Title of Invention

A METHOD FOR PRODUCING A CATALYST COMPRISING MOLYBDGNUM, BISMUTH AND IRON

Abstract A method for producing a catalyst comprising at least molybdenum, bismuth and iron for use in producing an unsaturated aldehyde and an unsaturated carboxylic acid through gas-phase catalytic oxidation of propylene, isobutylene, tertiary butly alcohol or methyl tertiary butly ether with molecular oxygen, comprising the steps of: kneading particles comprising catalyst components, an organic binder and a liquid to form a kneaded mixture; and extrusion molding the kneaded mixture, wherein the organic binder comprises at least a high-viscosity organic binder having a visocisty of from 5,000 mPa.s to 25,000 mPa.s and a low- viscosity organic binder having a viscosity of from 10 mPa.s to less than 5,000 mPa.s, wherein viscosity is measured with a 1% by mass water solution or dispersion of the binder at 20°C.
Full Text DESCRIPTION
CATALYST FOR PRODUCING UNSATURATED ALDEHYDE AND
UNSATURATED CARBOXYLIC ACID, METHOD FOR PRODUCING SAME, AND
METHOD FOR PRODUCING UNSATURATED ALDEHYDE AND UNSATURATED
CARBOXYLIC ACID
TECHNICAL HELD
[0001]
The present invention relates to a catalyst containing at least molybdenum, bismuth
and iron for use in producing an unsaturated aldehyde and an unsaturated carboxylic
acid through gas-phase catalytic oxidation of propylene, isobutylene, tertiary butyl
alcohol (in some cases expressed as TEA) or methyl tertiary butyl ether (in some cases
expressed as MTBE) with molecular oxygen, a method for producing a catalyst for use
in producing an unsaturated aldehyde and an unsaturated carboxylic acid, and a method
for producing an unsaturated aldehyde and an unsaturated carboxylic acid.
BACKGROUND ART
[0002]
So far, there have been many proposals concerning catalysts for use in producing
unsaturated aldehydes and unsaturated carboxylic acids through gas-phase catalytic
oxidation of propylene, isobutylene, TBA or MTBE and methods for producing such
catalysts.
[0003]
Most of such catalysts have a composition containing at least molybdenum, bismuth
and iron and molded catalysts having such a composition are industrially used. These
catalysts are classified into an extrusion-molded catalyst, a supported catalyst or the like
depending on their methods of molding. Normally, the extrusion-molded catalyst is
produced through the steps of kneading particles containing catalyst components and
molding the resultant kneaded mixture.
[0004]
In Patent document 1, a method of adding a certain cellulose derivative when a
catalyst is extrusion-molded is disclosed. Further, in Patent document 1, it is disclosed
that a cellulose derivative having a viscosity of its 2% water solution in the range of
1,000 to 10,000 cps al 20°C is used, and when the viscosity exceeds 10,000 cps, an
extrusion moldability of the material to which the cellulose derivative has been added
becomes deteriorated and there is little effect on the improvement of the moldability.
[0005]
Further, in Patent document 2, a method for producing an extrusion-molded catalyst
is disclosed, wherein two kinds of binder, namely, hydroxypropyl methylcellulose and
curdlan are used, and it is further disclosed that as a cellulose derivative which can be
used as a molding aid, one having a viscosity of its 2% water solution in the range of
1,000 to 10,000 mPa-s at 20°C is preferable because of the good moldability.
[0006]
However, catalysts obtained by these publicly known methods are not always
sufficient as an industrial catalyst in respect of catalyst activity, selectivity to a target
product and the like and hence a further improvement has been generally desired from
the industrial point of view.
Patent document 1: Japanese Patent Application, First Publication No. Hei 7-16,464
Patent document 2: Japanese Patent Application, First Publication No. 2002-282,695
DISCLOSURE OF INVENTION
PROBLEM TO BE SOLVED BY THE INVENTION
[0007]
The objects of the present invention are to provide a catalyst for use in producing an
unsaturated aldehyde and an unsaturated carboxylic acid, which is excellent in catalyst
activity and selectivity to the unsaturated aldehyde and the unsaturated carboxylic acid,
a method for producing the catalyst and a method for producing an unsaturated
aldehyde and an unsaturated carboxylic acid in a high activity and a high selectivity by
using the catalyst.
MEANS FOR SOLVING PROBLEM
[0008]
To attain the objects described above, the present inventors have intensively
researched viscosity, a method of addition, amount of addition and the like of an organic
binder to be added at the time of extrusion molding, and have surprisingly found and
reached that by using two or more kinds of specified organic binders each of which is
different in its viscosity, it is possible to produce a catalyst which is excellent in catalyst
activity and selectivity and thus have completed the present invention.
[0009]
Namely, the present invention is a method for producing a catalyst containing at least
molybdenum, bismuth and iron for use in producing an unsaturated aldehyde and an
unsaturated carboxylic acid through gas-phase catalytic oxidation of propylene,
isobutylene, TBAor MTBE with molecular oxygen, comprising the steps of:
kneading particles containing catalyst components, an organic binder and a liquid; and
extrusion molding the resultant kneaded mixture,
wherein the organic binder contains at least a high-viscosity organic binder having a
viscosity (of its 1% water solution or dispersion at 20°C) of from 5,000 mPas to 25,000
mPas and a low-viscosity organic binder having a viscosity (of its 1% water solution or
dispersion at 20°C) of from 10 mPas to less than 5,000 mPas.
[0010]
Further, the present invention is a catalyst for use in producing an unsaturated
aldehyde and an unsaturated carboxylic acid produced by the above-mentioned method
for producing the cataljst.
[0011]
Furthermore, the present invention is a method for producing an unsaturated aldehyde
and an unsaturated carboxylic acid through gas-phase catalytic oxidation of propylene,
isobutylene, TBA or MTBE with molecular oxygen by using the above-mentioned
catalyst of the present invention.
EFFECT OF THE INVENTION
[0012]
The catalyst for us(; in producing an unsaturated aldehyde and an unsaturated
carboxylic acid of the present invention is excellent in catalyst activity and selectivity to
the unsaturated aldehyde and the unsaturated carboxylic acid, and by using this catalyst,
it is possible to produce the unsaturated aldehyde and the unsaturated carboxylic acid in
high yield.
BEST MODE FOR CARRYING OUT THE INVENTION
[0013]
The catalyst of the present invention is used in producing an unsaturated aldehyde
and an unsaturated carboxylic acid through gas-phase catalytic oxidation of propylene,
isobutylene, TBA or MTBE, which serves as a raw material of the reaction, with
molecular oxygen. The raw material of the reaction may be used alone or in
combination of two or more kinds.
[0014]
The unsaturated aldehyde and the unsaturated carboxylic acid mentioned above
specifically indicate acrolein and acrylic acid in the case that the raw material of the
reaction is propylene, and methacrolein and methacrylic acid in the case that the raw
material of the reaction is other than propylene.
[0015]
The catalyst of the present invention is an extrusion-molded catalyst containing at
least molybdenum, bismuth and iron as catalyst components. The catalyst components
may include, other than these components, silicon, cobalt, nickel, chromium, lead,
manganese, calcium, magnesium, niobium, silver, barium, tin, tantalum, zinc,
phosphorus, boron, sulfur, selenium, tellurium, cerium, tungsten, antimony, titanium,
lithium, sodium, potassium, rubidium, cesium, thallium and the like.
[0016]
The extrusion-molded catalyst containing at least molybdenum, bismuth and iron as
mentioned above is generally produced through the steps of (1) producing particles
containing catalyst components, (2) kneading the resultant particles containing catalyst
components and the like, (3) extrusion molding the resultant kneaded mixture, and (4)
drying and / or heat treating the resultant extrusion-molded article.
[0017]
In the present invention, the step (1) is not particularly limited and conventionally
known methods can be used. Normally, aqueous slurry containing at least molybdenum,
bismuth and iron is dried and further pulverized to particles when it is preferable.
[0018]
The method for producing the aqueous slurry containing at least molybdenum,
bismuth and iron is not particularly limited and a conventionally well-known
precipitation method, oxide mixing method or the like can be used, provided that they
don't cause undesirable maldistribution of the components.
[0019]
As the raw materials of the catalyst components to be dissolved in the aqueous slurry,
oxides, sulfates, nitrates, carbonates, hydroxides, ammonium salts, halides or the like of
each element can be used. For example, as a raw material of molybdenum, ammonium
paramolybdate and molybdenum trioxide can be exemplified. The raw materials of the
catalyst components may be used alone or in combination of two or more kinds to each
element.
[0020]
The method for drying the aqueous slurry to obtain particles is not particularly
limited and, for example, a drying method using spray dryer, a drying method using
slurry dryer, a drying method using drum dryer and a drying method using evaporation
followed by pulverizing the resultant dried block material can be applied. Among these
methods, the drying method using spray dryer to obtain dried spherical particles is
preferable because the particles can be obtained at the same time of drying and the
resultant dried particles have a regular spherical shape. A drying condition differs
depending on a drying method, and in the case of using spray dryer, the inlet
temperature is normally 100 to 500°C and the outlet temperature is normally 100°C or
more, preferably 105 to 200°C.
[0()21]
In some cases, the dried particles thus obtained contain salts such as nitrates
originating from the raw materials of the catalysts, and the strength of the molded
articles may be lowered when these salts are decomposed by calcinations after the
molding of the particles. Consequently, it is preferable not only to dry the particles but
also to calcine them and make them as calcined particles at this point of time. The
calcining condition is not particularly limited and publicly known calcining conditions
can be applied. Normally, calcination is carried out in the presence of oxygen, air,
nitrogen, nitrogen oxides or the like and in the temperature range of 200 to 600°C, and
the calcining time is properly chosen in accordance with a target catalyst.
[0022]
When average particle diameter of the particles containing catalyst components
becomes large, large voids are formed at the interstices of the particles, in other words,
large pores are formed so that a selectivity has a tendency to improve. On the other hand,
when the average particle diameter becomes small, number of contact points among the
particles per unit volume increases so that the mechanical strength of the resultant
molded catalyst has a tendency to improve. In view of these, the average particle
diameter is preferably 10 to 150^m, more preferably 20 to lOOjam.
[0023]
Then, in the step (2), the particles obtained in the step (1), a liquid and an organic
binder are kneaded. A apparatus to be used in kneading is not particularly limited and,
for example, a batch type kneader equipped with dual arm type mixing blade, a
continuous kneader such as axial rotation reciprocating screw type or self-cleaning type
can be used, however, the batch type is preferable, because kneading can be carried out
while checking the state of the kneaded material. Further, the end point of kneading can
be determined by the visual observation or the feel. The mixing method of the
aforementioned particles, the liquid and the organic binder is not particularly limited.
Specifically, a method in which the particles are dry mixed with the organic binder first,
and then the resultant mixture is mixed with the liquid, a method in which the organic
binder is dissolved or dispersed in the liquid first, and then the resultant mixture is
mixed with the particles or the like are exemplified. Above all, the method in which the
particles are dry mixed with the organic binder first, and then the resultant mixture is
mixed with the liquid is preferable.
[Q024]
As the liquid to be used in the step (2), water or alcohol is preferable, and as the
alcohol, lower alcohol such as ethyl alcohol, methyl alcohol, propyl alcohol or butyl
alcohol can be exemplified. Among these liquids, water is especially preferable from the
viewpoint of cost and easiness of handling. These liquids can be used alone or in
combination of two or more kinds.
[0025]
The amount of the liquid to be used is properly selected depending on the kind or size
of the particles, the kind of the liquid or the like, however, it is normally 10 to 60 parts
by mass, preferably 20 to 50 parts by mass per 100 parts by mass of the dried or
calcined particles obtained in the step (1).
[0026]
In the step (2), an organic binder containing at least two kinds of organic binders each
of which has a different viscosity is used. In the present invention, an organic binder
having the highest viscosity among organic binders contained in the organic binder is
expressed as high-viscosity organic binder and an organic binder having the lowest
viscosity is expressed as low-viscosity organic binder. The viscosity of the high-
viscosity organic binder or the low-viscosity organic binder means a viscosity measured
with a 1% by mass solution or dispersion of each organic binder at 20°C and can be
measured, for example, with a viscometer such as model B viscometer. The viscosity of
the binder should be measured with solution as long as possible and measurement with
dispersion should be limited only in the case that the binder does not dissolve under the
aforementioned conditions of concentration and temperature. On this occasion, the
viscosity of the dispersions should be measured under the condition that the liquid phase
thereof is in the state of saturated solution. Further, in the case of the organic binder of
polymer compound, the viscosity of it is sometimes different even among the products
having the same name because of the difference in the molecular weight and the like.
[0027]
The high-viscosity organic binder to be used in the present invention has a viscosity
of from 5,000 mPas to 25,000 mPas. The high- viscosity organic binder preferably has
a viscosity of from 10,i300 mPas to 20,000 mPas. Further, the low-viscosity organic
binder to be used in the present invention has a viscosity of from 10 mPas to less than
5,000. The low-viscosity organic binder preferably has a viscosity of from 10 mPa-s to
500 mPas, more preferably from 20 mPas to 350 mPas.
[0028]
When the high-viscosity organic binder having the viscosity of from 5,000 mPas to
25,000 mPa-s and the low-viscosity organic binder having the viscosity of from 10
mPas to less than 5,C»00 mPas are used in the form of mixture, the activity and
selectivity of the catalyst are improved.
[0029]
The reason is not clear why moldability and catalyst performance such as activity and
selectivity are improved by using the high-viscosity organic binder which has not been
used so far in the catalyst system such as those in the present invention because of its
deteriorated moldability in the form of mixture with the low-viscosity organic binder.
But, it is supposed, as for the improvement of the moldability, that a molding pressure is
partially lowered by the homogeneous existence of the kneaded material of the
low-viscosity organic binder, even in a small amount, within the kneaded material of the
high-viscosity organic binder to improve the moldability. Further, it is supposed, as for
the improvement of the catalyst performance, that preferable pores for the catalytic
reaction are formed during the drying step, owing to a slight difference in shrinking
behavior of each of the high viscosity and the low viscosity portion at the time of drying
after molding, to impro\'e the activity and selectivity of the catalyst.
[0030]
Moreover, when the high-viscosity organic binder is used, even in a small amount, a
molded article with high strength can be obtained so that the amount of the organic
binder to be used can be reduced and heat treatment for the removal of the binder after
drying is accordingly simplified. Consequently, the problem of the lowering of the
catalyst performance caused by the reduction of the catalyst at the time of the heat
treatment is considerably improved.
[0031]
The kind of the organic binder is not particularly limited, a cellulose derivative such
as methyl cellulose, ethyl cellulose, carboxymethyl cellulose, sodium carboxymethyl
cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropylmethyl
cellulose, hydroxyethylmethyl cellulose, hydroxybutylmethyl cellulose or
ethylhydroxyethyl cellulose, or a water soluble or water dispersible synthetic polymer
compound such as polyvinyl alcohol, or a P-1, 3-glucan such as curdlan, laminaran,
paramylon, callose, pachyman or scleroglucan can be exemplified.
[0032]
As the kind of the high-viscosity organic binder, methyl cellulose,
hydroxypropylmethyl cellulose and hydroxyethylmethyl cellulose are especially
preferable. The proportion of the high-viscosity organic binder to the total organic
binder is preferably 95 to 50% by mass, more preferably 85 to 65% by mass. When the
amount of the high-viscosity organic binder to be used is from 95 to 50% by mass, it is
preferable because strength of a molded article is greatly improved.
[0033]
As the kind of the low-viscosity organic binder, methyl cellulose,
hydroxypropylmethyl cellulose, hydroxyethylmethyl cellulose, curdlan and paramylon
are especially preferable, The proportion of the low-viscosity organic binder to the total
organic binder is preferably 5 to 50% by mass, more preferably 10 to 35% by mass.
When the amount of the low-viscosity organic binder to be used is from 5 to 50% by
mass, it is preferable because moldability is considerably improved.
[0034]
Further, it has been found in the present invention that temperature of the liquid to be
added or rate of adding the liquid at the time of kneading exerts influence on
moldability. The temperature of the liquid is preferably 20°C or less, more preferably
10°C or less. The rate of adding the liquid is preferably 0.3 part by mass / min. or less.
more preferably 0.2 part by mass / min. per 1 part by mass of the particles containing
catalyst components.
[0035]
The organic binder may be used either in a purified state or without purification,
however, it is preferable to keep the amount of impurities such as metals and residue on
ignition as small as possible because these impurities sometimes cause deterioration of
the catalyst performance.
[0036]
The amount of the organic binder to be used is properly selected depending on the
kind or size of the particles, the kind of the liquid or the like, however, it is normally
0.05 to 15 parts by mass, preferably 0.1 to 10 parts by mass per 100 parts by mass of the
particles obtained in the step (1). Moldability tends to be improved as the amount of the
organic binder to be added increases and post-treatment such as heat treatment after
molding tends to be simplified as the amount of the organic binder to be added
decreases.
[0037]
Further, in the present invention, inert carrier such as conventionally known inorganic
compounds which include silica, alumina, silica-alumina, silicon carbide, titania,
magnesia, graphite, diatomite, glass fiber, ceramic ball, stainless steel or inorganic fiber
such as ceramic fiber or carbon fiber can be added. Addition may be performed at the
time of kneading in the step (2).
[0038]
Then, in the step (3), the kneaded material obtained in the step (2) is extrusion
molded. When the kneaded material of the particles containing catalyst components, the
organic binder and the liquid are extrusion molded, auger type extruder, piston type
extruder or the like can be used.
[0039]
The shape of the molded article made by extrusion molding is not particularly limited
and ring shape, cylindrical shape, starlike shape or the like can be optionally chosen.
[0040]
Then, in the step (4), the molded article of the catalyst obtained in the step (3) is dried
and calcined to obtain a catalyst (product).
[0041]
The method of drying is not particularly limited and a publicly known method such
as hot air drying, wet drying, far infrared drying, microwave drying or the like can be
optionally used. The drying condition can be properly selected as long as it can realize a
target moisture content.
[0042]
The dried molded article is normally calcined, however, in the case that the particles
have been calcined in the step (1), the step of calcination can be omitted. The calcining
condition is not particularly limited and a publicly known calcining condition can be
applied. Normally, calcination is carried out in the temperature range of 200 to 600°C.
[0043]
The catalyst containing at least molybdenum, bismuth and iron to be produced by the
method of the present invention preferably has a composition represented by the
following general formula (1).
[0044]
MOa Bib Fee Md Xe Yf Zg SihOi (1)
(In the formula, Mo, Bi, Fe, Si and O represent molybdenum. Bismuth, iron, silicon
and oxygen, respectiv(;ly; M represents at least one element selected from the group
consisting of cobalt and nickel; X represents at least one element selected from the
group consisting of chromium, lead, manganese, calcium, magnesium, niobium, silver,
barium, tin, tantalum, and zinc; Y represents at least one element selected from the
group consisting of phosphorus, boron, sulfur, selenium, tellurium, ceriimi, tungsten,
antimony and titanium; Z represents at least one element selected from the group
consisting of lithium, sodium, potassium, rubidium, cesium and thallium; and subscripts
a, b, c, d, e, f, g h and i represent an atomic ratio of each element, respectively; when a
is 12, b is in the range of from 0.01 to 3, c is in the range of from 0.01 to 5, d is in the
range of from 1 to 12, e is in the range of from 0 to 8, f is in the range of from 0 to 5, g
is in the range of from 0.001 to 2 and h is in the range of from 0 to 20 and i represents
the atomic ratio of oxygen necessary for fulfilling the requirement of the valence of
each element mentioned above.)
[0045]
In the method for producing an unsaturated aldehyde and an unsaturated carboxylic
acid of the present invention, propylene, isobutylene, TBA or MTBE which is a raw
material of the reaction is subjected to gas-phase catalytic oxidation with molecular
oxygen in the presence of the catalyst produced by the method of the present invention.
The reaction is normally carried out in the fixed bed. The catalyst may be packed either
in one layer or in two or more layers.
[0046]
The concentration of propylene, isobutylene, TBA or MTBE which is raw material of
the reaction in the feed gas can be changed in a wide range. Normally, the concentration
of the raw material of the reaction in the feed gas is preferably 1 to 20% by volume.
[0047]
It is economical to use air as a source of molecular oxygen, however, pure oxygen-
enriched air can be used when it is necessary. The molar ratio (volume ratio) of the raw
material of the reaction to oxygen in the feed gas is preferably 1:05 to 1:3.
[0048]
The feed gas preferably contains water other than the raw material of the reaction and
molecular oxygen. The concentration of water in the feed gas is preferably 1 to 45% by
volume. Further, it is preferable to use water diluted with inert gas such as nitrogen or
carbon dioxide.
[0049]
The reaction pressun? is preferably from normal pressure (atmospheric pressure) to
several hundred kilopa&cals. The reaction temperature can be selected normally in the
range of from 200 to 450°C and preferably from 250 to 400°C in particular. The contact
time is preferably 1.5 to 15 seconds.
EXAMPLES
[0050]
Hereinafter, the present invention will be entered into details with reference to the
examples and comparative examples.
[0051]
The term "part" in the examples and comparative examples means part by mass and a
batch type kneader equipped with dual arm type mixing blade was used in kneading.
Further the feed gas and the product gas were analyzed with gas chromatograph. The
catalyst composition was determined from the charged amount of the raw materials of
the catalyst.
[0052]
The conversion of propylene, isobutylene, TBA or MTBE in the examples and
comparative examples (hereinafter expressed as conversion) and the selectivity to an
unsaturated aldehyde and an unsaturated carboxylic acid to be produced were
determined by the foliow^ing formulae.
[0053]
Conversion (%) = A / B x 100
The selectivity to an unsaturated aldehyde (%) = C / A x 100
The selectivity to an unsaturated carboxylic acid (%) = D / A x 100
In these formulae, A is a number of mol(s) of the reacted propylene, isobutylene,
TBA or MTBE, B is a number of mol(s) of the supplied propylene, isobutylene, TBA or
MTBE, C is a number of mol(s) of the produced unsaturated aldehyde and D is a
number of mol(s) of the produced unsaturated carboxylic acid.
[0054]
Further, the viscosit)' of an organic binder was measured with 1% by mass water
solution or dispersion of the organic binder at 20°C by using a model B viscometer. The
solution or dispersion oi' the organic binder was prepared by using hot water method and
the like to prevent it from coagulation.
[0055]
Example 1
To 1,000 parts of pure water, 500 parts of ammonium paramolybdate, 6.2 parts of
ammonium paratungstate, 1.4 parts of potassium nitrate, 27.5 parts of antimony trioxide
and 495 parts of bismuth trioxide were added and stirred under heating (Liquid A).
Separately, to 1,000 parts of pure water, 114.4 parts of ferric nitrate, 281.6 parts of
cobalt nitrate and 42.1 parts of zinc nitrate were added in this order and dissolved
(Liquid B). Liquid B was added to Liquid A to obtain an aqueous slurry and the
resultant slurry was dried by using spray dryer to obtain dried spherical particles having
an average particle diameter of 60)Lim. The resultant dried spherical particles were
calcined at 300°C for 1 hour to obtain a calcined catalyst.
[0056]
To 500 parts of the resultant calcined catalyst, 15 parts of hydroxypropylmethyl
cellulose, the viscosity (of a 1% water solution at 20°C) of which was 16,000 mPas,
and 10 parts of hydroxypropylmethyl cellulose, the viscosity (of a 1% water solution at
20°Q of which was 40 mPas, were added and dry mixed. To the resultant mixture, 190
parts of pure water, the temperature of which was 5°C, was mixed at a rate of 25 parts /
min. (0.05 part / min. per 1 part of the calcined catalyst) and mixed (kneaded) by
kneader to the extent to obtain a clayey material and the resultant material was extrusion
molded by an auger type extruder to obtain a molded catalyst having an external
diameter of 5 mm, an internal diameter of 2 mm and an average length of 5 mm.
[0057]
Then, the resultant molded catalyst was dried at 110°C by using hot air dryer to
obtain a dried molded catalyst. Then, the resultant dried molded catalyst was calcined
again at 510°C for 3 hours to obtain a finally calcined molded catalyst.
[0058]
The elemental composition exclusive of oxygen of the resultant molded catalyst was
Moi2 Wo.i Bio.9 Fei.2 Sbo^ C04.1 Zno.e Ko.o6-
[0059]
The molded catalyst was packed in a tubular reactor made of stainless steel and the
reaction was carried out by using a feed gas containing 5% by volume of propylene,
12% by volume of oxygen, 10% by volume of water vapor and 73% by volume of
nitrogen under the condition of normal pressure, contact time of 3.6 seconds and
reaction temperature of 310°C.
As the result, conversion of propylene was 99.0%, the selectivity to acrolein was 91.1%
and the selectivity to acrylic acid was 6.5%.
[0060]
Example 2
The preparation of th(; molded catalyst and the reaction were carried out in the same
manner as in Example 1 except that 10 parts of curdlan, the viscosity (of a 1% water
solution at 20°C) of which was 35 mPas, was used instead of 10 parts of
hydroxypropylmethyl cellulose, the viscosity (of a 1% water solution at 20°C) of which
was 40 mPas. As the result, conversion of propylene was 99.0%, the selectivity to
acrolein was 91.1% and the selectivity to acrylic acid was 6.6%.
[0061]
Example 3
The preparation of the; molded catalyst and the reaction were carried out in the same
manner as in Example 1 except that 15 parts of methyl cellulose, the viscosity (of a 1%
water solution at 20°C) of which was 9,000 mPas, was used instead of 15 parts of
hydroxypropylmethyl cellulose, the viscosity (of a 1% water solution at 20°C) of which
was 16,000 mPa-s, and 10 parts of curdlan, the viscosity (of a 1% water solution at
20°C) of which was 60 mPas, was used instead of 10 parts of hydroxypropylmethyl
cellulose, the viscosity (of a 1% water solution at 20°Q of which was 40 mPas. As the
result, conversion of propylene was 98.9%, the selectivity to acrolein was 90.9% and
the selectivity to acrylic acid was 6.4%.
[0062]
Example 4
The preparation of the molded catalyst and the reaction were carried out in the same
manner as in Example 1 except that 40 parts of hydroxypropylmethyl cellulose, the
viscosity (of a 1% water solution at 20°C) of which was 16000 mPas, was used instead
of 15 parts of hydroxypropylmethyl cellulose, the viscosity (of a 1% water solution at
20°C) of which was 16,000 mPas, and 20 parts of curdlan, the viscosity (of a 1% water
solution at 20°C) of which was 40 mPas, was used instead of 10 parts of
hydroxypropylmethyl cellulose, the viscosity (of a 1% water solution at 20°C) of which
was 40 mPa-s. As the result, conversion of propylene was 98.8%, the selectivity to
acrolein was 90.8% and the selectivity to acrylic acid was 6.4%.
[0063]
Example 5
The preparation of the molded catalyst and the reaction were carried out in the same
manner as in Example 2 except that two kinds of organic binder were homogeneously
dispersed into 190 parts of hot water and the resultant dispersion was cooled to 5°C and
then added to 500 parts of the calcined catalyst at a rate of 25 parts / min. (0.05 part /
min. per 1 part of the calcined catalyst) and kneaded. As the result, conversion of
propylene was 98.9%, the selectivity to acrolein was 91.0% and the selectivity to acrylic
acid was 6.4%.
[0064]
Comparative Example 1
The preparation of the molded catalyst and the reaction were carried out in the same
manner as in Example 3 except that 25 parts of curdlan, the viscosity (of a 1% water
solution at 20°C) of which was 60 mPa-s, was used instead of 15 parts of methyl
cellulose, the viscosity (of a 1% water solution at 20°C) of which was 9,000 mPas, and
10 parts of curdlan, the viscosity (of a 1% water solution at 20°C) of which was 60
mPa-s. As the result, conversion of propylene was 98.8%, the selectivity to acrolein was
90.3% and the selectivity to acrylic acid was 6.2% were obtained. Further, the strength
of the catalyst thus obtained was deteriorated in comparison with that obtained in
Example 3.
[0065]
Comparative Example 2
The preparation of the molded catalyst and the reaction were carried out in the same
manner as in Example 3 except that 25 parts of methyl cellulose, the viscosity (of a 1%
water solution at 20°C) of which was 9,000 mPas, was used instead of 15 parts of
methyl cellulose, the viscosity (of a 1% water solution at 20°C) of which was 9,000
mPas, and 10 parts of curdlan, the viscosity (of a 1% water solution at 20°C) of which
was 60 mPa-s. As the result, conversion of propylene was 98.7%, the selectivity to
acrolein was 90.4% and the selectivity to acrylic acid was 6.3%.
[0066]
Comparative Example 3
The preparation of the molded catalyst and the reaction were carried out in the same
manner as in Example 1 except that 25 parts of hydroxypropylmethyl cellulose, the
viscosity (of a 1% water solution at 20°C) of which was 40 mPa-s, was used instead of
15 parts of hydroxypropylmethyl cellulose, the viscosity (of a 1% water solution at
20°C) of which was 16,000 mPas, and 10 parts of hydroxypropylmethyl cellulose, the
viscosity (of a 1% water solution at 20°C) of which was 40 mPas. As the result,
conversion of propylene was 98.9%, the selectivity to acrolein was 90.3% and the
selectivity to acrylic acid was 6.1%. Further, the strength of the catalyst thus obtained
was deteriorated in comparison with that obtained in Example 1.
[0067]
Comparative Example 4
The preparation of tlie molded catalyst and the reaction were carried out in the same
manner as in Example 1 except that 25 parts of hydroxypropylmethyl cellulose, the
viscosity (of a 1% water solution at 20°Q of which was 16,000 mPas, was used instead
of 15 parts of hydroxypropylmethyl cellulose, the viscosity (of a 1% water solution at
20°C) of which was 16,000 mPas, and 10 parts of hydroxypropylmethyl cellulose, the
viscosity (of a 1% water solution at 20°C) of which was 40 mPa-s. The moldability and
the product yield of the catalyst were considerably deteriorated. As the result,
conversion of propylene was 98.9%, the selectivity to acrolein was 90.4% and the
selectivity to acrylic acid was 6.2%.
[0068]
Example 6
To 1,000 parts of pure water, 500 parts of ammonium paramolybdate, 6.2 parts of
ammonium paratungstate, 23.0 parts of cesium nitrate, 24.0 parts of antimony trioxide
and 33.0 parts of bismuth trioxide were added and stirred under heating (Liquid A).
Separately, to 1,000 parts of pure water, 209.8 parts of ferric nitrate, 75.5 parts of nickel
nitrate, 453.3 parts of cobalt nitrate, 31.3 parts of lead nitrate and 2.8 parts of 85%
phosphoric acid were sequentially added in this order and dissolved (Liquid B). Liquid
B was added to Liquid A to obtain an aqueous slurry and the resultant slurry was dried
by using spray dryer to obtain dried spherical particles having an average particle
diameter of 60|i.m.
[0069]
The resuhant dried spherical particles were calcined at 300°C for 1 hour and at 510°C
for 3 hours to obtain a calcined catalyst.
[0070]
To 500 parts of the resultant calcined catalyst, 20 parts of hydroxypropylmethyl
cellulose, the viscosity (of a 1% water solution at 20°C) of which was 15,000 mPas,
and 5 parts of curdlan, the viscosity (of a 1% water solution at 20°Q of which was 40
mPa-s, were added and dry mixed. To the resultant mixture, 190 parts of pure water, the
temperature of which was 5°C, was mixed at a rate of 25 parts / min. (0.05 part / min.
per 1 part of the calcined catalyst) and mixed (kneaded) by kneader to the extent to
obtain a clayey material and the resultant material was extrusion molded by an piston
type extruder to obtain a molded catalyst having an external diameter of 5 mm, an
internal diameter of 2 mm and an average length of 5 mm.
[0071]
Then, the resultant molded catalyst was dried at 110°C by using hot air dryer to
obtain a dried molded catalyst. Then, the resultant dried molded catalyst was calcined
again at 400°C for 3 hours to obtain a finally calcined molded catalyst.
[0072]
The elemental composition exclusive of oxygen of the resultant molded catalyst was
Moi2 Wo.i Bio.6 Fe2.2 Sbo.7 Ni].] Coe.e Pbo.4 Po.i Cso.5.
[0073]
The molded catalyst was packed in a tubular reactor made of stainless steel and the
reaction was carried out by using a feed gas containing 5% by volume of isobutylene,
12% by volume of oxygen, 10% by volume of water vapor and 73% by volume of nitrogen
under the condition of normal pressure, contact time of 3.6 seconds and reaction
temperature of 340°C.
As the result, conversion of isobutylene was 98.0%, the selectivity to methacrolein
was 89.9% and the selectivity to methacrylic acid was 4.0%.
[0074]
Example 7
The preparation of the molded catalyst and the reaction were carried out in the same
manner as in Example 6 except that pure water was added at a rate of 175 parts / min.
(0.35 part / min. per 1 part of the calcined catalyst). The moldability and the product
yield of the catalyst were slightly deteriorated in comparison with those in Example 6.
As the result, conversion of isobutylene was 97.9%, the selectivity to methacrolein was
89.9% and the selectivity to methacrylic acid was 3.9%.
[0075]
Example 8
The preparation of the molded catalyst and the reaction were carried out in the same
manner as in Example 6 except that the temperature of pure water was 26°C. The
moldability and the product yield of the catalyst were slightly deteriorated in
comparison with those in Example 6. As the result, conversion of isobutylene was
97.8%, the selectivity to methacrolein was 89.8% and the selectivity to methacrylic acid
was 3.9%.
[0076]
Comparative Example 5
The preparation of the; molded catalyst and the reaction were carried out in the same
manner as in Example 6 except that 25 parts of curdlan, the viscosity (of a 1% water
solution at 20°C) of which was 40 mPas, was used instead of 20 parts of
hydroxypropylmethyl cellulose, the viscosity (of a 1% water solution at 20°C) of which
was 15,000 mPa-s, and 5 parts of curdlan, the viscosity (of a 1% water solution at 20°C)
of which was 40 mPas. As the result, conversion of isobutylene was 915%, the
selectivity to methacrolein was 89^% and the selectivity to methacrylic acid was 35%.
Further, the strength of the catalyst thus obtained was deteriorated in comparison with
that obtained in Example 6.
[0077]
Comparative Example 6
The preparation of the molded catalyst and the reaction were carried out in the same
manner as in Example 6 except that 25 parts of hydroxypropylmethyl cellulose, the
viscosity (of a 1% water solution at 20°Q of which was 15,000 mPas, was used instead
of 20 parts of hydroxypropylmethyl cellulose, the viscosity (of a 1% water solution at
20°C) of which was 15,000 mPa-s and 5 parts of curdlan, the viscosity (of a 1%
dispersion at 20°C) of which was 40 mPas. As the result, conversion of isobutylene was
97.6%, the selectivity to methacrolein was 89.6% and the selectivity to methacrylic acid
was 3.5%.
[0078]
Comparative Example 7
The preparation of the molded catalyst and the reaction were carried out in the same
manner as in Exampl(i 6 except that 20 parts of hydroxypropylmethyl cellulose, the
viscosity (of a 1% water solution at 20°Q of which was 1,600 mPas, was used instead
of 20 parts of hydroxypropylmethyl cellulose, the viscosity (of a 1% water solution at
20°C) of which was 15,000 mPas. As the result, conversion of isobutylene was 97.6%,
the selectivity to methacrolein was 89.7% and the selectivity to methacrylic acid was
3.5%. Further, the strength of the catalyst thus obtained was deteriorated in comparison
with that obtained in Example 6.
INDUSTRIAL APPLICABILITY
By the method for producing a catalyst of the present invention, a catalyst excellent
in catalyst activity and selectivity to an unsaturated aldehyde and an unsaturated
carboxylic acid can be produced and by the use of the catalyst of the present invention,
the unsaturated aldehyde and the unsaturated carboxylic acid can be produced in a high
yield.
We Claim:
1. A method for producing a catalyst comprising at least molybdenum,
bismuth and iron for use in producing an unsaturated aldehyde and an
unsaturated carboxylic acid through gas-phase catalytic oxidation of
propylene, isobutylene, tertiary butly alcohol or methyl tertiary butly
ether with molecular oxygen, comprising the steps of:
kneading particles comprising catalyst components, an organic binder
and a liquid to form a kneaded mixture; and
extrusion molding the kneaded mixture,
wherein the organic binder comprises at least a high-viscosity organic
binder having a visocisty of from 5,000 mPa.s to 25,000 mPa.s and a
low-viscosity organic binder having a viscosity of from 10 mPa.s to less
than 5,000 mPa.s, wherein viscosity is measured with a 1% by mass
water solution or dispersion of the binder at 20°C.
2. The method for producing the catalyst as claimed in claim 1, wherein
the liquid is added at the time of kneading at a rate of 0.2 parts by
mass/min per 1 part by mass of the particles or less comprising the
catalyst components.
3. The method for producing the catalyst as claimed in claim 1, wherein
the temperature of the liquid is 20°C or less.


A method for producing a catalyst comprising at least molybdenum, bismuth and
iron for use in producing an unsaturated aldehyde and an unsaturated carboxylic
acid through gas-phase catalytic oxidation of propylene, isobutylene, tertiary
butly alcohol or methyl tertiary butly ether with molecular oxygen, comprising the
steps of: kneading particles comprising catalyst components, an organic binder
and a liquid to form a kneaded mixture; and extrusion molding the kneaded
mixture, wherein the organic binder comprises at least a high-viscosity organic
binder having a visocisty of from 5,000 mPa.s to 25,000 mPa.s and a low-
viscosity organic binder having a viscosity of from 10 mPa.s to less than 5,000
mPa.s, wherein viscosity is measured with a 1% by mass water solution or
dispersion of the binder at 20°C.

Documents:

01645-kolnp-2006 abstract.pdf

01645-kolnp-2006 claims.pdf

01645-kolnp-2006 correspondence others.pdf

01645-kolnp-2006 correspondence.pdf

01645-kolnp-2006 description(complete).pdf

01645-kolnp-2006 form-1.pdf

01645-kolnp-2006 form-18.pdf

01645-kolnp-2006 form-2.pdf

01645-kolnp-2006 form-3.pdf

01645-kolnp-2006 form-5.pdf

01645-kolnp-2006 international publication.pdf

01645-kolnp-2006 international search authority report.pdf

01645-kolnp-2006 pct form.pdf

01645-kolnp-2006 priority document.pdf

01645-kolnp-2006-correspondence others-1.1.pdf

01645-kolnp-2006-form-26.pdf

1645-KOLNP-2006-CORRESPONDENCE.1.1.pdf

1645-KOLNP-2006-FORM-27.pdf

1645-kolnp-2006-granted-abstract.pdf

1645-kolnp-2006-granted-claims.pdf

1645-kolnp-2006-granted-correspondence.pdf

1645-kolnp-2006-granted-description (complete).pdf

1645-kolnp-2006-granted-examination report.pdf

1645-kolnp-2006-granted-form 1.pdf

1645-kolnp-2006-granted-form 18.pdf

1645-kolnp-2006-granted-form 2.pdf

1645-kolnp-2006-granted-form 26.pdf

1645-kolnp-2006-granted-form 3.pdf

1645-kolnp-2006-granted-form 5.pdf

1645-kolnp-2006-granted-reply to examination report.pdf

1645-kolnp-2006-granted-specification.pdf

1645-KOLNP-2006-OTHER PATENT DOCUMENT.pdf

1645-KOLNP-2006-PETITION UNDER RULE 137.pdf

1645-KOLNP-2006-TRANSLATED COPY OF PRIORITY DOCUMENT.pdf


Patent Number 236245
Indian Patent Application Number 1645/KOLNP/2006
PG Journal Number 42/2009
Publication Date 16-Oct-2009
Grant Date 13-Oct-2009
Date of Filing 14-Jun-2006
Name of Patentee MITSUBISHI RAYON CO., LTD.
Applicant Address 6-41, KONAL 1-CHOME, MINATO-KU TOKYO
Inventors:
# Inventor's Name Inventor's Address
1 MASAHIDE KONDO C/O CORPORATE RESEARCH LABORATORIES, MITSUBISHI RAYON CO., LTD., 20-1, MIYUKICHO, OTAKE-SHI, HIROSHIMA 739-0693
2 HIROYUKI NAITOU C/O CORPORATE RESEARCH LABORATORIES, MITSUBISHI RAYON CO. LTD., 20-1, MIYUKICHO, OTAKE-SHI, HIROSHIMA 739-0693
3 TORU KURODA C/O CORPORATE RESEARCH LABORATORIES, MITSUBISHI RAYON CO. LTD., 20-1, MIYUKICHO, OTAKE-SHI, HIROSHIMA 739-0693
PCT International Classification Number B01J 37/00, 23/888
PCT International Application Number PCT/JP2004/018402
PCT International Filing date 2004-12-09
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 2003-421279 2003-12-18 Japan