Title of Invention

DETERGENT ALKYLATION USING A RARE EARTH EXCHANGED CATALYST

Abstract A process is disclosed using a new catalyst for use in the alkylation of benzene with a substantially linear olefin. The catalyst allows for cation exchange with a rare earth element to increase the alkylation of benzene while reducing the amount of isomerization of the alkyl group. This is important for increasing the quality of the alkylbenzene by increasing the linearity of the alkylbenzene.
Full Text DETERGENT ALKYLATION USING A RARE EARTH EXCHANGED CATALYST
FIELD OF THE INVENTION
[0001] The present invention is directed to highly selective, modified catalysts and the
process of using the catalysts. The catalysts are for use in the alkylation of aromatic
compounds.
BACKGROUND OF THE INVENTION
[0002] Alkylation of benzene produces alkylbenzenes that may find various commercial
uses, e.g., alkylbenzenes can be sulfonated to produce surfactants, for use in detergents. In
the alkylation process, benzene is reacted with an olefin the desired length to produce the
sought alkylbenzene. The alkylation conditions comprise the presence of homogeneous or
heterogeneous alkylation catalyst such as aluminum chloride, hydrogen fluoride, or zeolitic
catalysts and elevated temperature.
[0003] Various processes have been proposed to alkylate benzene. One commercial
process involves the use of hydrogen fluoride as the alkylation catalyst. The use and
handling of hydrogen fluoride does provide operational concerns due to its toxicity,
corrosiveness and waste disposal needs. Solid catalytic processes have been developed that
obviate the need to use hydrogen fluoride. Improvements in these solid catalytic processes
are sought to further enhance their attractiveness through reducing energy costs and
improving selectivity of conversion while still providing an alkylbenzene of a quality
acceptable for downstream use such as sulfonation to make surfactants.
[0004] Alkylbenzenes, to be desirable for making sulfonated surfactants must be capable
of providing a sulfonated product of suitable clarity, biodegradability and efficacy. With
respect to efficacy, alkylbenzenes having higher 2-phenyl contents are desired as they tend,
when sulfonated, to provide surfactants having better solubility and detergency. Thus,
alkylbenzenes having a 2-phenyl isomer content in the range from 25 to 35 percent are
particularly desired.
[0005] Improvements in the catalysts have facilitated the production of linear
alkylbenzenes, as shown in US 6,133,492, US 6,521,804, US 6,977,319, and US 6,756,030.
However, problems exist with many existing catalysts, and a better understanding, can lead to
further improvements in the catalysts.
SUMMARY OF THE INVENTION
[0006] The present invention provides for a process for producing a monoalkylated
aromatic compound having an increased linearity of the alkyl group. The process comprises
reacting an aromatic feedstock with an olefinic compound in an alkylation reactor at reaction
conditions using a catalyst, where the catalyst has a rare earth element incorporated into the
zeolitic framework. The catalyst has a silica to alumina ratio of less than 8, and the rare earth
element is exchanged to a degree such that the molar ratio of rare earth element to aluminum
is between 0.17 and 0.4. When taking valance charge into account, the ratio is between 0.51
and 1.2, with the balance being alkali, alkaline earth, ammonium cations or a mixture thereof.
[0007] In one embodiment, the process includes adding water to the feed to the reactor.
The water is added in an amount to keep the water below 1000 ppm by weight of the total
feed to the reactor. The process is operated at conditions to keep the reactants in the liquid
phase.
[0008] Other objects, advantages and applications of the present invention will become
apparent to those skilled in the art from the following drawings and detailed description.
BRIEF DESCRIPTION OF THE DRAWING
[0009] Figure 1 shows the linearity of catalysts that have retained some alkali cations.
DETAILED DESCRIPTION OF THE INVENTION
[0010] Catalysts are strongly affected by materials that either combine with the catalyst,
or can in one form or another reduce the catalytic activity of the catalyst. These materials are
poisons to the catalyst, and include materials such as alkali metals, alkaline earth metals,
ammonia, amine and their ions. These poisons are typical, and lead to pretreatments of feeds
to catalytic reactors to protect the catalyst, by removing any poisons in the process stream.
As shown by Venuto, P. B., et al., J of Catal, 4, 81-98, 87 (1966), "[l]ow sodium levels were
critical for high alkylation activity with REX catalyst." As the sodium level was increased
from 0.22 wt. % to 0.79 wt. %, the activity decreased to almost half.
[001 1 ] The alkylation of aromatics with olefins in important for several commercially
important technologies. Ethyl benzene (EB), cumene (isopropyl benzene), and larger chained
alkylbenzenes (detergents) are the three most economically important examples. The
detergents preferably made using longer chained linear alkyl groups, such as C8 to CI3, to
form linear alkyl benzenes. These alkylation reactions are carried out using acid catalysts,
either homogeneous catalysts such as HF, or heterogeneous catalyst such as A1C13, silicaalumina,
and zeolites. Although these are all acid catalyzed processes, there are enough
differences that they are all practiced with different catalysts. Skeletal isomerization is an
example of a concern in the LAB process, and which makes the use of catalysts suitable for
EB or cumene of less value in the LAB process.
[OO 12] The production of linear alkylbenzenes has traditionally been made in two
commercial forms, low 2-phenyl and high 2-phenyl. Low 2-phenyl LAB is made by HF
alkylation and results in a 2-phenyl concentration between 15 and 20 mass percent of the
LAB. This is due to the homogeneous acid, HF, lack of preference for catalyzing the
attachment of the benzene to the olefin chain. There is not alkylation on the terminal
carbons, and the internal carbons have a nearly equal probability of alkylation, and which
produces shorter chained alkyl groups extending from the benzene. High 2-phenyl LAB has
historically been made using AICI 3 alkylation and results in a 2-phenyl concentration
between 30 and 35 mass percent of the LAB. While it is possible to produce LAB with
different 2-phenyl contents, there is no market for these products, and consequently the
efforts have been to replace these environmentally unfriendly catalysts.
[0013] In 1995, UOP and Cepsa introduced a detergent alkylation process using the first
environmentally friendly solid bed alkylation process for the production of LAB. The
catalyst was a fluorided silica-alumina catalyst, and the process produces a high 2-phenyl
LAB product. This process has nearly completely replaces the use of AICI 3 in detergent
alkylation. However, it uses considerably more energy than the HF process due to the much
higher benzene to olefin ratio in the process, and produces slightly more dialkylate than the
HF process.
[0014] While ethylbenzene, cumene and LAB are all produced in processes using acid
catalysts, there are a number of key features that differentiate LAB from either ethylbenzene
or cumene. One is the length of the olefin and the reactions that the olefin can undergo.
Solid acid catalysts are know to catalyze both double bond isomerization and skeletal
isomerization in linear olefins. Most studies of double bond and skeletal isomerization of
linear olefins has focused on 1-butene. This is due to the desire to make isobutene for
MTBE, an oxygenate for gasoline, or polyisobutene. Gee and Prampin, Applied Catalysis A:
General 360 (2009), 71-80. Even a week acid catalyst, like SAPO-1 1, produces skeletal
isomerization, and is easily observed at 142C, and that skeletal isomerization is temperature
dependent.
[0015] It is known that skeletal isomerization of linear olefins occurs in the production of
LAB over solid acid catalysts. In 1965, in an article titled "Hydroisomerization of Normal
Olefins Under Alkylation Conditions" showed that skeletal isomerization was favored by
high acid concentrations and high temperatures (Peterson, A. H.; Phillips, B. L.; and
Kelly, J . T.; I&EC, 4, No. 4, 261-265, 1965). Also, as shown in US 4,301,317 to Young,
Table 2, in the reference, compares the amount of linear phenyldodecane produced by
alkylation of 1-dodecene with benzene over eight different zeolites. All of the zeolites
exhibited skeletal isomerization. Inhibiting skeletal isomerization is an important challenge
to be addressed, if one is to produce highly linear detergent range alkylbenzenes. It is further
worth noting that Beta zeolite, which is commonly used in the production of ethylbenzene
and cumene is unsuitable for detergent range LAB production due to its tendency to
skeletally isomerizes the linear olefins prior to their alkylation. Because ethylene and
propylene only have one isomer, both the double bond and skeletal isomerization of the
catalyst are moot and for this reason one cannot predict that a process or catalyst for
ethylbenzene or cumene production will necessarily extend to LAB.
[0016] A second difference between alkylation of long chain linear olefins with benzene
differs from that of ethylbenzene or cumene is the number of products. Ethylbenzene and
cumene are unique chemical compounds whereas LAB is a mixture of compounds that results
from the fact that long chain linear olefins have multiple positions for the benzene to insert
itself. As can be seen from Young's data in US 4,301,317, molecular sieves can reduce or
prohibit the formation of some phenylalkane isomers. This is phenomena is called shape
selectivity and occurs because the molecular sieve doesn't possess enough space for the
molecule to be formed. Since the commercially desirable detergent range linear
alkylbenzenes, "low 2-phenyl LAB" and "high 2-phenyl LAB" have relative narrow
windows on their 2-phenylalkane content, an acidic molecular sieve catalyst that has good
characteristics for producing ethylbenzene or cumene cannot be assumed to be appropriate
for producing commercially acceptable detergent range LAB.
[00 17] A third way in which the alkylation of long chain linear olefins with benzene
differs from that of ethylbenzene or cumene is in the impact of the benzene to olefin ratio.
Alkylation processes to convert ethylene to ethylbenzene and propylene to cumene operate at
significantly low benzene to olefin ratios than solid detergent alkylation processes. It has
long been known that monoalkylate selectivity can be maximized by operating at high
benzene to olefin ratios. High benzene to olefin ratios also means the ratio of benzene to
monoalkylate is high and the higher the weight fraction of benzene relative to other
aromatics, the higher the yield of monoalkylate. In the production of ethylbenzene or
cumene low benzene to olefin ratios can be employed to minimize energy usage because the
polyethylbenzene or polypropylbenzene can be easily transalkylated with benzene to produce
the desired product, ethylbenzene or cumene. In the detergent alkylation process, where a
solid fluorided amorphous silica-alumina catalyst is employed, shape selectivity does not
come into play due to the very large pores and the only way to control the amount of
dialkylbenzene is to use high benzene to olefin ratios. Converting long chain linear
dialkylbenzenes back to long chain linear monoalkylbenzenes can be done, but with
significantly lower efficiency than for ethylbenzene or cumene. Some of the transalkylation
occurs though dealkylation followed by alkylation with benzene. When transalkylation
occurs through this pathway some of the olefin undergoes skeletal isomerization, which
lowers overall product linearity.
[0018] Low benzene to olefin ratios also promotes the skeletal isomerization of linear
olefins. Because skeletal isomerization is a monomolecular reaction and alkylation is a
bimolecular reaction, lowering the benzene to olefin ratio effectively increases the olefin
concentration which causes the rate of olefin skeletal isomerization to increase faster than the
rate of olefin alkylation. Thus, in solid detergent alkylation processes, one is faced with the
choice of operating at high benzene to olefin ratios and accepting the high energy cost or
finding catalysts with the appropriate acidity such that skeletal isomerization of the linear
olefins is minimal.
[0019] It has been found that incorporating some rare earth elements into a zeolite
supercage, the efficiency is increased in producing a primary alkylation product. The means
to achieve an increasing amount of rare earth into the structure is by using a lower ratio
Faujasite and a designed rare earth incorporation technique. By low ratio, it is meant to
indicate the silica to alumina ratio.
[0020] The incorporation of rare earth exchanged low ratio zeolite reduces the geometric
space in the supercage, and it also reduces acidity due to an increase in the number of
framework aluminum at the low ratios. The reduced space and acidity significantly
suppresses the isomerization and cracking pathways, while the primary alkylation pathway is
not affected. This increases product by decreasing the undesired side reactions that occur.
One of the benefits from the new catalyst is a high linearity of the alkylbenzene for use in
detergent alkylation. Contrary to what one would expect, it was found that incorporating or
leaving some alkali or alkaline earth cations in the catalyst significantly improves catalyst
performance. And especially in the performance around the linearity of the alkylbenzene,
and the retention of linearity at increased operating temperatures. The present invention is
aimed at producing a product having a linearity of at least 90%.
[002 1] The present invention comprises a new catalyst for alkylation of aromatics
comprising a zeolite having a silica to alumina molar ratio of less than 8, and a rare earth
element incorporated into the zeolitic framework. The silica to alumina molar ratio is
preferably less than 6 and more preferably less than 5.6. The catalyst can be a low silica to
alumina molar ratio Y type zeolite, X type zeolite, or a zeolite have EMT/FAU intergrowth.
[0022] The catalyst is formed by using a Y zeolite or X zeolite and modified with an
alkali or alkaline earth element or nitrogen compound, such as sodium, barium, ammonia or
amine to control the acidity. The catalyst is then ion exchanged with a rare earth element to
remove a portion of the alkali or alkaline earth elements, and to provide for larger ions in the
zeolites cages. The catalyst can be in extruded or bead form. The catalyst can be prepared
by first exchanging the zeolite powder with a rare earth element and then forming the zeolite
into pellets or beads. An alternative is to form the zeolite into pellets or beads and then
perform the rare earth exchange.
[0023] When the catalyst is a Y type zeolite, the silica to alumina molar ratio is between
2.8 and 8, and preferably between 3 and 6, and when the catalyst is an X type zeolite, the
silica to alumina molar ratio is between 2 and 2.8.
[0024] The catalyst includes a rare earth element that is incorporated into the supercages
of the zeolite to provide some steric restraint. The supercages are large cavities, relative to
the pores, in the zeolites that usually have a diameter greater than 1 nm. The supercages are
sometimes cavities formed with the intersection of different pores in the zeolite. This is a
region where there is less steric hindrance for some catalytic reactions when compared with
the pores. This limits undesirable side reactions. Rare earth elements that can be used
include at least one of the following: scandium (Sc), yttrium (Y), lanthanum (La), cerium
(Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium
(Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thullium
(Tm), ytterbium (Yb), and lutetium (Lu). Preferred rare earth elements include at least one
of yttrium (Y), lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd),
gadolinium (Gd), dysprosium (Dy), erbium (Er), and ytterbium (Yb).
[0025] The rare earth element is cation exchanged with the zeolite sufficient to where the
rare earth element to aluminum molar ratio is between 0.5 1 and 1.2. The catalyst is further
cation exchanged with an alkali, an alkaline earth element, or nitrogen compound cation.
[0026] The catalyst can further include a binder wherein the binder comprises alumina,
silica, magnesium silicates, zirconia, and mixtures thereof. The binder can also comprise
natural or synthetic clays, which are made up of various metal oxides. The binder provides
hardness to the catalyst to improve the physical durability of the catalyst from abrasion
during operation.
[0027] In one embodiment, the catalyst is an X type zeolite having an alumina molar ratio
less than 2.8. A rare earth element is incorporated into the zeolitic framework. The rare
earth elements include yttrium (Y), lanthanum (La), cerium (Ce), praseodymium (Pr),
neodymium (Nd), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium
(Ho), erbium (Er), thullium (Tm), ytterbium (Yb), and lutetium (Lu). Preferred rare earth
elements include yttrium (Y), lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium
(Nd), gadolinium (Gd), dysprosium (Dy), erbium (Er) and ytterbium (Yb). The rare earth
elements contribute to developing steric hindrance within the zeolite pores, and modifying
the acidity of the X type zeolite, to reduce the acidity from strong to moderate. It is preferred
that the silica to alumina molar ratio is less than 2.8, and more preferably less than 2.5, with a
most preferred ratio between 1 and 2.4.
[0028] The catalyst has the rare earth elements exchanged to a degree that the molar ratio
of rare earth elements to aluminum in the catalyst is in the range between 0.5 1 and 1.2. A
balance of the cation exchange to control the acidity is with alkali or alkaline earth elements.
[0029] In the detergent alkylation process, the retention of linearity of the alkyl group is
important for the quality of the detergents produced from alkylaromatics. It was found that
the incorporation of some alkali, or alkaline earth, elements on the catalyst improved the
catalyst performance with respect to retaining linearity of the alkyl group without affecting
the activity adversely. The results of alkylation tests with the rare earth exchanged catalyst
show the high degree of linearity of the product over a wide range of operating temperatures
in Figure 1.
[0030] The process for producing a monoalkylated aromatic compound comprises:
passing an aromatic feedstock and an olefinic compound to an alkylation reactor. The
alkylation reactor has an alkylation catalyst comprising a zeolite having a silica to alumina
molar ratio less than 8 and includes a rare earth element incorporated into the zeolitic
framework. The reactor generates an effluent stream comprising the monoalkylated aromatic
compound, and is passed to a separation unit. The separation unit recovers the
monoalkylated aromatic compound, and generates an aromatic stream and a non-product
alkylated aromatic stream. The non-product alkylated aromatic stream generally comprises
dialkylated aromatic compounds and can be passed to a transalkylation reactor to improve the
product yield.
[0031] Aromatic compounds and olefins are reacted under alkylation conditions in the
presence of a solid alkylation catalyst. The alkylation conditions generally include a
temperature in the range between 80°C and 200°C, most usually at a temperature not
exceeding 175°C, e.g., 100°C to 160°C. Typically, as the catalyst ages, the temperature of
the alkylation is increased to maintain desired activity. The alkylation is an exothermic
reaction and thus in a substantially adiabatic reactor, the effluent is at a higher temperature
than that of the feed. A substantially adiabatic reactor is one where the increase in
temperature of the effluent over that of the feed accounts for at least 75 percent of heat
generated by the reactions in the reaction zone. The preferred aromatic compound is
benzene, and the preferred olefins are linear alpha olefins having from 8 to 20 carbon atoms.
During the alkylation process, the catalyst deactivates, and the temperature is allowed to
increase to compensate for catalyst deactivation. With deactivation, and with increases in
temperature, product linearity is reduced. This catalyst minimizes the changes in the product
linearity over the life of the catalyst and extends the useful life of the catalyst, by maintaining
a higher product linearity during the process, such that with increasing temperature, there is
still a high degree of linearity maintained over prior catalysts.
[0032] The temperature within a reaction zone is maintained within a suitable range by
providing a large excess of aromatic compound to the reaction zone to absorb heat. Where
the aliphatic feedstock contains paraffins, the paraffins also serve to absorb heat from the
exothermic reactions. High exothermic temperatures during the alkylation can result in
untoward effects in terms of not only catalyst deactivation but also in product quality
degradation, especially skeletal isomerization, and, in particular, skeletal isomerization of the
olefin.
[0033] The alkylation reactor is generally a fixed bed type reactor, where the reactants
flow over the catalyst as the reactants flow through the reactor. The catalyst can be
regenerated in the alkylation reactor to remove carbon deposits by taking the reactor off-line.
[0034] The alkylation reactor can also comprise a plurality of reactors with intercoolers
between the reactors to remove heat and maintain the operation in a desirable temperature
range.
[0035] In one embodiment, the catalyst in the present alkylation reaction process is an X
type zeolite having a silica to alumina molar ratio less than 2.8, and the zeolite includes a rare
earth element incorporated into the zeolitic framework. The rare earth elements include at
least one from the group comprising: yttrium (Y), lanthanum (La), cerium (Ce),
praseodymium (Pr), neodymium (Nd), europium (Eu), gadolinium (Gd), terbium (Tb),
dysprosium (Dy), holmium (Ho), erbium (Er), thullium (Tm), ytterbium (Yb), and lutetium
(Lu).
[0036] The alkylation process with the new catalyst also can include the addition of water
to the alkylation reactor. The water in the reactor adsorbs onto the catalyst during the
reaction, and comprises between 0.5 and 6 weight percent of the total catalyst weight. A
preferred amount of water adsorbed onto the catalyst comprises between 1 and 3 weight
percent of the total catalyst weight. The amount of water is low and kept to below 1000 ppm
by weight of the combined feed of aromatic compound and olefin to the alkylation reactor.
Preferably, the amount of water is less than 900 ppm by weight of the combined feed to the
reactor.
[0037] The alkylation process for detergent alkylation is preferably operated in the liquid
phase. To maintain the reactants in the liquid phase, the reactor is operated at a pressure
between 1300 and 7000 kPa, with a preferred operating pressure between 2500 and 4500 kPa.
[0038] In an alternate embodiment, the process of benzene alkylation comprises passing
an aromatic feedstock and an olefinic compound to an alkylation reactor. The alkylation
reactor has an alkylation catalyst comprising a Y or X type zeolite having greater than
16.5 wt% of rare earth in the zeolite with the balance being alkali, alkaline earth element, or
nitrogen compound cations incorporated into the zeolitic framework. The choice of rare
earth elements is as stated above. In the preferred operation the catalyst has a silica to
alumina molar ratio between 3 and 6.
[0039] Experiments were performed where catalyst A is the catalyst of the present
invention and catalysts B, C, D and E were prepared for comparative purposes. Catalyst A
was prepared by rare earth exchange of Y-54 of 0.3 M of rare earth solution made up from
rare earth stock solution obtained from Moly Corp. at 75-80°C for 2 hours. The exchange
utilizes 1.0 gm of rare earth solution per gram of Y-54 powder on an as received basis. At
the end of the rare earth exchange, the slurry is filtered under vacuum and the resulting filter
cake is washed with 10 grams of de-ionized water per gram of powder. The filter cake is
dried and then steamed at 550°C at 50% steam for 1.5 hours. The steamed rare earth
exchanged powder is exchanged with a second rare earth solution and water wash following
the same procedure as above. The powder is formulated into a catalyst of cylindrical pellets
with 1/16" (0.16 cm) diameter consisting of 80 wt% zeolite and 20 wt% binder on a volatile
free basis.
[0040] Catalysts B, C, D and E are prepared following the same procedure used for
preparing catalyst A, with the exception that no second rare earth exchange is performed.
Instead, an ammonium exchange step of various degrees is performed following the steaming
step to yield a final powder of different rare earth and sodium contents. The ammonium
exchange is typically done at 70°C for 1 to 2 hours using a 10 wt% NH4NO3 solution.
Table - Catalyst Property and Sensitivity of Product Linearity to Temperatures
[0041] The catalyst is tested in a plug flow reactor operating at inlet temperatures from
95 to 130°C. The test condition includes a benzene to olefin molar ratio of the feed of 30, a
pressure of 500 psig, and catalyst LHSV is 3.75 hr 1. The reaction is carried out in liquid
phase condition. The olefin conversions are 100% or close to 100% with the calculations
based on the Bromine Index in the feed and the product. The composition of the product is
analyzed by gas chromatography. The product linearity is summarized in Figure 1. The
sensitivity of product linearity to temperature is shown in Figure 1 and reported also in the
Table along with the zeolite properties. The data show that product linearity and the
sensitivity of product linearity to temperatures are a function of rare earth and sodium
contents. As shown in the Table, Catalyst A contains greater than 16.5 wt% rare earth and
has higher sodium content. It shows higher product linearity, which is not sensitive to
temperature changes. Conceivably, the catalyst is capable of operating over a wide range of
temperatures without incurring changes in product linearity. Furthermore, as the catalyst
deactivates with time, the operating temperature needs to be adjusted upward to compensate
for the activity degradation. Catalyst A can achieve the goal of maintaining the activity via
raising the operating temperature without sacrificing the product linearity.
[0042] While the invention has been described with what are presently considered the
preferred embodiments, it is to be understood that the invention is not limited to the disclosed
embodiments, but it is intended to cover various modifications and equivalent arrangements
included within the scope of the appended claims.











CLAIMS:
1. A process for producing a monoalkylated aromatic compound comprising:
passing an aromatic feedstock and an olefinic compound to an alkylation reactor,
wherein the alkylation reactor comprises a catalyst comprising a zeolite having a silica to
alumina molar ratio less than 8 and a rare earth element incorporated into the zeolitic
framework, wherein the rare earth element is in an amount greater than 16.5 wt % of the
zeolite with the balance being alkali, alkaline earth, nitrogen compound cations, or a mixture
thereof, thereby generating an effluent stream;
passing the effluent stream to a separation process thereby generating an aromatic
stream, a product stream comprising a monoalkylated aromatic compound, and a non-product
alkylated aromatic stream.
2. The process of claim 1 further comprising adding water to the alkylation reactor, wherein
the water is added in an amount to keep the water concentration below 1000 ppm by weight
of the combined feed to the alkylation reactor.
3. The process of claim 1 further comprising adding water to the alkylation reactor where the
water adsorbs on the catalyst and comprises between 0.5 and 6 wt.% of the catalyst.
4. The process of claim 1 wherein the catalyst comprises:
an X type zeolite having a silica to alumina molar ratio less than 2.8; and
a rare earth element incorporated into the zeolitic framework wherein the rare earth
element is selected from the group consisting of yttrium (Y), lanthanum (La), cerium (Ce),
praseodymium (Pr), neodymium (Nd), europium (Eu), gadolinium (Gd), terbium (Tb),
dysprosium (Dy), holmium (Ho), erbium (Er), thullium (Tm), ytterbium (Yb), lutetium (Lu),
and mixtures thereof.
5. The process of claim 4 wherein the catalyst has at least one rare earth element selected
from the group consisting of yttrium (Y), lanthanum (La), cerium (Ce), praseodymium (Pr),
neodymium (Nd), gadolinium (Gd), dysprosium (Dy), erbium (Er), ytterbium (Yb), and
mixtures thereof.
6. The process of claim 4 wherein the rare earth elements in the catalysts are exchanged to a
degree that the rare earth to aluminum molar ratio is in the range from 0.51 to 1.2 with the
balance being alkali, alkaline earth element, nitrogen compound cations, or a mixture thereof.
7. The process of claim 1 wherein the alkylation reactor is operated at a temperature between
80°C and 200°C
8. The process of claim 1 wherein the alkylation reactor is operated at a pressure between
1300 to 7000 kPa.
9. The process of claim 1 wherein the catalyst comprises:
a low ratio Y type zeolite having a silica to alumina molar ratio less than 8; and
a rare earth element incorporated into the zeolitic framework wherein the rare earth
element is selected from the group consisting of yttrium (Y), lanthanum (La), cerium (Ce),
praseodymium (Pr), neodymium (Nd), europium (Eu), gadolinium (Gd), terbium (Tb),
dysprosium (Dy), holmium (Ho), erbium (Er), thullium (Tm), ytterbium (Yb), lutetium (Lu),
and mixtures thereof.
10. The process of claim 9 wherein the zeolite is a Y type zeolite with a silica to alumina
molar ratio between 3 and 8.

Documents:

http://ipindiaonline.gov.in/patentsearch/GrantedSearch/viewdoc.aspx?id=2xDYRk4c/31PCNB+mlBwyw==&loc=+mN2fYxnTC4l0fUd8W4CAA==


Patent Number 280004
Indian Patent Application Number 6202/DELNP/2012
PG Journal Number 06/2017
Publication Date 10-Feb-2017
Grant Date 07-Feb-2017
Date of Filing 12-Jul-2012
Name of Patentee UOP LLC
Applicant Address 25 East Algonquin Road P. O. Box 5017 Des Plaines Illinois 60017 5017
Inventors:
# Inventor's Name Inventor's Address
1 JAN Deng Yang UOP LLC 25 East Algonquin Road P. O. Box 5017 Des Plaines Illinois 60017 5017
2 RILEY Mark G. UOP LLC 25 East Algonquin Road P. O. Box 5017 Des Plaines Illinois 60017 5017
3 SOHN Stephen W. UOP LLC 25 East Algonquin Road P. O. Box 5017 Des Plaines Illinois 60017 5017
4 MOSCOSO Jaime G. UOP LLC 25 East Algonquin Road P. O. Box 5017 Des Plaines Illinois 60017 5017
5 MILLER Raelynn M. UOP LLC 25 East Algonquin Road P. O. Box 5017 Des Plaines Illinois 60017 5017
PCT International Classification Number C07C2/66,C07C15/00,B01J29/08
PCT International Application Number PCT/US2010/048754
PCT International Filing date 2010-09-14
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 12/639968 2009-12-16 U.S.A.