USOO7645897B2

(12) United States Patent (10) Patent No.: US 7,645,897 B2

Tu et al. (45) Date of Patent: Jan. 12, 2010
(54) PROCESS FOR PRODUCING METAL OXIDE (56) References Cited
CATALYST
U.S. PATENT DOCUMENTS
(76) Inventors: Xinlin Tu, c/o Toagosei Co., Ltd., 1-1, 5,994,580 A
2002/0115879 A1
11/1999 Takahashi et al.
8/2002 Hinago et al.
Funami-cho, Minato-ku, Nagoya-shi, 2004/0030202 A1 2/2004 Chaturvedi et al.
Aichi (JP) 455-0027; Naomasa Furuta,
c/o Toagosei Co., Ltd., 1-1, Funami-cho, FOREIGN PATENT DOCUMENTS
Minato-ku, Nagoya-shi, Aichi (JP) EP O761645 A2 3, 1997
455-0027: Yuuichi Sumida, c/o JP O7-010801 A 1, 1995
Toagosei Co., Ltd., 1-1, Funami-cho, JP O9-316O23 A 12/1997
JP 10-028862 A 2, 1998
Minato-ku, Nagoya-shi, Aichi (JP) JP 10-036311 A 2, 1998
455-0027 JP 10-137585 A 5, 1998
JP 2002-219362 A 8, 2002
(*) Notice: Subject to any disclaimer, the term of this JP 2004-025 178 A 1, 2004
patent is extended or adjusted under 35 WO 2004/024665 A1 3, 2004
U.S.C. 154(b) by 447 days. OTHER PUBLICATIONS
(21) Appl. No.: 11/665,153 Extended European Search Report dated Nov. 27, 2008.
(22) PCT Filed: Jul. 13, 2005 Primary Examiner Kamal A Saeed
(74) Attorney, Agent, or Firm Sughrue Mion, PLLC
(86). PCT No.: PCT/UP2005/O12896
(57) ABSTRACT
S371 (c)(1), A process for producing a high-performance catalyst for use
(2), (4) Date: Apr. 12, 2007 in a reaction for acrylic acid production from propane or
(87) PCT Pub. No.: WO2006/040863 propylene through air oxidation, is provided. A process for
producing a metal oxide catalyst having the following com
PCT Pub. Date: Apr. 20, 2006 position formula, the process comprising the following steps
(1) and (2):
(65) Prior Publication Data MoVA,B,C.O., Composition formula
US 2009/OO3O224A1 Jan. 29, 2009 (wherein A is Te or Sb; B is at least one element selected from
the group consisting of Nb, Ta, and Ti; C is Si or Ge; i and
(30) Foreign Application Priority Data each are 0.01-1.5 andj/i is from 0.3 to 1.0; k is 0.001-3.0; x is
0.002-0.1; and y is a number determined by the oxidized
Oct. 15, 2004 (JP) - - - - - - - - - - - - - - - - - - - - - - - - - - - - - 2004-301 355
states of the other elements),
Apr. 14, 2005 (JP) - - - - - - - - - - - - - - - - - - - - - - - - - - - - - 2005-116545
Step (1): a step in which an aqueous liquid containing Mo,
V, metal A and metal B is evaporated to dryness and the
(51) Int. Cl. Solid matter obtained is calcined at a high temperature to
C07C 255/08 (2006.01) thereby obtain a metal oxide; and
BOI 2/06 (2006.01) Step (2): a step in which in an atmosphere containing
BOI 2.3/4 (2006.01) Substantially no water, a compound containing metallic
BOI. 23/22 (2006.01) element C is adhered to the metal oxide obtained in step
(52) U.S. Cl. ....................... 558/319; 502/242: 502/248; (1) to form an oxide of metal C on the surface of the
502/309; 502/312:562/547:562/549 metal oxide.
(58) Field of Classification Search ....................... None
See application file for complete search history. 4 Claims, No Drawings
 US 7,645,897 B2
1. 2
PROCESS FOR PRODUCING METAL OXDE and a second-stage reaction for converting the acrolein to
CATALYST acrylic acid, and this process is complicated. There is room
for improvement.
TECHNICAL FIELD An object of the invention is to provide a process for
producing a catalyst with which acrylic acid can be produced
The present invention relates to a process for producing a in high yield even under Such reaction conditions that the
metal oxide catalyst for use in the production of acrylic acid proportion of water vapor is about 3.3 molper mol of propane.
by the vapor-phase contact oxidation of propane or propylene
and in the production of acrylonitrile by the ammoxidation of Another object is to provide a process for producing a
propane. 10 catalyst with which acrylic acid can be produced from pro
pylene in one stage.
BACKGROUND ART
Means for Solving the Problems
In general, acrylic acid is produced by a two-stage oxida The present inventors made intensive investigations in
tion reaction process which comprises a contact reaction of 15 order to overcome the problems described above. As a result,
propylene and oxygen in the presence of a catalyst to produce they have found that when a composite metal oxide obtained
acrolein, and then a contact reaction of the resultant acrolein from an Mo, Te, V composite metal oxide or Mo, Sb, V
and oxygen. Recently, however, processes for producing composite metal oxide by adhering a specific metal com
acrylic acid in one stage using propane as a starting material pound thereto in the absence of wateris used, thenacrylic acid
are being investigated, and many proposals have been made can be produced in high yield even under Such reaction con
on catalysts for use therein. Representative examples thereof ditions that the proportion of water vapor to propane is rela
include metal oxide catalysts such as an Mo, Te. V. Nb tively low. They have further found that with this composite
system (patent document 1) and Mo, Sb, V. Nb systems metal oxide, acrylic acid can be produced in one stage from
(patent documents 2 and 3). propylene as a raw material. The invention has been thus
Furthermore, Some patent applications were recently filed 25
completed.
with respect to processes for producing a catalyst having Namely, the invention provides a process for producing a
improved performances as compared with those metal oxide metal oxide catalyst having the following composition for
catalysts. For examples, patent document 4 discloses a pro
cess for producing a catalyst which comprises reacting a mula, the process comprising the following steps (1) and (2):
molybdenum compound, a vanadium compound, and an anti 30
MoVA,B,C.O., Composition formula
mony compound in an aqueous medium at 70° C. or higher,
mixing the resultantaqueous reaction solution with a niobium (wherein A is Te or Sb; B is at least one element selected from
compound, Subsequently vaporizing the resultant mixture to the group consisting of Nb, Ta, and Ti; C is Si or Ge; i and
dryness, and calcining the solid matter at a high temperature. each are 0.01-1.5 andj/i is from 0.3 to 1.0; k is 0.001-3.0; x is
Patent document 5 discloses a method of catalyst modifi 35
cation which comprises impregnating an Mo, Te, V catalyst 0.002-0.1; and y is a number determined by the oxidized
or an Mo, Sb, V catalyst with a solution containing one or states of the other elements)
more elements selected from the group consisting of W. Mo, Step (1): a step in which an aqueous liquid containing Mo,
Cr, Zr, Ti,Nb, Ta, V, B, Bi, Te, Pd, Co, Ni, Fe, P, Si, rare-earth V, metal A, and metal B is evaporated to dryness and the
elements, alkali metals, and alkaline earth metals to thereby 40 Solid matter obtained is calcined at a high temperature to
deposit other metal(s) on the catalyst. The catalytic perfor thereby obtain a metal oxide; and
mances of the modified catalyst in the ammoxidation reaction Step (2): a step in which in an atmosphere containing
of propane are evaluated therein. Substantially no water, a compound containing metallic
Patent Document 1: JP-A-7-010801 (claims) 45
element C is adhered to the metal oxide obtained in step
Patent Document 2: JP-A-9-316023 (claims) (1) to form an oxide of metal C on the surface of the
Patent Document 3: JP-A-10-036311 (claims) metal oxide.
Patent Document 4: JP-A-10-137585 (claims) The invention further provides a process for producing
Patent Document 5: JP-A-10-28862 (claims) acrylic acid or acrylonitrile, which comprises Subjecting pro
DISCLOSURE OF THE INVENTION 50 pane or propylene to oxidation through a vapor-phase contact
reaction or to ammoxidation in the presence of a metal oxide
catalyst obtained by the process described above.
Problems that the Invention is to Solve
In order for the one-stage oxidation reaction of propane to Advantages of the Invention
attain a high selectivity to acrylic acid with any of the cata 55 According to a production process of the invention, a metal
lysts heretofore in use, it is necessary to heighten the propor oxide catalyst is easily obtained with which acrylic acid can
tion of water vapor to propane in the reaction gas. Specifi be produced from propane or propylene in high yield. This
cally, water vapor proportions of 8.0 mol and higher per mol metal oxide catalyst has such an excellent performance that
of propane have been used. However, there has been a prob even when low-water-vapor reaction conditions, which bring
lem that when conditions including such a high water vapor 60 about a reduction in wastewater treatment and purification
proportion are employed, the Succeeding rectification step costs, are used, a selectivity to acrylic acid is not impaired.
and wastewater treatment step require a considerable cost and The catalyst attaining Such a high selectivity is especially
the overall cost of acrylic acid production increases. advantageous whena so-called recycling process is employed
On the other hand, an industrial process for producing in which propane, in particular, is separated and recovered as
acrylic acid from propylene has already been established. 65 a raw material.
However, the existing process is a two-stage process compris According to another production process of the invention,
ing a first-stage reaction for converting propylene to acrolein acrylic acid can be produced from propylene in one stage.
 US 7,645,897 B2
3 4
Furthermore, this metal oxide catalyst can be used also for case where the proportion thereof exceeds 3.0, the catalyst
the ammoxidation of propane. obtained has reduced activity, resulting in a poor conversion
of propane.
BEST MODE FOR CARRYING OUT THE The amount of the ammonia water to be added is such that
INVENTION the molar proportion of the ammonia to the metal B is 0.4 or
higher, preferably 0.8-3.0. In case where the ammonia
The aqueous liquid containing Mo, V, metal A, and metal amount is less than 0.4 in terms of molar proportion to the
metal B, no effect is obtained. On the other hand, even when
B, which is to be used in step (1) in the invention, preferably ammonia is used in an amount exceeding 3.0, the effect is not
is an aqueous liquid obtained by the following method. 10 enhanced and a costly waste gas treatment is necessary.
Namely, the preferred aqueous liquid containing Mo, V. It is preferred that nitric acid or ammonium nitrate be
metal A, and metal B is one prepared by first producing an further added to the dispersion of a finely particulate precipi
aqueous liquid containing Mo, V, and metal Ain the following tate obtained by adding ammonia water and a metal B com
manner and adding a metal B compound to the aqueous liquid pound. The amount of the nitric acid or ammonium nitrate to
obtained. The aqueous liquid containing Mo, V, and metal A 15 be added is such that the molar proportion of nitrate ions to the
may be obtained by mixing an Mo compound, V compound, metal B is preferably 2.0-6.0, more preferably 2.2-4.0. In case
and metal A compound, examples of which will be shown where the amount of the nitrate ions added is outside the
later, together in an aqueous medium and heating the resultant range, the effect of the addition is low.
liquid mixture with stirring. The temperature at which the The aqueous liquid obtained (usually in a slurry form) is
liquid mixture is heated is preferably 40°C. or higher, more heated and evaporated to dryness. The dried matter obtained
preferably 40-100° C. The heating time is preferably 1-10 is calcined in the presence of oxygen at a temperature of
hours, more preferably 2-5 hours. Metal A is Te or Sb as stated 250-380° C., preferably 280-360° C., for 0.5-10 hours, pref
above. Examples of the Te compound include metallic tellu erably 1-3 hours.
rium, tellurium dioxide, orthotelluric acid, metatelluric acid, The solid obtained by the calcining is calcined in the
and ammonium tellurate. The metallic tellurium preferably is 25 absence of oxygen at a temperature of 480-640°C., prefer
one which has undergone wet pulverization beforehand or ably 570-620° C., for 0.1-5 hours, preferably 0.2-1.5 hours.
one in the form of fine particles of 5.0 Lim or smaller obtained Step (1) ends with this calcining.
by reducing tellurium dioxide and telluric acid with a reduc A compound containing metallic element C (which is Sior
ing agent in an aqueous medium. Preferred examples of the Ge) (hereinafter this compound is referred to as metal C
Sb compound are metallic antimony and antimony trioxide. 30 compound) is adhered to the metal oxide (hereinafter often
Examples of the Mo compound include ammonium referred to as catalyst precursor) obtained in step (1)
molybdate, molybdenum oxide, and molybdic acid. Ammo described above, in an atmosphere in which water is absent.
nium molybdate is preferred of these compounds because it is Examples of methods for adhesion include: a method in
water-soluble. Preferred examples of the V compound which the metal C compound is vaporized and this vapor is
include ammonium metavanadate and Vanadium pentoxide. 35 contacted with the metal oxide; and a method in which the
The amounts of the Mo compound, metal A compound, metal oxide is immersed in an anhydrous organic-solvent
and V compound to be added are as follows. The atomic Solution of the metal C compound and the organic solvent is
proportions of the V and metal A (i and j) to the Mo are then volatilized. The catalyst precursor to be subjected to this
0.01-1.5 each, and the atomic ratio of the metal Ato the V (j/i) adhesion of a metal C compound preferably is in the form of
is 0.3-1.0. In case where the proportion of any of the Mo, V. 40 particles having a particle diameter of about from 0.1 mm to
and metal A is outside the range, the target metal oxide cata several millimeters. The catalyst precursor having Such a
lyst having high catalytic performances cannot be obtained. particle size may be one obtained by sieving the metal oxide
By adding a metal B compound (metal B is at least one powder obtained in step (1) or may be one obtained by depos
iting the metal oxide powder on a Support and then classifying
element selected from the group consisting of Nb, Ta, and Ti) 45 it to obtain an even particle size.
to the reaction liquid obtained by the procedure described As the metal C compound, use can be made of a metal C
above, the aqueous liquid containing Mo, V, metal A, and compound in the form of a chloride, organometallic com
metal B is obtained. From the standpoint of the performances pound, alkoxide, or the like. However, an alkoxide is pre
of the metal oxide catalyst to be obtained, it is more preferred ferred from the standpoint of handleability. Examples thereof
to add ammonia water when the metal B compound is added. 50 include silicon tetrachloride, tetramethoxysilane, tetraethox
There are no particular limitations on the temperature of ysilane, trimethoxysilane, triethoxysilane, trimethylsilane,
the liquid to which ammonia water and the metal B compound triethylsilane, hexamethyldisilane, hexamethyldisilaZane,
are to be added. Usually, the temperature thereofmay be room hexamethylsiloxane, and tetraethoxygermanium. More pre
temperature. By the addition of ammonia water and the metal ferred are tetraethoxysilane, triethoxysilane, triethylsilane,
B compound, a finely particulate precipitate is formed in the 55 and tetraethoxygermanium.
reaction liquid. The method in which the vapor of a metal C compound is
Examples of the metal B compound include oxides, adhered to particles of the catalyst precursor can be any of all
nitrates, carboxylates, oxoacid salts, and oxalates. A metal B known methods as long as the adhesion can be conducted in
compound which is insoluble may be used in the form of a an atmosphere in which water is absent.
dispersion in water. In this case, however, the compound can 60 Simple methods usable on a laboratory scale include a
be dissolved in the water by using oxalic acid or the like in method in which use is made of a scrubbing bottle (equipped
combination therewith. The metal B compound is added in with a filter) for use in removing dust particles or the like from
Such an amount as to yield a metal oxide catalyst in which the a gas by passing the gas through a liquid placed in the cylin
atomic proportion of metal B is 0.001-3.0 when the Mo pro drical vessel. Namely, it is a method which comprises placing
portion is 1. In case where the proportion of metal B in the 65 a liquid metal C compound in a cylindrical scrubbing bottle
catalyst is lower than 0.001 when the Mo proportion is 1, the beforehand, passing a dehydrated inert gas (hereinafter often
catalyst obtained is apt to deteriorate. On the other hand, in referred to as carrier gas) Such as, e.g., dry nitrogen gas
 US 7,645,897 B2
5 6
through the liquid to thereby produce a dehydrated inert-gas The organic solvent to be used is not particularly limited.
stream containing the vapor of the metal C compound in an However, it is preferred to use a hydrocarbon, e.g., toluene or
amount corresponding to the vapor pressure, and bringing hexane. The water content in the organic solvent is preferably
this stream into contact with particles of the catalyst precur 0.005% by mass or lower, more preferably 0.002% by mass or
SO. lower. In the case where the organic solvent has a water
The vapor pressure of the metal C compound in the method content exceeding 0.005% by mass, it is preferred to conduct
described above depends on the temperature and pressure of dehydration by a known method, preferably the molecular
the atmosphere. A simple method for increasing the vapor sieve drying method.
pressure is to elevate the temperature of the metal C com The amount of the organic solvent to be used for the
pound placed in the cylindrical vessel. For selecting a tem 10 impregnation is 0.5-100 times, preferably 1-20 times, by vol
perature for this heating, it is advantageous to refer to the ume the amount of the catalyst. In case where the amount of
boiling point of the metal C compound. Examples of the the organic solvent used is less than 0.5 times, the effect of
boiling points of metal C compounds include 121.8° C. for modification is poor because the metal C compound cannot
tetramethoxysilane, 166.8° C. for tetraethoxysilane, 133.5° evenly adhere to the whole catalyst. On the other hand, even
C. for triethoxysilane, 107° C. for triethylsilane, 253° C. for 15 when the amount of the organic solvent used exceeds 100
tetraethoxygermanium, and 57.6°C. for silicon tetrachloride. times the amount of the catalyst, the effect is not enhanced
Besides the temperature of the metal C compound, the flow and the solvent cost increases for the limited effect. The
rate of the carrier gas influences the amount of the metal C concentration of the metal C compound in the organic solvent
compound to be adhered to the catalyst precursor. A Suitable is in the range of 0.5-300 umol/mL, preferably 5-150 umol/
carrier gas flow rate is 1,800-5,000 hr' in terms of space mL. In case where the concentration of the metal C compound
Velocity. It is preferred that a gas mixture having a metal C in the organic solvent is lower than 0.5umol/mL, it is difficult
compound vapor concentration of 0.1-10,000 ppm, more to deposit metal C and the effect of deposition is low. On the
preferably 1-1,000 ppm, be formed by using a suitable com other hand, in case where the concentration thereof exceeds
bination of a carrier gas flow rate and a vapor pressure of the 300 umol/mL, deposition becomes uneven and the original
metal C compound. 25 modification effect is not exhibited.
The carrier gas containing the metal C compound in that After the catalyst precursor is impregnated with a solution
concentration is kept in contact with the catalyst precursor for containing a metal C compound and then taken out of the
an appropriate time period, whereby metal C can be adhered Solution, the organic solvent is volatilized and removed from
in that amount in the metal oxide catalyst which is determined the precursor. The organic solvent may be directly volatilized.
by the composition formula given above, i.e., in an amount of 30 However, it is preferred that the catalyst precursorbe washed
0.002-0.1 mol per mol of the Mo. with the dehydrated organic solvent to remove the raw-mate
The adsorption of the metal C compound onto particles of rial C compound remaining unreacted before the organic
the catalyst precursor is preferably conducted in the inside of solvent is volatilized. This method can further heighten the
effect of modification.
a vessel blocked from the atmosphere, by fixed-layer adsorp 35 For removing the organic solvent after the washing, a
tion or fluidizing-layer adsorption. The temperature of the known method can be employed, such as distillation, cen
catalyst precursor particles during the adsorption of the metal trifugal separation, or filtration. Thereafter, the catalyst pre
C compound is preferably from room temperature to 350° C. cursor is heated to 50-300° C., whereby the metal C com
more preferably 50-300° C. When the vapor of the metal C pound which has adhered to the catalyst precursor can be
compound comes into contact with the catalyst precursor kept 40 converted to a metal oxide and fixed to the precursor Surface.
at this temperature, the metal C compound adsorbed on the The contents of the metal ingredients in the metal oxide
precursor Surface rapidly changes into a metal oxide and is catalyst of the invention obtained by fixing an oxide of metal
fixed to the precursor surface without fail. C can be determined by fluorescent X-ray analysis.
In the case where fixed-layer adsorption is employed, use is The mechanism by which the adhesion of a metal C com
made, for example, of a method comprising packing a cylin 45 pound to the catalyst precursor improves selectivity has not
drical vessel with particles of the catalyst precursor, exter been elucidated. However, it is presumed that sites which
nally heating this vessel beforehand, and passing the carrier participate in side reactions were blocked by chemical reac
gas containing the vapor of the metal C compound through tions between the ligand of the metal C compound and Surface
the vessel. Thus, an oxide of metal C can be formed on the functional groups of the catalyst precursor and the side reac
precursor Surface. 50 tions could hence be inhibited to thereby bring about the
A metal oxide catalyst having the same performances can selectivity improvement. Incidentally, it is presumed that in
be produced also by the method which comprises impregnat case where a metal C compound is adhered in the presence of
ing the catalyst precursor with a solution containing a metal C water, the metal C compound hydrolyzes and adheres not
compound to thereby adhere the metal C compound to the only to sites participating inside reactions but also to effective
catalyst precursor and then converting the adherend metal C 55 active sites to thereby considerably reduce activity.
compound to an oxide. It is preferred that the metal oxide catalyst obtained as
In the case where the catalyst precursor to be subjected to particles be used in this particulate form. Pulverizing the
the impregnation is temporarily exposed to the outside air, the particles may result in a decrease in catalytic performance.
catalyst precursor absorbs moisture in the outside air. It is Although the metal oxide catalyst is usable in the Support-free
therefore preferred that a dehydration treatment should be 60 state, it may be used after having been deposited on a known
conducted before the impregnation treatment. The tempera Support having an appropriate particle size, such as silica,
ture for the dehydration is 50-300° C., preferably70-250° C. alumina, silica-alumina, silicon carbide, or the like. There are
In case where the dehydration temperature is below 50°C., no no particular limitations on deposition amount, and a known
dehydration effect is obtained. In case where the dehydration deposition amount can be advantageously employed.
temperature exceeds 300° C., the surface properties of the 65 An explanation is given on the vapor-phase contact oxida
catalyst precursor change and a chemical reaction for depos tion reaction of propane in which the metal oxide catalyst
iting the metal C compound is difficult to proceed. produced by the process described above is used. Propane and
 US 7,645,897 B2
7 8
molecular oxygen (hereinafter referred to as oxygen gas) are In the case of propylene oxidation, the following were
introduced as raw materials for acrylic acid production into a used.
reactor packed with the metal oxide catalyst and kept at a high Conversion of propylene (%)=100x (propylene fed)-(un
temperature to thereby produce acrylic acid. Propane and reacted propylene)/(propylene fed)
oxygen gas may be separately introduced into the reactor and Selectivity to acrylic acid (%)=100x(acrylic acid yielded)/
mixed with each other in the reactor. Alternatively, the two (propylene fed)-(unreacted propylene)
may be mixed beforehand and introduced in a mixed state into Selectivity to acrolein (%)=100x(acrolein yielded)/(pro
the reactor. For reaction control, it is preferred to use nitrogen, pylene fed)-(unreacted propylene)
steam, carbon dioxide, or the like as a diluent gas in combi Yield of acrylic acid (%)=(conversion of propane)x(selec
nation with the reactants. 10
In the case where propane and air are used as raw materials, tivity to acrylic acid)/100
the proportion of the air to the propane is preferably up to 30 EXAMPLE 1.
times, more preferably 0.2-20 times, in terms of volume pro
portion. The proportion of the Steam to the propane is pref
erably in the range of 0.8-8. In case where the proportion of 15 Into a 500-mL flask made of glass were introduced 2.66 g
the steam to the propane is lower than 0.8, a combustion of ammonium metavanadate, 15.45 g of ammonium molyb
reaction occurs consecutively, resulting in a low selectivity to date, and 50 mL of distilled water. The solids were dissolved
acrylic acid. In case where the proportion thereof exceeds 8 with stirring at a temperature around 80°C. After completion
times, the cost of a rectification step and wastewater treatment of the dissolution, the heating was stopped and 30 mL of an
step increases, resulting in a disadvantage in profitability. The aqueous dispersion containing 1.46 g of tellurium metal par
reaction temperature is in the range of 300-460° C., prefer ticles (rod-shaped particles having an average major-axis
ably in the range of 350-420°C. A suitable space velocity of length of 0.3 um and an average minor-axis length of 0.1 um)
the raw-material gas is 1,000-8,000 hr'. In case where the obtained by reducing tellurium dioxide with hydrazine was
space velocity thereof is lower than 1,000 hr', the spacetime added to the solution. Furthermore, 1.0 g of 30% ammonia
yield of acrylic acid as the target compound decreases. In case 25 water was added dropwise thereto. The reaction liquid was
where the space velocity thereof exceeds 8,000 hr', the stirred for several minutes, through which the temperature
conversion decreases. thereof became 50° C.
The propane remaining unreacted and the propylene as an To this reaction liquid was added an aqueous Solution
intermediate product which are contained in the reaction gas obtained by dissolving 5.89 g of oxalic acid and 2.32 g of
discharged through the outlet of the reactor may be directly 30 niobic acid in 160 mL of distilled water. The liquid mixture
used as a fuel. However, the propane and propylene may be obtained was stirred for 5 minutes, and 4.0 g of ammonium
separated from other ingredients in the reaction gas, returned nitrate was further added thereto. Thereafter, this mixture was
to the reactor, and reused. As a method for separating the evaporated to dryness with a 120° C. dryer.
unreacted propanegas from other ingredients including reac The dried matter obtained was calcined at 320°C. for 1.5
tion products and the inert gas, use can be made of the known 35
hours in an air atmosphere. The Solid particles thus obtained
pressure-swing adsorption method (PSA method), organic were calcined at 590° C. for 1.5 hours in a stainless-steel
solvent adsorption method, or the like. The metal oxide cata calcining tube to thereby obtain a metal oxide. Furthermore,
lyst produced by the invention is applicable also to the oxi particles having a particle diameter of 0.5-1 mm were taken
dation of propylene and the ammoxidation of propane, and out with sieves, and were used in the following experiment.
acrylic acid or acrylonitrile can be synthesized in high yield. 40
As a result of fluorescent X-ray analysis for composition, the
Conditions of the oxidation of propylene or ammoxidation of metal oxide (hereinafter referred to as four-metal oxide) was
propane may be almost the same as the conditions of the found to have the following atomic ratio: Mo?V/Te/Nb=1.0/
vapor-phase contact oxidation of propane described above. 0.28/0.14/0.16 (molar ratio).
The invention will be explained below in more detail by The four-metal oxide obtained by the procedure described
reference to Examples and Comparative Examples. The 45
above was packed, in an amount of 1.0 g, into the space over
metal oxide catalysts obtained in the Examples and Compara a metal gauze placed in a silica tube. This tube was held at
tive Examples were evaluated for catalytic performances by 200° C. for about 30 minutes while passing dry nitrogen gas
the following method. Into a 10-mmdD reaction tube made of therethrough at a flow rate of 0.2L/min. Thereafter, the nitro
quartz was packed 1.0 g (0.8-1.0 mL) of a catalyst having an gen gas line was connected to a scrubbing bottle containing
average particle diameter of 0.5-1 mm. The reaction tempera 50
tetraethoxysilane kept at 50° C. While the flow rate of nitro
ture in this reaction tube (the temperature measured with a gen was kept at 0.5 L/min, the vapor of tetraethoxysilane was
thermocouple fixed to a central part of the catalyst layer) was brought for 5 minutes into contact with the metal oxide par
set at 370° C. A mixed gas composed of 7.6% by volume ticles kept at 200° C. Thus, a metal oxide catalyst was
propane, 14.2% by volume oxygen gas, 53.5% by volume obtained.
nitrogen gas, and 24.7% by Volume water vapor was fed to the 55
reaction tube at a space velocity of 2.200/hr to thereby This metal oxide catalyst was found to have the following
produce acrylic acid. composition: MO/V/TefNb/Si=1.0/0.28/0.1470.1670.011
The reaction products were analyzed for composition. (molar ratio). The yield of acrylic acid, etc. in the oxidation
Based on this, the conversion of the propane and the selectiv reaction of propane using this catalyst are as shown in Table
ity to acrylic acid which are represented by the following 60 1.
equations were calculated (each by mole).
Conversion of propane (%)=100x (propane fed)-(unre EXAMPLE 2
acted propane)/(propane fed)
Selectivity to acrylic acid (%)=100x(acrylic acid yielded)/ The same procedure as in Example 1 was conducted,
(propane fed)-(unreacted propane) 65 except only that the vapor of triethoxysilane was brought into
Yield of acrylic acid (%)=(conversion of propane)x(selec contact with the four-metal oxide produced as a catalyst pre
tivity to acrylic acid)/100 cursor in Example 1. Thus, a metal oxide catalyst having a
 US 7,645,897 B2
9 10
metal composition of Mo?V/Te/Nb/Si=1.0/0.28/0.14/0.16/ Before being used in the propane oxidation reaction, the
0.012 (molar ratio) was obtained. metal oxide catalyst is heated to 370°C. in a column packed
therewith to thereby convert the silicon atoms derived from
EXAMPLE 3 tetraethoxysilane adhered by the procedure described above
to an oxide. The metal oxide catalyst in this state had the
The same procedure as in Example 1 was conducted, following composition: Mo/V/Te/Nb/Si=1.0/0.28/0.14/0.16/
except only that the vapor of triethylsilane was brought into 0.014 (molar ratio).
contact with the four-metal oxide produced as a catalyst pre
cursor in Example 1. Thus, a metal oxide catalyst having a EXAMPLE 7
metal composition of Mo?V/Te/Nb/Si=1.0/0.28/0.14/0.16/ 10
0.033 (molar ratio) was obtained. The same catalyst as in Example 6 was used in reaction
evaluation, in which propylene was passed, in place of pro
EXAMPLE 4 pane, through a reactor at the same flow rate to conduct an
oxidation reaction. The reaction evaluation was conducted at
The same procedure as in Example 1 was conducted, 15
340°C. As a result, a conversion of the propylene of 98.4%,
except only that the vapor of triethoxygermanium was a selectivity to acrylic acid of 84.7%, and a selectivity to
acrolein of 1.1% were obtained.
brought into contact with the four-metal oxide produced as a
catalyst precursor in Example 1. Thus, a metal oxide catalyst COMPARATIVE EXAMPLE 1
having a metal composition of Mo?V/Te/Nb/Ge=1.0/0.28/
0.14/0.16/0.007 (molar ratio) was obtained. The four-metal oxide produced as a catalyst precursor in
The metal oxide catalysts obtained in Examples 2 to 4 were Example 1 was used as a catalyst to conduct a reaction for
used to conduct a reaction for acrylic acid synthesis by pro acrylic acid synthesis by propane oxidation in the same man
pane oxidation. The results thereof are as shown in Table 1. ner as in the Examples given above. The results thereof areas
shown in Table 1.
EXAMPLE 5 25
COMPARATIVE EXAMPLE 2
A 1.02-g portion of the four-metal oxide particles produced
as a catalyst precursor in Example 1 was dehydrated by heat The same procedure as in Comparative Example 1 was
ing it at 220°C for 30 minutes in nitrogen and subsequently conducted, except only that the reaction temperature was
treated in the following manner without being exposed to the 30 changed to 360° C.
air. In a nitrogen atmosphere, the metal oxide particles which
had been returned to room temperature were added to 7.5 mL COMPARATIVE EXAMPLE 3
of an n-hexane Solution having a tetraethoxysilane concen
tration of 12 umol/mL (the n-hexane used was one which had The same procedure as in Comparative Example 1 was
been dehydrated with molecular sieve 4A) and this mixture 35 conducted, except only that the reaction temperature was
was sufficiently stirred. Thereafter, the mixture was heated at changed to 350°C. It can be seen from the results of a propane
80° C. for 30 minutes or longer in a nitrogen stream to vapor oxidation reaction using the catalysts of Comparative
ize the hexane. Example 2 and Comparative Example 3 that the regulation of
The metal oxide catalyst obtained was used in the oxidation reaction temperature, when employed as the only measure, is
reaction of propane in the same manner as in the Examples 40 less effective in improving product selectivity in the oxidation
given above. Before being used in the propane oxidation reaction.
reaction, the metal oxide catalyst is heated to 370° C. in a COMPARATIVE EXAMPLE 4
column packed therewith to thereby convert the silicon atoms
derived from tetraethoxysilane adhered by the procedure
described above to an oxide. The metal oxide catalyst in this 45 In a beaker was placed 0.094 g of a silica sol manufactured
state had the following composition: Mo/V/Te/Nb/Si=1.0/ by Nissan Chemical Industries, Ltd. (trade name, Snowtex
0.28/0.14/0.16/0.016 (molar ratio). 30; aqueous dispersion of fine silica particles; SiO concen
tration, 30 wt %). Thereto was added 5.0 g of distilled water
EXAMPLE 6 to dissolve the sol. To this solution were added 2.5 g of the
50
four-metal oxide particles produced as a catalyst precursor in
A 1.02-g portion of the four-metal oxide particles produced Example 1. The resultant mixture was evenly mixed and then
as a catalyst precursor in Example 1 was dehydrated by heat dried at 120° C. for 2 hours. The metal oxide catalyst obtained
ing it at 90° C. for 30 minutes in nitrogen and subsequently had the following metal composition: Mo?V/Te/Nb/Si=1.0/
treated in the following manner without being exposed to the 0.28/0.14/0.16/0.053 (molar ratio).
a1. 55
The catalyst obtained was used to conduct a reaction for
acrylic acid synthesis by propane oxidation in the same man
In a nitrogen atmosphere, the metal oxide particles which ner as in the Examples and Comparative Examples given
had been returned to room temperature were added to 4.5 mL above.
ofa toluene solution having a tetraethoxysilane concentration
of 100 umol/mL (the toluene used was one which had been COMPARATIVE EXAMPLE 5
dehydrated with molecular sieve 4A) and this mixture was 60
sufficiently stirred and then heated at 90° C. for 1 hour. In this The four-metal oxide produced as a catalyst precursor in
heating, the solvent was refluxed. After completion of heat Example 1 was used as a catalyst to conduct a reaction for
ing, the mixture was allowed to cool to room temperature and acrylic acid synthesis by propylene oxidation in the same
filtered in the air. The particles recovered were washed with manner as in Example 7. A conversion of the propylene of
10 mL of a solvent, which was used in several portions. The 65 98.1%, a selectivity to acrylic acid of 73.4%, and a selectivity
metal oxide catalyst obtained was used in the oxidation reac to acrolein of 3.4% were obtained at a reaction temperature of
tion of propane in the same manner as in the Example 1. 340° C.
 US 7,645,897 B2
11 12
TABLE 1.
Results of reaction

C compound for vapor Molar ratio of deposit Conversion Selectivity Yield

deposition ingredients (MMo) of P.9% to AA,% of AA,%
Example 1 tetraethoxysilane SiMo = 0.011, 1.0 60.3 75.4 45.4
Example 2 triethoxysilane SiMo = 0.012, 1.0 53.5 80.8 43.2
Example 3 triethylsilane SiMo = 0.0331.0 59.2 73.8 43.7
Example 4 tetraethoxygermanium Ge/Mo = 0.045/1.0 57.8 74.6 43.1
Example 5 tetraethoxysilane SiMo = 0.016, 1.0 60.8 744 45.2
Example 6 tetraethoxysilane SiMo = 0.014f1.0 56.4 81.2 45.8
Results of reaction

C compound for Molar ratio of deposit Conversion Selectivity Yield

impregnant liquid ingredients (MMo) of P.9% to AA,% of AA,%
Comparative none 61.O 70.1 42.7
Example 1
Comparative none S4.3 71.2 35.8
Example 2
Comparative none 49.1 67.0 32.9
Example 3
Comparative silica Sol SiMo = 0.0531.0 59.0 69.6 41.1
Example 4 (Snowtex. 30)
P represents propane.
AA represents acrylic acid.
M is Sior Ge.

INDUSTRIAL APPLICABILITY Solid matter obtained is calcined at a high temperature to

thereby obtain a metal oxide; and
According to the metal oxide catalyst obtained by the Step (2): a step in which in an atmosphere containing
invention, acrylic acid can be produced in high yield using Substantially no water, a compound containing metallic
propane and air or propylene and air as raw materials. Fur element C is adhered to the metal oxide obtained in step
thermore, acrylonitrile can be produced with the catalyst in (1) to form an oxide of metal C on the surface of the
high yield using propane and ammonia as raw materials. 35
metal oxide.
2. The process for producing a metal oxide catalyst of claim
The invention claimed is: 1, wherein in step (2), a vapor obtained by heating the com
1. A process for producing a metal oxide catalyst having the pound containing metallic element C is adhered to the metal
following composition formula, the process comprising the oxide obtained in step (1) to form an oxide of metal C on the
following steps (1) and (2): surface of the metal oxide.
MoVA,B,C.O., Composition formula 3. A process for producing acrylic acid, which comprises
oxidizing propane or propylene through a vapor-phase con
(wherein A is Te or Sb; B is at least one element selected from tact reaction in the presence of a metal oxide catalyst pro
the group consisting of Nb, Ta, and Ti; C is Si or Ge; i and duced by the process of claim 1 or 2.
each are 0.01-1.5 andj/i is from 0.3 to 1.0; k is 0.001-3.0; x is 4. A process for producing acrylonitrile, which comprises
45
0.002-0.1; and y is a number determined by the oxidized Subjecting propane to ammoxidation in the presence of a
states of the other elements), metal oxide catalyst produced by the process of claim 1 or 2.
Step (1): a step in which an aqueous liquid containing Mo,
V, metal A and metal B is evaporated to dryness and the k k k k k