4 and SO3, said H2SO4 from oleum and
H2O, and any combination therein, wherein a mixture of a calcium sulfoxy salt and said
metal hydroxide is formed in said at least one gypsum unit by reacting a metal sulfoxy
salt from said at least one HAR, wherein a dry product comprising an anhydrous
calcium sulfoxy salt or a hydrated calcium sulfoxy salt is obtained from said at least
one dryer by drying a calcium sulfoxy salt formed in said at least one gypsum unit,
wherein a calcium hydroxide is formed in said at least one slaker by the reaction of
water with at least one of calcium and calcium oxide, wherein a metal hypohalite is
formed in said at least one bleach unit by reacting a halide acid from said at least one
HAR with a metal hydroxide from said at least one separator, and wherein a halide
acid and a metal sulfoxy salt is formed in said at least one HAR from the reaction of a
metal halide salt with a sulfoxy acid formed in said at least one SAR. It is preferred
that metal comprise a group IA or group IIA metal. It is most preferred that said
metal comprise sodium. It is most preferred that said halogen comprise chlorine.
It is a preferred embodiment that at least one gypsum unit, at least one slaker,
at least one separator, and at least one dryer, form a process flow path, wherein said
at least one separator is downstream of said at least one gypsum unit, wherein said at
least one slaker is upstream of said at least one gypsum unit, wherein said at least one
dryer is downstream of said at least one separator, wherein a mixture of a calcium

sulfoxy salt and said metal hydroxide is formed in said at least one gypsum unit by
reacting a metal sulfoxy salt with a calcium hydroxide, wherein a dry product
comprising an anhydrous calcium sulfoxy salt or a hydrated calcium sulfoxy salt is
obtained from said at least one dryer by drying a calcium sulfoxy salt formed in said at
least one gypsum unit, wherein a calcium hydroxide is formed in said at least one
slaker by the reaction of water with at least one of calcium and calcium oxide. It is
preferred that metal comprise a group IA or group IIA metal. It is most preferred that
said metal comprise sodium. It is most preferred that said halogen comprise chlorine.
It is a preferred embodiment to form a process flow path, wherein at least one
unit performs electrolysis, thereby producing O2 and H2 from H2O, wherein said
electrolysis is powered by electricity, wherein at least a portion of said electricity is
produced in a generator turned by a steam turbine, and wherein said steam turbine is
at least partially turned by converted energy from at least a portion of the energy of
formation of at least one selected from a list comprising: SO2 from S and air, SO2 from
S and O2, SO3 from SO2 and air, SO3 from SO2 and O2, said H2SO3 from SO2 and H2O;
said H2SO4 from SO3 and H2O; oleum from H2SO4 and SO3, said H2SO4 from oleum and
H2O, and any combination therein.
It is a preferred embodiment to form a process flow path, wherein at least
one unit electrolyzes O2 to O3, and wherein said O2 is obtained from electrolysis of
H2O, thereby producing O2 and H2, wherein at least a portion of the electricity for
said electrolysis is created in a generator driven by a steam turbine, wherein said
steam turbine is at least partially turned by steam obtained from at least a potion
of the energy of formation of at least one selected from a list comprising: SO2
from S and air, SO2 from S and O2, SO3 from SO2 and air, SO3 from SO2 and O2,
said H2SO3 from SO2 and H2O; said H2SO4 from SO3 and H2O; oleum from H2SO4
and SO3, said H2SO4 from oleum and H2O, and any combination therein.
It is a preferred embodiment to form a process flow path, wherein at least
one ASP separates O2 from air, wherein said at least one ASP is powered by at least
one of a steam engine powered by steam and an electric motor powered by
electricity, wherein said O3 is obtained from electrolysis of O2, wherein at least a
portion of the electricity for said electrolysis is produced from a generator turned by
a steam turbine, and wherein steam to power said steam engine and said steam

turbine is at least partially obtained from at least a portion of the energy of
formation of at least one selected from a list comprising: SO2 from S and air, SO2
from S and O2, SO3 from SO2 and air, SO3 from SO2 and O2, said H2SO3 from SO2
and H2O; said H2SO4 from SO3 and H2O; oleum from H2SO4 and SO3, said H2SO4
from oleum and H2O, and any combination therein.
It is a preferred embodiment to form a process flow path, wherein at least
one unit electrolyzes H2O2 from H2SO4 via H2S2O8 and H2O, wherein the electricity for
said electrolysis is created in a generator driven by a steam turbine, wherein said
steam turbine is turned by steam obtained from at least a portion of the energy of
formation of at least one selected from a list comprising: SO2 from S and air, SO2
from S and O2, SO3 from SO2 and air, SO3 from SO2 and O2, said H2SO3 from SO2 and
H2O; said H2SO4 from SO3 and H2O; oleum from H2SO4 and SO3, said H2SO4 from
oleum and H2O, and any combination therein.
It is a preferred embodiment to form a process flow path, wherein at least one
unit recycles at least a portion of the H2 byproduct from electrolysis as an energy
source to make electricity, wherein said electricity is generated in at least one of a
combustion engine and a fuel cell. It is a preferred embodiment to utilize at least a
portion of said electricity in the EU to manufacture at least one disinfectant and/or
oxidant. It is preferred to convert steam energy into electricity with a steam turbine,
as is known in the art.
It is a preferred embodiment to form a process flow path, wherein at least one
unit recycles at least a portion of the H2 byproduct from electrolysis as an energy
source to heat the reaction of said metal halide salt with said sulfoxy acid.
It is a preferred embodiment that at least one MPR, one MAS sulfoxy acid
from said SACP is transferred to said HAR, wherein said sulfoxy acid heat energy
and/or temperature is as near that of the temperature in said SAP as is practical, so
that said heat energy within said sulfoxy acid is available to said HAR.
Materials of Construction
It is an embodiment that all materials of construction in the instant invention be
those as are known in the art of each chemistry processed. It is preferred that
materials which contact said sulfoxy acid be at least one selected from a list consisting

of: carbon steel, Hastelloy, Inconel®, Incoloy®, titanium, zirconium, ceramic, plastic
and any combination therein. It is preferred that materials which contact said halide
acid be at least one selected from a list consisting of: Hastelloy, Inconel®, Incoloy®,
titanium, zirconium, ceramic, plastic, and any combination therein, wherein Hastelloy
C, zirconium and PVC are most preferred. It is preferred that materials which contact
hot water be at least one selected from a list consisting of: Hastelloy, inconel,
titanium, zirconium, ceramic, stainless steel and plastic.
Testing
Bench scale tests reacting ACS in solution with aluminum hydroxide at a
temperature of 110 - 140 °C (230 - 284 °F) for 1.5 to 5 hours, whereby the reaction
of AlxCIY(OH)z is formed have been performed. The formation of ACS from aluminum
metal was performed in one case and aluminum hydroxide was performed in the
second case. In both cases, HCI was formed by the reaction of chlorine gas into
water, where the water solution was heated continuously to 60 °C (140 °F) for 15
minutes to assure complete chloride formation. In the third test, a portion of the
aluminum hydroxide was replaced with MgO forming AlxMgwCIY(OH)z. In a fourth test,
a portion of the ACS was replaced with MgCfe again forming AIXCIY(OH)Z. In a fifth
test, a portion of the aluminum hydroxide was replaced with lime, CaO, forming
AlxCawCly(OH)z. In a sixth test, sulfuric acid was added to the ACS forming
AlxMgwClY(OH)z(SO4)v. In a seventh and poor-performing test, a portion of the ACS
was replaced with ferric chloride. In an eighth test, a portion of the aluminum was
replaced with copper forming AIXCUWCIY(OH)Z; this rather green product revealed a
shelf life of over 2.5 years before forming a precipitate. In test nine, the ACS was
replaced with a waste catalyst stream form Dow Chemical containing ACS. Test ten
was a field coagulation test of the final MP made in Example "8." In an eleventh test,
an MAS was prepared by dissolving CuCl3 in water, which was then reacted with MgO.
In all cases, the relationship OH:AI or OH:metal in the resulting compound became 0.5
to 1.5; where, this relationship is preferably greater than 1.2. In all cases the pH of
the final solution was between 4.0 and 5.0. In all cases, improved results were
obtained with high-shear mixing as compared to low. It was found that at high shear

mixing energies, a greater proportion of the aluminum went into the MP and the
tendency to form a gelatinous precipitate was reduced.
In test twelve, salts were reacted with concentrated sulfuric acid. While
ammonium is not a metal, a test was performed with ammonium chloride since the
ammonium cation has "metal-like" qualities in salt formation. Even though the
ammonium cation is not the most practical "metal-like" cation, given the results, the
term "metal" in metal halides is to include "metal-like" moieties, preferably the
ammonium cation. The test results are reviewed below:
EXAMPLE 1
Chlorine gas is slowly bubbled into a 1-L beaker until the Sg of the aqueous
solution is approximately 1.08 to 1.1. The acidic solution is continuously stirred and
heated to 60 °C for 15 minutes; after which, 50 grams of aluminum metal are
dissolved into solution while slowly stirring for 15 minutes to prepare the ACS. 300 ml
of this ACS having an aluminum content of approximately 5 % is then heated to 120
°C and stirred vigorously while slowly adding 30 gm of AI(OH)3 powder. The system is
kept at 120 °C and stirred vigorously for 3 hours, after which all of the powder is noted
to have gone into solution. The liquid was allowed to cool. The final product was a
cloudy liquid having an aluminum content of approximately 10 %.
EXAMPLE 2
Chlorine gas is slowly bubbled into a 1-L beaker until the Sg of the aqueous
solution is approximately 1.08 to 1.1. The acidic solution is continuously stirred and
heated to 60 °C for 15 minutes; after which 100 grams of AI(OH)3 powder is
dissolved into solution while slowly stirring for 165 minutes to prepare the ACS.
300 ml of this ACS having an aluminum content of approximately 5 percent is then
heated to 130 °C and stirred vigorously while slowly adding 30 gm of AI(OH)3
powder. The system is kept at 130 °C and stirred vigorously for 3 hours, after
which all of the powder is noted to have gone into solution. The liquid was allowed
to cool. The final product was a cloudy liquid having an aluminum content of
approximately 10 percent.

EXAMPLE 3
An ACS from Gulbrandsen Technologies, GC 2200, was utilized for the ACS.
This sample of GC 2200 measured 10.1 percent AI2O3 having a Sg of 1.28 and due
to the yellow color contained iron. To an autoclave, provided with a stirrer, 300 ml
of the ACS were added along with 5 gm of MgO from Premiere Services and 25 gm
of laboratory grade Al(OH)3 powder. The mixture was heated to 120 °C and stirred
vigorously for five hours. The liquid was allowed to cool. The final product was
clear having an aluminum content of approximately 6 percent and a magnesium
content of approximately 2 percent.
EXAMPLE 4
An ACS from Gulbrandsen Technologies, GC 2200, was utilized for the ACS.
This sample of GC 2200 measured 10.1 percent Al2O3 having a Sg of 1.28 and due to
the yellow color contained iron. To a 2-L beaker, 300 ml of the ACS were added along
with 10 gm of MgCI2 X 6 H2O crystals and 25 gm of laboratory grade AI(OH)3 powder.
The mixture was heated to 110 °C and stirred vigorously for four hours. The liquid was
allowed to cool. The final product was clear having an aluminum content of
approximately 10 percent and a magnesium content of approximately 2 percent.
EXAMPLE 5
An ACS from Gulbrandsen Technologies, GC 2200, was utilized for the ACS.
This sample of GC 2200 measured 10.1 percent AI2O3 having a Sg of 1.28 and due to
the yellow color contained iron. To an autoclave, 300 ml of the ACS were added
along with 10 gm of CaO and 20 gm of laboratory grade AI(OH)3 powder. The
mixture was heated to 100 °C and stirred vigorously for four hours. The liquid was
allowed to cool. The final product was cloudy having an aluminum content of
approximately 7 percent and a calcium content of approximately 3 percent.

EXAMPLE 6
An ACS from Gulbrandsen Technologies, GC 2200, was utilized for the ACS.
This sample of GC 2200 measured 10.1 percent AI2O3 having a Sg of 1.28 and due to
the yellow color contained iron. To an autoclave, 300 ml of the ACS were added
along with 10 ml of concentrated sulfuric acid and 10 gm of laboratory grade Al(OH)3
powder. The mixture was heated to 140 °C and 25 psig stirring vigorously for four
hours. The liquid was allowed to cool. The final product was clear having an
aluminum content of approximately 6 percent.
EXAMPLE 7
An ACS from Gulbrandsen Technologies, GC 2200, was utilized for the ACS.
This sample of GC 2200 measured 10.1 percent Al2O3 having a Sg of 1.28 and due to
the yellow color contained iron. To an autoclave, 300 ml of the ACS were added
along with 30 gm of alum and 10 gm of laboratory grade AI(OH)3 powder. The
mixture was heated to 140 °C and 25 psig and turned gelatinous.
EXAMPLE 8
An ACS from Gulbrandsen Technologies, GC 2200, was utilized for the ACS.
This sample of GC 2200 measured 10.1 percent AI2O3 having a Sg of 1.28 and due
to the yellow color contained iron. To a 2-L beaker, 300 ml of the ACS were
added along with 10 gm of CuCI2 X 6 H2O crystals and 25 gm of laboratory grade
AI(OH)3 powder. The mixture was heated to 100 °C and stirred vigorously for four
hours. The liquid was allowed to cool. The final product was clear with a
greenish tint having an aluminum content of approximately 8 percent and a
copper content of approximately 2 percent.
EXAMPLE 9
A waste catalyst from Dow Chemical (Freeport, Texas) containing ACS was
utilized for the ACS. The sample measured 18 percent AI2O3 having a Sg of 1.3;
due to the greenish color the sample had a small amount of organic
contamination. To a 2-L beaker, 300 ml of the ACS were added along with 35 gm

of laboratory grade AI(OH)3 powder. The mixture was heated to 105 °C and
stirred vigorously for four hours. The liquid was allowed to cool. The final
product was clear with a greenish tint having an aluminum content of
approximately 10 percent.
EXAMPLE 10
At the time of this test, the city of Marshall, Texas was in drinking water
production using CV 1703 as the coagulant. (CV is a registered trademark of
ClearValue.) CV 1703 is a blend that is by volume: 38% CV 1120, 42% CV 1130,
8% CV 3210 and 12% CV 3650. CV 1120 is an ACH measuring 23% Al2O3 at 84%
basicity, CV 1130 is an ACS that measures 10% Al2O3, CV 3210 is a 50% active Epi-
DMA solution that measures 100 +/- 20 cps, and CV 3650 is a 20% active diallyl
dimethyl ammonium chloride polymer that measures 2000 +/- 200 cps. Prior to
using CV 1703, Marshall utilized CV 3650 in concert with alum. Alum was, at that
previous time, used at 30 to 35 ppm along with CV 3650 at 1.5 ppm.
Marshall's raw water quality makes water purification difficult:
- The raw alkalinity is less than 20 ppm and often as low as 6 ppm,
- The raw turbidity is normally 2 to 7 NTU and infrequently 10 to 15 NTU,
- The raw color varies from 20 to 400 Apparent Color Units (ACU), and
- The raw TOC ranges form 5 to 20 ppm; and UV absorbance 0.2 to 0.7 m-1.
Prior to the use of CV 3650 with alum, Marshall operated with just alum
and often went out of US EPA and Texas State permit having a final water
turbidity of greater than 0.5 NTU; on Alum operation, Marshall frequently
measured in excess of 0.20 mg/L of aluminum in the final drinking water. While
CV 3650 significantly improved alum operations, water color values of over 200
ACU often required the use of CV 1703.
Prior to using CV 1703, Marshall produced filtered water at a turbidity of
near 0.15 to 0.30 NTU under normal operating conditions and higher when the
raw water color was a challenge. During operation with CV 1703, Marshall has
had the ability to keep the filtered water turbidity under 0.08 NTU under all
operating conditions with the settled water turbidity varying from 0.4 to 0.7 NTU.

Per US EPA guidelines, Marshall must remove, at times, 45% of the raw water
TOC and, at times, 50% of the raw water TOC. During the year 2000, when the
raw water had a lower organic content and nearly all of the raw TOC measured
DOC per the standard industry test, Marshall was frequently unable to obtain 45%
TOC removal. Operation during this time did not produce any final filtered water
that had an aluminum concentration of over 0.20 mg/L.
On 12/15/99, the MP made in Example 8 was jar-tested in comparison to CV
1120 and CV 1703. On that day the raw color measured 55, NTU measured 4.1 and
UV measured 0.185 m-1. At 15 ppm, CV 1703 obtained a settled turbidity of 0.96
NTU, 14 ACU and 0.071 m-1. At 15 ppm, the MP from Example 8 obtained a settled
turbidity of 0.69 NTU, 11 ACU and 0.074 m-1.
EXAMPLE 11
To a 2-L beaker, 250 ml of water was added prior to 50 gm of CuCl2 X 6 H2O
crystals; the solution was pH adjusted to 1.0 with HCI. The resulting solution was then
mixed with 30 gm of MgO powder. The mixture was heated to 100 °C and stirred
vigorously for four hours. The liquid was allowed to cool. The final product was clear
with a greenish tint having a copper content of approximately 5 percent and a
magnesium content of approximately 5 percent.
EXAMPLE 12
Five salt compositions are reacted with concentrated sulfuric acid to test the
efficacy of halide acid formation and sulfate/bisulfite formation.
In the first test, 4 gm of normal table salt (sodium chloride) is placed in a
beaker containing 2 g of concentrated sulfuric acid. In this test a rather violent
reaction takes place, wherein HCI gas is obviously released due to the tell tale
chlorine odor; in the bottom of the beaker a solid precipitate forms which is
obviously sodium bisulfate.
In the second test, 4 gm of ammonium chloride is placed into a beaker
containing 2 gm of concentrated sulfuric acid. In this test a rather violent reaction
takes place, wherein HCI gas is obviously released due to the tell tale chlorine odor;

in the bottom of the beaker a solid precipitate forms which is obviously the
ammonium sulfate salt-
In the third test, 4 gm of CuCI3 X 6 H2O crystals are placed into a beaker
containing 2 gm of concentrated sulfuric acid. In this test an aggressive reaction takes
place, wherein HCI gas is obviously released due to the tell tale chlorine odor; in the
bottom of the beaker a solid precipitate forms which is obviously copper sulfate.
In the fourth test, 4 gm of AICI3 X 6 H2O crystals are placed into a beaker
containing 2 gm of concentrated sulfuric acid. In this test an aggressive reaction takes
place, wherein HCI gas is obviously released due to the tell tale chlorine odor; in the
bottom of the beaker a solid precipitate forms which is obviously aluminum sulfate.
In the fifth test, 4 gm of MgCI3 X 6 H2O crystals are placed into a beaker
containing 2 gm of concentrated sulfuric acid. In this test an aggressive reaction takes
place, wherein HCI gas is obviously released due to the tell tale chlorine odor; in the
bottom of the beaker a solid precipitate forms which is obviously magnesium sulfate.
Certain objects are set forth above and made apparent from the foregoing
description. However, since certain changes may be made in the above description
without departing from the scope of the invention, it is intended that all matters
contained in the foregoing description shall be interpreted as illustrative only of the
principles of the invention and not in a limiting sense. With respect to the above
description, it is to be realized that any descriptions, drawings and examples
deemed readily apparent and obvious to one of skill in the art and all equivalent
relationships to those described in the specification are intended to be
encompassed by the instant invention.
Further, since numerous modifications and changes will readily occur to those
skilled in the art, it is not desired to limit the invention to the exact construction and
operation shown and described, and accordingly, all suitable modifications and
equivalents may be resorted to, falling within the scope of the invention. It is also to
be understood that the following claims are intended to cover all of the generic and
specific features of the invention herein described, and all statements of the scope of
the invention, which, as a matter of language, might be said to fall in between.

WE CLAIM:
1. A method for the preparation of a polynucleate metal compound, comprising at
least one metal in the +2 or the +3 valence state, wherein
said polynucleate metal compound is formed by the aqueous reaction of a
metal halide solution with at least one metal, wherein
said metal halide solution comprises at least one metal in the +2 or +3 valence
state, wherein
said at least one metal is in the 0, +2 or +3 valence state, and if in the 0 valence

state is capable of entering the +2 or +3 valence state, wherein
said metal halide solution is formed by the aqueous reaction between said
metal(s) within said metal halide solution and a halide acid, and wherein
said halide acid is formed by the reaction of a metal halide salt, comprising the
corresponding halide of said halide acid, with a sulfoxy acid.
2. The method as claimed in claim 1, wherein at least one of:
said metal in said metal halide solution is aluminum and said at least one metal
is aluminum,
said metal in said metal halide solution is aluminum and said at least one metal
is at least one metal other than aluminum,
said metal in said metal halide solution is a metal other than aluminum and said
at least one metal is aluminum, and
said metal in said metal halide solution and said at least one metal is-a metal
other than aluminum.
3. The method as claimed in claim 1, wherein the same vessel,
a) an aqueous solution of said halide acid is formed from the reaction of said
halide acid in water,
b) said metal halide solution is formed by the reaction of said metal(s) in said
halide acid, and
c) said polynucleate metal compound is formed by the reaction of said at least
one metal(s) in said metal halide solution.

4. The method as claimed in claim 1, wherein said at least one metal comprises at
least one metal selected from a list consisting of: aluminum, calcium, magnesium, zirconium,
copper, tin, gold, silver, and any combination therein.]'
5. The method as claimed in claim 1, wherein said at least one metal is in a form
selected from a list consisting of: base metal, oxide, hydroxide, carbonate and any
combination therein.
6. The method as claimed in claim 1, wherein said halide in said polynucleate
metal compound comprises at least one of: chlorine and bromine.
7. The method as claimed in claim 1, wherein said polynucleate metal compound
further comprises at least one selected from a list consisting of: sulfate, phosphate, carbonate,
silicate, nitrate and any combination therein.
8. The method as claimed in claim 1, wherein the metal(s) in said metal halide
solution or said at least one metal comprise at least one selected from a group consisting of:
ammonium, a Group IA metal, a Group IIA metal, a Group IIIB metal, a Group VIII metal, a
Group 1B metal, a Group IIB metal, a Group IIIA metal, sodium, calcium, potassium,
magnesium, aluminum, copper and any combination therein.
9. The method as claimed in claim 1, wherein said metal halide solution
comprises a waste catalyst or waste brine.
10. The method as claimed in claim 1, wherein said sulfoxy acid comprises H2SO4.
11. The method as claimed in claim 1, wherein said aqueous reaction is performed
with high shear.
12. The method as claimed in claim 1, wherein the metal in said metal halide salt
comprises a group IA or IIA metal.

13. The method as claimed in claim 1, wherein the metal in said metal halide salt
comprises sodium.
14. The method as claimed in claim 1, wherein there is no vehicular transportation
of at least one selected from list consisting of said: halide acid, metal halide solution, sulfoxy
acid, and any combination therein.
15. The method as claimed in claim 1, wherein said aqueous reaction is performed
in at least one selected from a list consisting of a: a batch stirred tank reactor, a continuous
stirred tank reactor, a plug flow reactor, and any combination therein.
16. The method as claimed in claim 1, wherein said sulfoxy acid is formed by the
sulfuric acid contact process.
17. The method as claimed in claim 1, wherein said reaction of a metal halide salt
with a sulfoxy acid produces a metal sulfoxy salt comprising a moiety of at least one selected
from a list consisting of: sulfate, bisulfate, sulfite, bisulfite and any combination therein.
18. The method as claimed in claim 17, comprising reacting said metal sulfoxy salt
with calcium hydroxide in aqueous solution, wherein
said metal in said metal sulfoxy salt comprises a group IA or group IIA metal, wherein
a mixture is produced comprising said metal, water, a hydroxide and a solid, and
wherein
said solid comprises at least one selected from a of list consisting of: calcium sulfate,
calcium sulfate ½ hydrate, calcium sulfate di-hydrate, calcium sulfite, calcium hydrogen
sulfite, calcium sulfite di-hydrate and any combination therein.
19. The method as claimed in claim 18, wherein said calcium hydroxide is formed
by reacting with water at least one of: calcium and calcium oxide.

20. The method as claimed in claim 18, wherein the energy from at least one
selected from a list consisting of: an SAR or SCAP; sulfoxy salt formation; calcium
hydroxide formation; an electrolysis unit; formation of a calcium sulfoxy salt; pH adjustment;
halogen dioxide formation; metal halate formation; metal halide acid formation, halide acid
formation, and any combination therein
is used to heat water and/or steam.
21. The method as claimed in claim 20, wherein
said heated water and/or steam is at least partially used to heat at least one
selected from a list consisting of:
said aqueous reaction,
the reaction of a metal hydroxide with a halide acid to form a metal hypohalite,
heating and/or drying of a calcium sulfoxy salt,
heating and/or drying of a metal sulfoxy salt, and
any combination therein.
22. The method as claimed in claim 18, comprising a separation of said aqueous
solution from said solid, such that
an aqueous solution is obtained comprising said group IA or group IIA metal
hydroxide, and
a moist solid phase is obtained comprising said solid, said group IA or group
IIA metal hydroxide and water.
23. The method as claimed in claim 22, comprising water dilution of said moist
solid phase thereby creating a mixture comprising group IA or group IIA metal hydroxide,
water, and a solid, wherein
said solid comprises at least one selected from a of list consisting of: calcium
sulfate, calcium sulfate ½ hydrate, calcium sulfate di-hydrate, calcium sulfite, calcium
hydrogen sulfite, calcium sulfite di-hydrate and any combination therein, wherein

the concentration of said group IA or group IIA metal hydroxide in said
mixture is less than previous, and wherein
said aqueous solution is separated from said solid, such that
an aqueous solution is obtained comprising said group IA or group IIA metal hydroxide, and
a moist solid phase is obtained comprising said solid, said group IA or group
IIA metal hydroxide and water.
24. The method as claimed in claim 23, performed a number of times, such that
the concentration is lowered of said group IA or group IIA metal hydroxide in
aqueous solution, and
a final moist solid phase is crated.
25. The method as claimed in claims 22, 23 or 24, wherein said separation is
enhanced by vibration of said mixture.

26. The method as claimed in claims 22, 23 or 24, wherein at least a portion of said
aqueous group IA or group IIA metal hydroxide solution is reacted with a halide acid to form
a group IA or group IIA metal hypohalite solution, and wherein
said group IA or group IIA metal hypohalite solution formation comprises at
least one selected from a list consisting of: continuous stirred tank reaction, batch stirred tank
reaction, plug flow reaction and any combination therein.
27. The method as claimed in claim 24, comprising pH adjustment of said final
moist solid phase with a sulfoxy acid.
28. The method as claimed in claims 24 or 27, comprising drying of said final
moist solid phase.
29. The method as claimed in claim 1, wherein said polynucleate metal compound
comprises the SOx moiety from the addition of a sulfoxy acid to said aqueous reaction of a
metal halide solution with at least one metal.

30. The method as claimed in claim 29, wherein said aqueous reaction is
performed with high shear.
31. The method as claimed in claim 1, comprising the creation of steam from the
formation of at least one selected from a list consisting of: SO2 from S and air, SO2 from S
and O2, SO3 from SO2 and air, SO3 from SO2 and O2, said H2 SO3 from SO2 and H2O; said
H2SO4 from SO3 and H2O; oleum from H2SO4 and SO3, said H2SO4 from oleum and H2O, and
any combination therein.
32. The method as claimed in claim 31, wherein said steam is at least partially used
to power an air separation process, and wherein
said air separation process provides at least one of O2 and N2.
33. The method as claimed in claim 31, wherein said SO2 is reacted with at least
one selected from a list consisting of:
a metal hydroxide to form a metal sulfite,
a metal carbonate to form a metal bi-sulfite,
a metal halate and H2SO4 to form the corresponding halogen dioxide, and
any combination therein.
34. The method as claimed in claim 33, wherein at least a portion of said steam is
at least partially used to perform at least one selected from a list consisting of: refine bauxite
to alumina, heat said aqueous reaction of a metal halide solution with at least one metal,
evaporate H2O from a metal sulfoxy salt, degrade a halite to a halide, heat S, turn a steam
turbine which turns a generator to create electricity, heat the reaction of a metal hydroxide and
a halide acid to form a metal hypohalite, and any combination therein.
35. The method as claimed in claim 34, wherein said electricity is at least partially
used to power an air separation process, and wherein
said air separation process produces at least one of O2 and N2.

36. The method as claimed in claim 34, wherein said electricity is at least partially
used in an electrolysis unit to form at least one selected from a list consisting of: O2 from
H2O, O3 from O2, H2 from H2O, H2S2O8 from H2SO4 in the production of H2O2, a metal

hypohalite from a metal halide solution, a metal halate from a metal halide salt, a metal
hydroxide and a halide acid from a metal halide salt, and any combination therein.
37. The method as claimed in claim 36, wherein the metal(s) in said metal halide
salt comprises at least one selected from a list consisting of: ammonium, a Group IA metal, a
Group IIA metal, a Group IIIB metal, a Group VIII metal, a Group 1B metal, a Group IIB
metal, a Group IIIA metal, sodium, calcium, potassium, magnesium, aluminum, copper and
any combination therein.
38. The method as claimed in claim 36, wherein said the halogen of said halide,
hypohalite, halite or halate comprises chlorine or bromine.
39. The method as claimed in claim 36, wherein said metal halide solution
comprises a waste catalyst or waste brine.
40. The method as claimed in claim 36, wherein at least a portion of said halide
acid is used to form at least one selected from a list consisting of the corresponding:
hypohalite, halite, halate, available oxide form of said halide, said halide in the form of a
dioxide, and any combination therein.
41. The method as claimed in claim 36, comprising the formation of an available
oxide form of a halogen, including a halogen dioxide, wherein
said formation is performed with at least one selected from a list consisting of
said corresponding: halide, hypohalite, halide acid, halite, halate and any combination therein,
wherein
at least one of said halide acid, hypohalite, halide acid, halite and halate is
formed in said EU.

42. The method as claimed in claim 36, wherein said H2 is at least partially used in
at one least selected from a list consisting of:
an engine to turn a generator to generate electricity,-
a fuel cell to generate electricity, and
heating the reaction between a metal halide salt with, a sulfoxy acid.
43. The method as claimed in claim 42, wherein said electricity is at least partially
used in said electrolysis unit
44. A manufacturing apparatus for - producing a polynucleate metal compound, said
manufacturing apparatus comprising;
one or more units defining a process flow path, wherein .
at least one or more units form said polynucleate metal compound from the
aqueous reaction of a metal halide solution with at least one metal wherein
said metal halide solution comprises' at least one metal in the +2 or +3 valence
state, wherein
said at least one metal comprises a metal(s) in the 0, +2 or +3 valence state,
and if in the 0 valence state capable of entering the +2 or +3 valence state, wherein
one or more units form said metal halide solution by reacting the metal(s) of
said metal halide solution with a halide acid, wherein
said halide acid formation comprises the reaction of a metal halide salt,
comprising the corresponding halide of said halide acid, wherein
said one or more units which form said halide acid by reacting a metal halide
salt, comprising the corresponding halide of said halide acid, with a sulfoxy acid, are
upstream of

one or more units form said metal halide solution by reacting the metal(s) or
said metal halide solution with a halide acid, as well as upstream of
said one or more units forming said metal halide solution by reacting the
metal(s) of said metal halide solution with a halide acid.
45 . The apparatus as claimed in claim 44, wherein at least one of:
said metal in said metal halide- solution is aluminum and said at least one metal
is aluminum,
said metal in said metal halide solution is aluminum and said at least one metal
is at least one metal other than aluminum,
said metal in said metal halide solution is a metal other than aluminum and said
at least one metal is aluminum, and
said metal in said metal halide solution and said at least one metal is a metal
other than aluminum.
46. The apparatus as claimed in claim 44, wherein said at least one or
more units forming said polynucleate metal compound from the aqueous reaction of a metal
halide solution with at least one metal, and
said one or more units which form said metal halide solution by reacting the
metal(s) of said metal halide solution with a halide acid,
comprise the same one or more units.
47. The apparatus as claimed in claim 44, wherein said metal in said
metal halide solution or said at least one metal comprises at least one metal selected from a
list consisting of: aluminum, calcium, magnesium, zirconium, copper, tin, gold, silver,
and any combination therein.

48. The apparatus as claimed in claim 44, wherein said at least one
metal is in a form selected from a list consisting of: base metal, oxide, hydroxide, carbonate
and any combination therein.



49. The apparatus as claimed in claim 44, wherein said halide
comprises at least one of chlorine and bromine.
50. The apparatus as claimed in claim 44, wherein said polynucleate
metal compound further comprises at least one selected from a list consisting of: sulfate,
phosphate, carbonate, silicate, nitrate and any combination therein.
51. The apparatus as claimed in claim 44, wherein the metal(s) in said
metal halide solution or said at least one metal comprise at least one selected from a group
consisting of: ammonium, a Group IA metal, a Group IIA metal, a Group IIIB metal, a Group
VIII metal, a Group 1B metal, a Group IIB metal, a Group IIIA metal, sodium, calcium,
potassium, magnesium, aluminum, copper and any combination therein.
52. The apparatus as claimed in claim 44, wherein said metal halide
solution comprises a waste catalyst or waste brine.
53. The apparatus as claimed in claim 44, wherein said sulfoxy acid
comprises. H2SO4.
54. The apparatus as claimed in claim 44, wherein said aqueous
reaction of a metal halide solution with at least one metal is performed with high shear.
55. The apparatus as claimed in claim 44, wherein the metal in said
metal halide salt comprises a group IA or IIA metal.
56. The apparatus as claimed in claim 44, wherein the metal in said
metal halide salt comprises sodium.

57. The apparatus as claimed in claim 44, wherein there is no vehicular
transportation of at least one selected from a group consisting of said: halide acid, metal
halide solution, sulfoxy acid, and any combination therein.
58. The apparatus as claimed in claim 44, wherein said aqueous
reaction of a metal halide solution with at least one metal is performed in a unit comprising at
least one selected from a consisting of a: batch stirred tank reactor, continuous stirred tank
reactor, plug flow reactor, and any combination therein.
59. The apparatus as claimed in claim 44, wherein said sulfoxy acid is
formed by a unit comprising the sulfuric acid contact process.
60. The The apparatus as claimed in claim 44, wherein said reaction of a
metal halide salt with a sulfoxy acid produces a metal sulfoxy salt comprising at least one
selected from a list consisting of: sulfate, bisulfate, sulfite, bisulfite and any combination
therein.
61. The apparatus as claimed in claim 60, comprising at least one unit
reacting said metal sulfoxy salt with calcium hydroxide in aqueous solution is downstream of
said one or more units reacting a metal halide salt, comprising the corresponding halide of
said halide acid, with a sulfoxy acid, wherein
said metal in said metal sulfoxy salt is a group IA or group IIA metal, wherein
a mixture is produced in said at least one unit reacting said group IA or group -
IIA metal sulfoxy salt with calcium hydroxide in aqueous solution,
said mixture comprises group IA or group IIA metal hydroxide, water, and a
solid, wherein
said solid comprises at least one selected from a of list consisting of: calcium
sulfate, calcium sulfate ½ hydrate, calcium sulfate di-hydrate, calcium sulfite, calcium
hydrogen sulfite, calcium sulfite di-hydrate and any combination therein.

62 . The apparatus as claimed in claim 61, wherein said calcium
hydroxide is formed in a unit reacting with water at least one of: calcium and calcium oxide,
and wherein said unit reacting with water at least one of: calcium and calcium oxide is
upstream of
said at least one unit reacting said group IA or group IIA metal sulfoxy salt
with calcium hydroxide in aqueous solution.
63.The apparatus as claimed in claim 61, wherein the energy from the
formation of at least one selected from a list consisting of said:
mixture, metal sulfoxy salt, metal halide solution, halide acid, sulfoxy acid,
calcium hydroxide, and any combination therein
is transferred to water and/or steam via equipment performing heat transfer
thereby providing to said water and/or steam a higher temperature or energy.
64. The apparatus as claimed in claim 62, wherein
said water and/or steam energy is at least partially transferred via equipment
performing heat transfer to at least one selected from a list consisting of:
said aqueous reaction of a metal halide solution with at least one metal,
a unit reacting a metal hydroxide with a halide acid to form a metal hypohalite,
a unit performing heating and/or drying of a solid, and
any combination therein.
65. The apparatus as claimed in claim 61, comprising at least one unit
separating said aqueous solution from said solid, such that
an aqueous solution is obtained comprising said group IA or group IIA metal
hydroxide, and
a moist solid phase is obtained comprising said solid, said group IA or group DA metal
hydroxide and water, wherein
said unit separating said aqueous solution from said solid is downstream of said at
least one unit reacting said group IA or group IIA metal sulfoxy salt with calcium hydroxide
in aqueous solution.

66. The apparatus as claimed in claim 65, comprising a unit adding
water to said moist solid phase thereby creating a mixture comprising said group IA or group
IIA metal hydroxide, water, and a solid, wherein
said unit adding water to said moist solid phase is downstream of said at least
one unit separating said aqueous solution from said solid, and wherein
said solid comprises at least one selected from a of list consisting of: calcium
sulfate, calcium sulfate ½ hydrate, calcium sulfate di-hydrate, calcium sulfite, calcium
hydrogen sulfite, calcium sulfite di-hydrate and any combination therein, wherein
said aqueous solution is separated from said solid, such that
an aqueous solution is obtained comprising said group IA or group IIA metal
hydroxide, and
a moist solid phase is obtained comprising said solid, said group IA or group
IIA metal hydroxide and water.
67. The apparatus as claimed in claim 66, performed a number of times
in sequence, such that
the concentration is lowered of said group IA or group IIA metal hydroxide in
said aqueous solution, and
a final moist solid is crated.
68. The apparatus as claimed in claims 65, 66 or 67 wherein said
separation is enhanced by equipment adding vibration to said mixture.
69. The apparatus as claimed in claims 65, 66, or 67 wherein at least
a portion of said group IA or group IIA metal hydroxide aqueous solution is reacted with a
haiide acid in a bleach unit to form a metal hypohalite solution, and wherein
said bleach unit comprises at least one selected from a list consisting of: a
continuous stirred tank reactor, a batch stirred tank reactor, a plug flow reactor, and any
combination therein.

70. The apparatus as claimed in claim 67, comprising a unit performing
pH adjustment of said final moist solid phase with a sulfoxy acid.
71. The apparatus as claimed in claims 67, or 69 comprising a unit
drying said final moist solid phase.
72. The apparatus as claimed in claim 64, wherein said polynucleate
metal compound comprises the SOx moiety from the addition of a sulfoxy acid to said
aqueous reaction of a metal halide solution with at least one metal
73. The apparatus as claimed in claim 72. wherein said aqueous
reaction of a metal halide solution with at least one metal is performed with equipment
providing high shear.
74. The apparatus as claimed in claim 44, comprising equipment
performing heat transfer to water and/or steam, the energy of formation of at least one
selected from a list consisting of: SO2 from S and air, SO2 from S and O2, SO3 from SO2 and
air, SO3 from SO2 and O2, said H2SO3 from SO2 and H2O; said H2SO4 from SO3 and H2O;
oleum from H2SO4 and SO3, said H2SO4 from oleum and H2O, and any combination therein,
such that
said water and/or steam has a higher temperature or energy.
75. The apparatus as claimed in claim 74, wherein said steam energy is
at least partially used to power an air separation process, such that
said air separation process provides at least one of O2 and N2.
76.The apparatus as claimed in claim 74, wherein said SO2 is reacted
in at least one unit with at least one selected from a list consisting of:
a metal hydroxide to form a metal sulfite,
a metal carbonate to form a metal bi-sulfite,
a metal halate and H2SO4 to form the corresponding halogen dioxide, and any
combination therein.

77. The apparatus
as claimed in claim 74, wherein at least a portion of
said steam energy is used in at least one unit to perform at least one selected from a list
consisting of: refine bauxite to alumina, heat said aqueous reaction of a metal halide solution
with at least one metal, evaporate H2O from a metal sulfoxy salt, degrade a halite to a halide,
heat S, turn a steam turbine which turns a generator to create electricity, heat the reaction of a
metal hydroxide and a halide acid to form a metal hypohalite, and any combination therein.
78. The apparatus as claimed in claim 77, wherein said electricity is at
least partially used in an air separation process to separate air, and wherein
said air separation process produces at least one of O2 and N2.
79. The apparatus as claimed in claim 77, wherein said electricity is at
least partially used in an electrolysis unit to form at least one selected from a list consisting of:
O2 from H2O, O3 from O2, H2 from H2O, H2S2O8 from H2SO4 in the production of H2O2, a
metal hypohalite from a metal halide solution, a metal halate from a metal halide salt, a metal
hydroxide and a halide acid from a metal halide salt, and any combination therein.
80. The apparatus as claimed in claim 79, wherein the metal(s) in said
metal halide salt comprises at least one selected from a list consisting of: ammonium, a Group
IA metal, a Group IIA metal, a Group IIIB metal, a Group VIII metal, a Group 1B metal, a
Group IIB metal, a Group IIIA metal, sodium, calcium, potassium, magnesium, aluminum,
copper and any combination therein.
81. The apparatus as claimed in claim 79, wherein said halogen of said
halide, hypohalite, halite or halate comprises at least one of chlorine and bromine.
82. The apparatus as claimed in claim 79, wherein said metal halide
solution comprises a waste catalyst or waste brine.

83. The apparatus as claimed in claim 79, wherein at least a portion of
said halide acid is used in at least one unit to form at least one selected from a list consisting
of the corresponding: hypohalite, halite, halate, available oxide form of said halide, said
halide in the form of a dioxide, and any combination therein.
84.The apparatus as claimed in claim 79, comprising a unit forming an
available oxide form of said halide, including a halide dioxide, wherein
said formation is performed with at least one selected from a list consisting of said
corresponding: halide, hypohalite, halide acid, halite, halate and any combination therein.
85. The apparatus as claimed in claim 79, wherein said H2 is at least
partially used in at least one selected from a list consisting of:
a combustion engine to turn a generator to generate electricity,
a fuel cell to generate electricity, and
a heater to heat the reaction between a metal halide salt with a sulfoxy acid.
86. The apparatus as claimed in claim 85, wherein said electricity is at
least partially used in said electrolysis unit.



ABSTRACT


A METHOD AND APPARATUS FOR THE PREPARATION OF A POLYNUCLEATE METAL
COMPOUND

The present invention discloses a method for the preparation of a polynucleate metal compound,
comprising at least one metal in the +2 or the +3 valence state, wherein
said polynucleate metal compound is formed by the aqueous reaction of a metal halide solution
with at least one metal, wherein
said metal halide solution comprises at least one metal in the +2 or +3 valence state, wherein
said at least one metal is in the 0, +2 or +3 valence state, and if in the 0 valence state is capable
of entering the +2 or +3 valence state wherein
said metal halide solution is formed by the aqueous reaction between said metal(s) within said
metal halide solution and a halide acid, and wherein
said halide acid is formed by the reaction of a metal halide salt, comprising the corresponding
halide of said halide acid, with a sulfoxy acid.
The present invention also discloses a manufacturing apparatus for producing a polynucleate metal
compound, said manufacturing apparatus comprising:
one or more units defining a process flow path, wherein
at least one or more units form said polynucleate metal compound from the aqueous reaction of
a metal halide solution with at least one metal, wherein
said metal halide solution comprises at least one metal in the +2 or +3 valence state, wherein
said at least one metal comprises a metal(s) in the 0, +2 or +3 valence state, and if in the 0
valence state capable of entering the +2 or +3 valence state, wherein
one or more units form said metal halide solution by reacting the metal(s) of said metal halide
solution with a halide acid, wherein
said halide acid formation comprises the reaction of a metal halide salt, comprising the
corresponding halide of said halide acid, wherein
said one or more units which form said halide acid by reacting a metal halide salt, comprising
the corresponding halide of said halide acid, with a sulfoxy acid, are upstream of
one or more units form said metal halide solution by reacting the metal(s) or said metal halide
solution with a halide acid, as well as upstream of
said one or more units forming said metal halide solution by reacting the metal(s) of said metal
halide solution with a halide acid.

Documents:

03074-kolnp-2007-abstract.pdf

03074-kolnp-2007-claims.pdf

03074-kolnp-2007-correspondence others.pdf

03074-kolnp-2007-description complete.pdf

03074-kolnp-2007-drawings.pdf

03074-kolnp-2007-form 1.pdf

03074-kolnp-2007-form 3.pdf

03074-kolnp-2007-form 5.pdf

03074-kolnp-2007-international publication.pdf

3074-KOLNP-2007-(01-04-2013)-CLAIMS.pdf .pdf

3074-KOLNP-2007-(01-04-2013)-CORRESPONDENCE.pdf

3074-KOLNP-2007-(08-01-2013)-CORESPONDENCE.pdf

3074-KOLNP-2007-(09-01-2013)-CORRESPONDENCE.pdf

3074-KOLNP-2007-(17-07-2012)-ABSTRACT.pdf

3074-KOLNP-2007-(17-07-2012)-AMANDED CLAIMS.pdf

3074-KOLNP-2007-(17-07-2012)-DESCRIPTION (COMPLETE).pdf

3074-KOLNP-2007-(17-07-2012)-DRAWINGS.pdf

3074-KOLNP-2007-(17-07-2012)-EXAMINATION REPORT REPLY RECEIVED.pdf

3074-KOLNP-2007-(17-07-2012)-FORM-1.pdf

3074-KOLNP-2007-(17-07-2012)-FORM-2.pdf

3074-KOLNP-2007-(20-07-2012)-ANNEXURE TO FORM 3.pdf

3074-KOLNP-2007-(20-07-2012)-CORRESPONDENCE.pdf

3074-KOLNP-2007-(20-07-2012)-OTHERS PCT FORM.pdf

3074-KOLNP-2007-(20-07-2012)-PA-CERTIFIED COPIES.pdf

3074-KOLNP-2007-(20-07-2012)-PETITION UNDER RULE 137.pdf

3074-KOLNP-2007-(27-09-2012)-ASSIGNMENT.pdf

3074-KOLNP-2007-(27-09-2012)-CORRESPONDENCE.pdf

3074-KOLNP-2007-(30-07-2012)-ASSIGNMENT.pdf

3074-KOLNP-2007-(30-07-2012)-CORRESPONDENCE.pdf

3074-KOLNP-2007-(30-07-2012)-PETITION UNDER RULE 137.pdf

3074-KOLNP-2007-CANCELLED PAGES.pdf

3074-KOLNP-2007-CORRESPONDENCE.pdf

3074-KOLNP-2007-EXAMINATION REPORT.pdf

3074-kolnp-2007-form 18.pdf

3074-KOLNP-2007-GPA.pdf

3074-KOLNP-2007-GRANTED-ABSTRACT.pdf

3074-KOLNP-2007-GRANTED-CLAIMS.pdf

3074-KOLNP-2007-GRANTED-DESCRIPTION (COMPLETE).pdf

3074-KOLNP-2007-GRANTED-DRAWINGS.pdf

3074-KOLNP-2007-GRANTED-FORM 1.pdf

3074-KOLNP-2007-GRANTED-FORM 2.pdf

3074-KOLNP-2007-GRANTED-FORM 3.pdf

3074-KOLNP-2007-GRANTED-FORM 5.pdf

3074-KOLNP-2007-GRANTED-SPECIFICATION-COMPLETE.pdf

3074-KOLNP-2007-INTERNATIONAL PUBLICATION.pdf

3074-KOLNP-2007-OTHERS.pdf

3074-KOLNP-2007-REPLY TO EXAMINATION REPORT.pdf

abstract-03074-kolnp-2007.jpg


Patent Number 256767
Indian Patent Application Number 3074/KOLNP/2007
PG Journal Number 31/2013
Publication Date 02-Aug-2013
Grant Date 26-Jul-2013
Date of Filing 21-Aug-2007
Name of Patentee HAASE RICHARD
Applicant Address 4402 RINGROSE DRIVE, MISSOURI CITY, TEXAS
Inventors:
# Inventor's Name Inventor's Address
1 HAASE RICHARD 4402 RINGROSE DRIVE,, MISSOURI CITY, TEXAS 77459
2 SMAARDYK JOHN 2331 RIVER ROCK TRAIL, KINGWOOD, TEXAS 77345
PCT International Classification Number C01F 7/22,C25D 17/00
PCT International Application Number PCT/US2006/002527
PCT International Filing date 2006-01-24
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 11/041329 2005-01-24 U.S.A.
2 60/728607 2005-10-20 U.S.A.
3 60/716323 2005-09-12 U.S.A.