CN1697702A - Process for producing composite oxide catalyst - Google Patents
Process for producing composite oxide catalyst Download PDFInfo
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- CN1697702A CN1697702A CN 200480000370 CN200480000370A CN1697702A CN 1697702 A CN1697702 A CN 1697702A CN 200480000370 CN200480000370 CN 200480000370 CN 200480000370 A CN200480000370 A CN 200480000370A CN 1697702 A CN1697702 A CN 1697702A
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- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- B01J23/88—Molybdenum
- B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8877—Vanadium, tantalum, niobium or polonium
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- B01J23/85—Chromium, molybdenum or tungsten
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
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- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
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- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
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Abstract
A process for producing a composite oxide catalyst with which an unsaturated aldehyde is catalytically oxidized in a vapor phase with a gas containing molecular oxygen to stably produce the corresponding unsaturated carboxylic acid in high yield over long. The process, which is for producing a composite oxide catalyst represented by the formula Mo12VaXbCucYdCeSifOg (wherein X represents at least one element selected between niobium and tungsten; Y represents at least one element selected from the group consisting of antimony, magnesium, calcium, strontium, barium, and zinc; and a, b, c, d, e, f, and g, which indicate the atomic proportions of the respective elements, are as follows: 0<a<=12, 0<=b<=12, 0<c<=12, 0<=d<=8, 0<=e<=1,000, and 0<=f<=1,000 when the number of molybdenum atoms is 12, and g is the number of oxygen atoms satisfying the oxidized states of the constituent elements excluding silicon and carbon in the formula), comprises uniting source compounds for the respective elements in an aqueous medium system in the presence of an organic acid, drying the resultant aqueous solution or dispersion of the united matter to prepare a powder, molding the powder, and burning the molding.
Description
Technical field
The present invention relates to utilize the gas that contains molecular oxygen to make unsaturated aldehyde carry out catalytic gas phase oxidation and stable for a long time and prepare the preparation method of the composite oxide catalysts that corresponding unsaturated carboxylic acid uses with high yield.
Background technology
Past attempts proposes to utilize molecular oxygen to make unsaturated aldehydes such as methacrylaldehyde, MAL carry out all schemes that catalytic gas phase oxidation prepares the catalyst that unsaturated carboxylic acids such as acrylic acid, methacrylic acid use.From considering by the viewpoint of the rationalization of effective utilization of the unsaturated aldehyde raw material of olefin production and course of reaction, the often demanding unsaturated aldehyde conversion ratio of these catalyst or as the high selectivity of the unsaturated carboxylic acid of object.This occasion, for example, prepare acrylic acid reaction, carry out with 3,000,000 tons/year scale usually by methacrylaldehyde, even, also can increase significantly with the level of hundreds of～thousands of tons of as the acrylic acid amount of products therefrom so above-mentioned conversion ratio or selection rate improved 0.1% o'clock.Therefore, improve the catalyst performance of conversion ratio or selection rate etc., although be to improve seldom, also greatly help the rationalization of resources effective utilization or technology.
Past is for the catalyst performance of the feed stock conversion that improves these reactions or selection rate etc. has proposed all schemes.As the composite oxide catalysts with these excellent properties, the applicant has also proposed for example scheme such as patent documentation 1.Patent documentation 1 is to have the Mo of containing
12Nb
aV
bCu
cSi
dC
eX
fY
gZ
hO
i(in the formula, X represents to be selected from least a kind of element among alkali metal and the Tl, and Y represents to be selected from least a kind of element among Mg, Ca, Sr, Ba and the Zn, and Z represents to be selected from least a kind of element among W, Ce, Sn, Cr, Mn, Fe, Co, Y, Nd, Sm, Ge and the Ti.A, b, c, d, e, f, g and h represent each atoms of elements ratio, with respect to molybdenum atom 12, then a is 0＜a≤12,0＜b≤10,0＜c≤8,0＜d≤1000,0＜e≤1000,0≤f≤2,0≤g＜5,0≤h＜5, i is the number that oxidizability determined of removing each composition of Si and C in aforementioned each composition) the catalyst of composition.
In addition, patent documentation 2 relates to the applicant and other applicants, and the catalyst as same reaction is used discloses formula: Mo
12V
gSb
hA
iB
jC
k(in the formula, A is one or more the element that is selected among Nb and the Ta, and B is Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Cr, W, Mn, Fe, Ru, Co, Ni or P, and C is Ag, Zn, Ti, Sn, Pb, Cu, As or Se.G and h are respectively 0.01～1.5, and h/g=0.3～1.0, and i is 0.001～3.0, J is 0.0001～0.1, K is 0～0.05) shown in catalyst.
Yet though these composite oxide catalysts in the past demonstrate excellent performance respectively, but still expectation further improves the performance of raw material unsaturated aldehyde conversion ratio or unsaturated carboxylic acid selection rate.
Patent documentation 1: the spy opens the 2003-200055 communique
Patent documentation 2: the spy opens the 2000-317309 communique
Summary of the invention
The problem that invention will solve
The invention provides a kind of novel preparation method of composite oxide catalysts, the gas that this catalyst contains molecular oxygen in utilization makes unsaturated aldehyde carry out catalytic gas phase oxidation when preparing unsaturated carboxylic acid, the performance that shows is, give the high conversion of raw material unsaturated aldehyde and the high selectivity of unsaturated carboxylic acid, and long-time stable.
Solve the means that problem is used
What the present inventor studied with great concentration in order to achieve the above object found that, identical and even similar with above-mentioned patent documentation 1 or patent documentation 2 Mo that contains, V, X (is selected from least a element among Nb and the W, Y (is selected from Sb, Mg, Ca, Sr, at least a element among Ba and the Zn), Cu, the composite oxide catalysts of Si and C, but when this catalyst of preparation, by in the presence of organic acid in aqueous medium the starting compound each element integrated, and the integrated thing that will obtain carries out drying, moulding, roasting, then improved the performance of this catalyst and the conversion ratio of unsaturated aldehyde, especially improved selection rate as the unsaturated carboxylic acid of object.
In the preparation of the above-mentioned composite oxide catalysts of the present invention, in the presence of organic acid, in the aqueous medium supply source compound of each element is carried out incorporate method, be and patent documentation 1 or patent documentation 2 disclosed usual method diverse ways.Do not use organic acid in the catalyst preparation process of patent documentation 1.Though patent documentation 2 has used in catalyst preparation process as organic acid oxalic acid used in the present invention, but forming with Cu after all be that the catalyst for preparing of the present invention of necessary composition is different, in addition, the occasion of patent documentation 2, this oxalic acid is in order to form the organic acid that makes water-insoluble niobic acid dissolving behind the complex and use with niobic acid reaction, but the present invention is for supply source compound integrated oxalic acid that do not use in aqueous medium of each composition of making catalyst.
Preparation method of the present invention, in the supply source compound of each composition that makes catalyst incorporate occasion in the aqueous medium in the presence of organic acid, utilize organic acid that each the composition element that constitutes catalyst is carried out coordination, suppress the combination between the composition element, by making the structure of the composite oxide catalysts that finally obtains, redox state, and the dispersity of catalyst component on carrier changes and improves the characteristic of catalyst.
Therefore, the present invention is to be the invention of feature with following aim.
(1) preparation method of composite oxide catalysts is characterized in that in formula: Mo
12V
aX
bCu
cY
dC
eSi
fO
g(in the formula, each symbol of element Mo represents that molybdenum, V represent that vanadium, Cu represent that copper, C represent that carbon, Si represent that silicon, O represent oxygen, and X represents to be selected from least a element among Nb and the W, and Y represents to be selected from least a element among Sb, Mg, Ca, Sr, Ba and the Zn.A, b, c, d, e, f and g represent each atoms of elements ratio, satisfy 0＜a≤12 respectively, 0≤b≤12,0＜c≤12,0≤d≤8,0≤e≤1000,0≤f≤1000, g is the determined number of the necessary oxygen atomicity of the state of oxidation that satisfies other elements except that Si and C in aforementioned each composition) in the preparation of represented composite oxide catalysts, make the supply source compound of each composition element integrated in the presence of organic acid, and the aqueous solution or the dispersion liquid of the integrated thing of gained carried out drying preparation powder, and the article shaped of this powder moulding is carried out roasting.
(2) wherein there is 0.001～1 mole of organic acid in the preparation method of above-mentioned (1) described composite oxide catalysts with respect to 1 mole of molybdenum.
(3) preparation method of above-mentioned (1) or (2) described composite oxide catalysts, wherein organic acid is at least a kind that is selected from citric acid, oxalic acid and the malic acid.
(4) preparation method of any one described composite oxide catalysts of above-mentioned (1)～(3), wherein composite oxide catalysts is to utilize the gas that contains molecular oxygen to make unsaturated aldehyde carry out catalytic gas phase oxidation to prepare the catalyst that corresponding unsaturated carboxylic acid is used.
(5) under the existence with the composite oxide catalysts of any one described preparation method's preparation in above-mentioned (1)～(4), utilize the gas that contains molecular oxygen to make methacrylaldehyde carry out catalytic gas phase oxidation and prepare corresponding acrylic acid.
The invention effect
According to the preparation method who the invention provides a kind of composite oxide catalysts, the gas that the gained catalyst contains molecular oxygen in utilization makes unsaturated aldehyde carry out catalytic gas phase oxidation when preparing unsaturated carboxylic acid, can give the high conversion of raw material unsaturated aldehyde and the high selectivity of unsaturated carboxylic acid, and exhibit stabilization energy for a long time.
Especially, can prepare the conversion ratio of the methacrylaldehyde that improves the per unit catalyst, can improve acrylic acid selection rate of catalyst again, can carry out the high activity composite oxide catalysts of the gas phase catalytic oxidation reaction of methacrylaldehyde expeditiously.
The preferred plan that carries out an invention
The composite oxide catalysts of the present invention's preparation is represented with aforementioned formula.X, Y, a, b, c, d, e, f and g are respectively as previously mentioned in the above-mentioned formula.Wherein most preferably 0.1≤a≤6,0.1≤b≤6,0.1≤c≤6,0.01≤d≤6,5≤e≤500,5≤f≤500.
This composite oxide catalysts of the present invention is by making integrated be prepared of supply source compound in the presence of organic acid of each catalyst component that constitutes above-mentioned formula.Here, so-called supply source compound with each catalyst component is integrated, is meant that the supply source compound that is preferably in the aqueous medium system that the aqueous solution or aqueous dispersions constitute each catalyst component element mixes.Carry out maturation process as required.Promptly, (1) each above-mentioned one step of supply source compound is mixed in the method that each above-mentioned one step of supply source compound is mixed, (2), carries out the method for maturation process, the method that mix each above-mentioned supply source compound step by step (3), the method that (4) mix each above-mentioned supply source compound maturation process repeatedly step by step and/or the method that (1)～(4) are made up again and all is included in the integral method of supply source compound in the aqueous medium system of above-mentioned each catalyst component element.
In addition, above-mentioned " slaking " is as described in the chemical voluminous dictionary (altogether upright publish), be meant " raw material of industry or semi-finished product are handled under the specified conditions of certain hour, uniform temperature etc.; seeking to obtain to improve required physical property, chemical property or realize the operation that specific reaction etc. is carried out ".Moreover above-mentioned certain hour refers to the scope that the present invention is preferred 1 minute～24 hours, and above-mentioned uniform temperature is the scope of room temperature～200 ℃ preferably.In addition, the above-mentioned supply source compound that not only contains each element that constitutes catalyst in integrated also can contain carrier materials such as aluminium oxide, silica, heat-resistant oxide as this incorporate object.
The organic acid that exists when integrated as the supply source compound of each element that constitutes this catalyst of the present invention can use the organic acid that ease of solubility matter is arranged in water.Wherein, preferably be selected from citric acid, oxalic acid and the malic acid at least a kind.The organic acid amount is with respect to preferred 0.001～1 mole of 1 mole of Mo, most preferably 0.01～0.5 mole.The organic acid amount can not improve catalyst performance during less than 0.001 mole, and on the contrary, the organic acid amount is during greater than 1 mole, and catalyst performance reduces.
The supply source compound of each composition of composite oxide catalysts of the present invention is except that the carbonization silicon compound, so long as become the chemical combination of oxide through roasting, no matter then be water-soluble or slightly water-soluble does not all have particular restriction.As the concrete example of compound, can enumerate halide, sulfate, nitrate, ammonium salt, oxide, carboxylate, ammonium carboxylate salt, ammonium halide salt, hydracid, acetylacetonate (ア セ チ Le ア セ ト Na one ト), alkoxide of each composition etc.In addition, as the concrete example of the starting compound of silicon and carbon, can enumerate green silicon carbide, black silicon carbide etc., the carborundum of the preferred powder body of carborundum.Starting compound can be with the compound that contains each composition separately, also can be with the starting compound that contains composition more than 2 kinds or 2 kinds.
If preferred concrete scheme among the preparation method of the present invention is sequentially described, then at first prepares the aqueous solution or aqueous dispersion that above-mentioned catalyst constitutes the supply source compound of elemental composition.Among the present invention, these the aqueous solution or aqueous dispersions are also referred to as slurry solution.Slurry solution can carry out mixed getting equably with the supply source compound and the water of each constituent.The usage ratio of the starting compound of each constituent of slurry in the solution, each catalyst constitute atoms of elements than can being the scope shown in the above-mentioned formula.Organic acid can be behind preparation slurry solution, or add in the preparation way, but wherein preferably the stage behind dissolving Mo and V adds.
The water yield of slurry in the solution, so long as the starting compound of each composition can be dissolved fully or homodisperse amount does not then have particular restriction, but can suitably determine according to the drying condition of the drying means that then carries out or baking temperature or drying time etc.The amount of water is with respect to total 100 weight portions of starting compound, normally 100～2000 weight portions.The amount of water is during less than above-mentioned set amount a small amount of, dissolved compound fully sometimes, or can not evenly mix.And the amount of water is when being volume, and the energy cost during heat treatment might increase.By mixing or the stirring in preparation slurry solution process, constitute each elemental composition integrated of above-mentioned catalyst, but it is integrated in order further to promote, preferred room temperature～200 ℃, most preferably 70～100 ℃, preferred 1 minute～24 hours, carried out maturation process in most preferably 30 minutes～6 hours.
Then, the above-mentioned aqueous solution or aqueous dispersions become powder by drying.Dry so long as can the dry fully aqueous solution or the aqueous dispersions method that obtains powder then do not have particular restriction, for example can enumerate roller drying, freeze drying, spray-drying etc. as preferable methods.Spray-drying is owing to being dried to the powder state of homogeneous by the aqueous solution or aqueous dispersions at short notice, so be the method that the present invention can preferably use.
The temperature of above-mentioned drying is different according to the concentration etc. of slurry solution, but usually at 90～200 ℃, preferably carries out at 130～170 ℃.The particle diameter of the powder that obtains by such drying is preferably 10～200cm.Therefore this powder also can according to circumstances be pulverized after drying.
Powder through above-mentioned drying obtains then carries out moulding.Forming method does not have particular restriction, preferably uses the binding agent moulding.Preferred adhesive is selected among the group of silica, graphite and crystallinity cellulose composition.Adhesive can preferably use about about 1～50 weight portion with respect to powder 100 weight portions.In addition, can also use the material of inorfils such as ceramic fibre, whisker as required as the mechanical strength that improves catalyst granules.But the fiber that potassium titanate crystal whisker or this class of basic magnesium carbonate whisker and catalyst component react is bad.In order to improve most preferably ceramic fibre of intensity.The use amount of these fibers is with respect to preferred 1～30 weight portion of powder 100 weight portions.Above-mentioned shaping assistant can mix use usually in advance with powder.
With the powder that the shaping assistant of binding agent etc. mixes, can adopt the method for the carrier method of forming etc. of shapes such as (A) compression molding, (B) extrusion molding, (C) be spherical to carry out moulding.The shape of formed body is preferably spherical, cylindric, the suitable shape of ring-type etc.The article shaped of moulding is carried out roasting then and can be obtained composite oxide catalysts like this.Sintering temperature can adopt 250～500 ℃ usually, and preferred 300～420 ℃, roasting time is 1～50 hour.Roasting can be carried out in the ambiance in the presence of inert gas or the molecular oxygen.The thermal diffusion of molybdenum element was insufficient when sintering temperature was too low, and the worry of loss is arranged owing to the molybdenum element distillation when too high.
Use is according to the catalyst of the present invention preparation, and the gas that utilizes molecular oxygen or contain molecular oxygen makes unsaturated aldehyde carry out gaseous oxidation, prepares the method for corresponding unsaturated carboxylic acid, can adopt original method to carry out.For example, as reactor, use the fixed bed tube-type reactor to carry out.This occasion, reaction can be that single flow through methods also can be a round-robin method by reactor, this reaction can be implemented under the general condition of using.
For example, to contain the mist that inert gas 20～80 volume % such as methacrylaldehyde 1～15 volume %, molecular oxygen 0.5～25 volume %, water vapour 0～40 volume %, nitrogen, carbon dioxide etc. form, depress at 250～450 ℃, adding of 0.1～1MPa, adopted space velocity (SV) 300～5000 hours
-1Be passed on the catalyst layer of each reaction zone of each reaction tube that is filled in the preferred 15～50mm of internal diameter.Even the present invention, also can be turned round under for example higher raw gas concentration or the high space velocity condition in order further to enhance productivity under the high load capacity reaction condition.Therefore, use the catalyst of the present invention's preparation can high selectivity and prepare acrylic acid with high yield.
Embodiment
Below, enumerate embodiment and comparative example is described more specifically the present invention, can not be interpreted as the present invention certainly and only be defined in these embodiment.Moreover the nitre that uses among the embodiment is bathed and is meant reaction tube is put into the salt bath that thermal medium that alkali-metal nitrate forms makes it to react.This thermal medium is in fusion more than 200 ℃ or 200 ℃, even can be 400 ℃ of uses, because heat extraction is effective, so be the reactive bath technique of the oxidation reaction that is applicable to that thermal discharge is big.In addition, acrolein conversion rate, acrylic acid selection rate, acrylic acid yield define with following formula.
Acrolein conversion rate (mole %)=100 * (the methacrylaldehyde molal quantity of reaction)/(the methacrylaldehyde molal quantity of supply)
Propylene is to selection rate (mole %)=100 * (the acrylic acid molal quantity of generation)/(the methacrylaldehyde molal quantity of conversion)
Acrylic acid yield (mole %)=100 * (the acrylic acid molal quantity of generation)/(the methacrylaldehyde molal quantity of supply)
Embodiment 1
Preparation is Mo except that the empirical formula of the constituent of deoxidation as follows
12V
2.4Nb
1Cu
2Si
200C
200Composite metal oxide.
At first, pure water 1446ml is heated to 80 ℃, ammonium paramolybdate 207g is sequentially dissolved, ammonium metavanadate 27.5g and citric acid 12.0g to its stirring limit in the limit then.In this aqueous solution, add the copper sulfate solution that is dissolved with copper sulphate 48.6g among the pure water 204ml, add niobium hydroxide 19.3g again and stir, obtain pulpous state solution.
In this pulpous state solution, add silicon carbide powder 782g, mix fully.This pulpous state liquid is heated to 130 ℃ carries out drying.Mix to the graphite that wherein adds 1.5 weight % then, use small-sized compression molding machine to carry out moulding, with its with roaster in nitrogen stream 3 hours article shaped of 380 ℃ of following roastings as catalyst.
In order to estimate the catalyst that obtains, being ground into the whole grain of 20～28 purposes catalyst 0.3g, be filled in the U font reaction tube of internal diameter 4mm, this reaction tube is put into the nitre of heating and bathed (temperature: 288 ℃), in this reaction tube, import and form gas (methacrylaldehyde 5 volume %, oxygen 8 volume %, water vapour 15 volume % and nitrogen 72 volume %), in SV (space velocity: the apparent volume of the catalyst of the flow/filling of the unstripped gas of time per unit) 14900 hours
-1React under the condition.Reaction result is acrolein conversion rate=99.0%, acrylic acid selection rate=98.6%, acrylic acid yield=97.6%.
Embodiment 2
Preparation is Mo except that the empirical formula of the constituent of deoxidation as follows
12V
2.4Nb
1Cu
2Si
200C
200The composition metal oxygenate.
At first, pure water 1446ml is heated to 80 ℃, then it is sequentially dissolved ammonium paramolybdate 207g while stirring, ammonium metavanadate 27.5g and citric acid 12.0g.Add the copper sulfate solution that is dissolved with copper sulphate 48.6g among the pure water 204ml then, add niobium hydroxide 19.3g again and stir, obtain pulpous state solution.
In this pulpous state solution, add silicon carbide powder 782g, mix fully.This pulpous state liquid is heated to 130 ℃ carries out drying.Mix to the graphite that wherein adds 1.5 weight % then, use small formed compression molding machine to carry out moulding, with its with roaster in nitrogen stream 3 hours article shaped of 380 ℃ of following roastings as catalyst.
In order to estimate the catalyst that obtains, be filled in the U font reaction tube of internal diameter 4mm being ground into the whole grain of 20～28 purposes catalyst 0.3g, this reaction tube is put into the nitre of heating and bathed (temperature: 290 ℃), in this reaction tube, import and form gas (methacrylaldehyde 5 volume %, oxygen 8 volume %, water vapour 15 volume % and nitrogen 72 volume %), in SV (space velocity: the apparent volume of the catalyst of the flow/filling of the unstripped gas of time per unit) 14900 hours
-1React under the condition.
Reaction result is acrolein conversion rate=99.0%, acrylic acid selection rate=97.2%, acrylic acid yield=96.2%.
Embodiment 3
Preparation is Mo except that the empirical formula of the constituent of deoxidation as follows
12V
2.4Nb
1W
0.5Cu
2Sb
1Si
200C
200The composition metal oxygenate.
At first, pure water 1446ml is heated to 80 ℃, then it is sequentially dissolved ammonium paramolybdate 201g while stirring, ammonium metavanadate 26.7g, citric acid 12.0g and ammonium metatungstate 21.9g to wherein adding antimony trioxide 13.8g, add the copper sulfate solution that is dissolved with copper sulphate 47.3g among the pure water 204ml again, add niobium hydroxide 18.7g and stir, obtain pulpous state solution.
In this pulpous state solution, add silicon carbide powder 761g, mix fully.This pulpous state liquid is heated to 130 ℃ carries out drying.Mix to the graphite that wherein adds 1.5 weight % then, use small formed compression molding machine to carry out moulding, with its with roaster in nitrogen stream 3 hours article shaped of 380 ℃ of following roastings as catalyst.
In order to estimate the catalyst that obtains, be filled in the U font reaction tube of internal diameter 4mm being ground into the whole grain of 20～28 purposes catalyst 0.3g, this reaction tube is put into the nitre of heating and bathed (temperature: 290 ℃), in this reaction tube, import and form gas (methacrylaldehyde 5 volume %, oxygen 8 volume %, water vapour 15 volume % and nitrogen 72 volume %), in SV (space velocity: the apparent volume of the catalyst of the flow/filling of the unstripped gas of time per unit) 14900 hours
-1React under the condition.
The result of reaction is acrolein conversion rate=99.0%, acrylic acid selection rate=98.7%, acrylic acid yield=97.7%.
Comparative example
Preparation is Mo except that the empirical formula of the constituent of deoxidation as follows
12V
2.4Nb
1Cu
2Si
200C
200Composite metal oxide.
At first, pure water 1446ml is heated to 80 ℃, then it is sequentially dissolved ammonium paramolybdate 207g while stirring, and ammonium metavanadate 27.5g.In wherein adding pure water 204ml, be dissolved with the copper sulfate solution of copper sulphate 48.6g, add niobium hydroxide 19.3g again and stir, obtain pulpous state solution.
In this pulpous state solution, add silicon carbide powder 782g, mix fully.This pulpous state liquid is heated to 130 ℃ carries out drying.The graphite that adds 1.5 weight % then mixes, and uses small formed compression molding machine to carry out moulding, with its with roaster in nitrogen stream 3 hours article shaped of 380 ℃ of following roastings as catalyst.
With the fully same condition of embodiment under estimate the reactivity of gained catalyst.296 ℃ of results that react down are acrolein conversion rate=99.0%, acrylic acid selection rate=97.0%, acrylic acid yield=96.0% at the nitre bath temperature.
Therefore, not adding the organic acid comparative example is that the acrylic acid selectivity is low, and yield is than the result of embodiment 1 low 1.6%.
So interpolation organic acid embodiment 1, embodiment 2, embodiment 3 all are that acrolein conversion rate, acrylic acid selection rate and acrylic acid yield are good, can carry out the gas phase catalytic oxidation reaction of methacrylaldehyde expeditiously.
The possibility of utilizing on the industry
Adopt the catalyst of method preparation of the present invention, can be used for utilizing the gas that contains molecular oxygen to make Unsaturated aldehyde carries out catalytic gas phase oxidation and can prepare with high yield corresponding unsaturated carboxylic acid. Made The unsaturated carboxylic acid of acrylic acid etc. at the raw material as various chemicals, the monomer of resins for universal use, The monomer of the functional resin of water-absorbing resins etc., flocculating agent, tackifier etc. use in the purposes widely.
Claims (5)
1. the preparation method of composite oxide catalysts is characterized in that, at formula: Mo
12V
aX
bCu
cY
dC
eSi
fO
g(in the formula, X represents to be selected from least a element among Nb and the W, Y represents to be selected from Sb, Mg, Ca, Sr, at least a element among Ba and the Zn, a, b, c, d, e, f and g represent each atoms of elements ratio, satisfy 0＜a≤12 respectively, 0≤b≤12,0＜c≤12,0≤d≤8,0≤e≤1000,0≤f≤1000, g is the necessary oxygen atomicity of the state of oxidation that satisfies other elements except that Si and C in aforementioned each composition element) in the preparation of composite oxide catalysts of expression, make the supply source compound of each composition element integrated in the presence of the organic acid in the aqueous medium system, and the aqueous solution or the dispersion liquid of the integrated thing of gained carried out drying, moulding, roasting.
2. wherein there is 0.001～1 mole of organic acid in the preparation method of the described composite oxide catalysts of claim 1 with respect to 1 mole of molybdenum.
3. the preparation method of claim 1 or 2 described composite oxide catalysts, wherein organic acid is at least a kind that is selected from citric acid, oxalic acid and the malic acid.
4. the preparation method of any one described composite oxide catalysts in the claim 1～3, wherein composite oxide catalysts is to utilize the gas that contains molecular oxygen to make unsaturated aldehyde carry out catalytic gas phase oxidation to prepare the catalyst that corresponding unsaturated carboxylic acid is used.
5. utilize the gas that contains molecular oxygen to make methacrylaldehyde carry out catalytic gas phase oxidation and prepare corresponding acrylic acid, this method is to carry out in the presence of the composite oxide catalysts for preparing with any one described preparation method in the claim 1～4.
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| CN110505917A (en) * | 2017-03-31 | 2019-11-26 | 三菱化学株式会社 | The manufacturing method of unsaturated carboxylic acid catalyst for producing, the manufacturing method of unsaturated carboxylic acid and esters of unsaturated carboxylic acids |
| CN115038521A (en) * | 2020-01-31 | 2022-09-09 | 三菱化学株式会社 | Method for producing catalyst and method for producing acrylic acid |
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| JP5190994B2 (en) * | 2006-03-20 | 2013-04-24 | 旭化成ケミカルズ株式会社 | Oxidation or ammoxidation catalyst and method for producing the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3959182A (en) * | 1969-08-19 | 1976-05-25 | Rohm And Haas Company | Catalyst compositions and process for producing acrylic acid or methacrylic acid utilizing such catalyst |
| JPS5025914B1 (en) * | 1970-12-28 | 1975-08-27 | ||
| JPS49169B1 (en) * | 1970-12-28 | 1974-01-05 | ||
| JPS5946934B2 (en) * | 1976-02-09 | 1984-11-15 | 東ソー株式会社 | Method for manufacturing methacrylic acid |
| EP0811597B1 (en) * | 1994-11-14 | 2000-08-23 | Nippon Shokubai Co., Ltd. | Process for production of acrylic acid |
| JP2000317309A (en) * | 1999-05-17 | 2000-11-21 | Toagosei Co Ltd | Production of catalyst for producing acrylic acid |
| DE10046928A1 (en) * | 2000-09-21 | 2002-04-11 | Basf Ag | Process for the preparation of multimetal oxide materials |
| JP2003200055A (en) * | 2002-01-09 | 2003-07-15 | Mitsubishi Chemicals Corp | Method for manufacturing compound oxide catalyst |
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| CN110505917A (en) * | 2017-03-31 | 2019-11-26 | 三菱化学株式会社 | The manufacturing method of unsaturated carboxylic acid catalyst for producing, the manufacturing method of unsaturated carboxylic acid and esters of unsaturated carboxylic acids |
| CN110505917B (en) * | 2017-03-31 | 2023-06-06 | 三菱化学株式会社 | Catalyst for producing unsaturated carboxylic acid, process for producing unsaturated carboxylic acid, and process for producing unsaturated carboxylic acid ester |
| CN115038521A (en) * | 2020-01-31 | 2022-09-09 | 三菱化学株式会社 | Method for producing catalyst and method for producing acrylic acid |
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