CN104107697B - The preparation method of acrylic acid catalyst - Google Patents
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Abstract
The present invention relates to a kind of preparation method being prepared acrylic acid catalyst by acrolein oxidation, mainly solve the problem that acrylic acid catalyst selectivity and stability in prior art are not high.The present invention is by adopting with selected from SiO2、Al2O3In at least one be carrier, containing by the active component Mo of following general formula12VaCubXcYdZeOx ,Wherein X is at least one in W, Cr, Sn；Y is at least one in Fe, Bi, Co, Ni, Sb, Ce, La, Zr, Sr；Z is at least one in alkali metal or alkaline-earth metal；In oxygen-containing atmosphere, preroast is carried out before shaping of catalyst；Shaping of catalyst process adds SiO2Or Al2O3At least one in colloidal sol is as binding agent；Roasting in atmosphere after shaping of catalyst；The technical scheme processing 2-30 hour in the gaseous mixture that catalyst comprises oxygen, steam and acrylic aldehyde before using at 360-420 DEG C solves this problem preferably, can be used in the commercial production of acrylic acid catalyst.
Description
Technical field
The present invention relates to a kind of preparation method being prepared acrylic acid catalyst by acrolein oxidation.
Background technology
α, β unsaturated aldehyde is prepared in the selective oxidation of alkene and unsaturated acids is important chemical process, is wherein contained the catalyst of Mo, V by acrylic aldehyde system a kind of active component of acrylic acid production and application.Improving mainly from the activity of catalyst, selectivity and what stability aspect carried out of catalyst, as added transition metal in active constituent to improve activity, the list increasing product is received；Add rare earth element and improve redox ability, improve catalyst stability；Add the elements such as Fe, Co, Ni to suppress the distillation of Mo, stabilizing catalyst activity component, improves the service life etc. of catalyst.
A lot of patent report is had for acrylic aldehyde selective oxidation:
USPat7220698B2, by adding the catalyst poison of a kind of trace in catalyst preparation process, controls catalyst reaction bed focus, it is suppressed that the thermal degradation of catalyst, improves catalyst stability.Acrolein conversion rate reaches 98.8%, and remains stable for for a long time.USPat7378367B2 describes a kind of acrylic acid catalyst, and acrylic acid yield is up to 95.1%, and has good stability, and in use procedure, reactor temperature rise is little.USPat7456129B2 improves catalyst performance, acrolein conversion rate 98.9%, acrylic acid selectivity 95.1% by controlling support acid strength.CN1183088C introduces a kind of method for preparing catalyst, and by selecting specifically to prepare raw material, acrolein conversion rate is up to 99.6%, and acrylic acid selectivity is up to 96.0%, and acrylic acid yield is up to 95.2%.These methods play a role in suppressing hot spots temperature, but still can affect the stability of catalyst after the oxidation reaction of long period.
Summary of the invention
One of the technical problem to be solved is the problem that in prior art, in acrylic acid catalyst use, selectivity is not high and stability is bad, the preparation method that a kind of new acrylic acid catalyst is provided, the advantage that this catalyst has high selectivity, high stability.
The two of the technical problem to be solved are the catalyst that above-mentioned preparation method obtains.
The three of the technical problem to be solved be adopt above-mentioned technical problem two described in catalyst acrolein oxidation prepare acrylic acid.
For solving one of above-mentioned technical problem, the technical solution used in the present invention is as follows: the preparation method of acrylic acid catalyst, and described catalyst is with selected from SiO2、Al2O3In at least one be carrier, active constituent is by following general formula:
Mo12VaCubXcYdZeOx
In formula, X is at least one in W, Cr, Sn；
Y is at least one in Fe, Bi, Co, Ni, Sb, Ce, La, Zr or Sr；
Z is at least one in alkali metal or alkaline-earth metal；
The span of a is 1.0～10.0；
The span of b is 0.5～8.0；
The span of c is 0.8～11.0；
The span of d is 0.5～6.0；
The span of e is 0.5～5.0；
X meets the oxygen atom sum needed for other element valence；
In catalyst, the consumption of carrier is the 5～60% of catalyst weight, comprises the steps:
A) hydroxide of the desired amount of ammonium molybdate and Z is dispersed in water, is subsequently adding the desired amount of carrier and obtains material I；
B) will provide for the ammonium metavanadate of aequum V to be dissolved in water and form material II；
C) will provide for the copper nitrate of aequum Cu and X slaine and Y dissolving metal salts in water, form material III；
D) under agitation, material II and material III is separately added into materialForm catalyst pulp；
E) catalyst pulp obtains powder catalyst presoma 1 by precipitation, dry, pulverizing or spray drying；
F) catalyst precursor 1 in oxygenous atmosphere at 240-360 DEG C preroast 2-8 hour；
G) add selected from SiO in the catalyst precursor 1 after preroast2Or Al2O3At least one inorganic binder in colloidal sol obtains catalyst precursor 2 through mediating extrusion molding；
H) by catalyst precursor 2 in oxygen-containing atmosphere in 350-450 DEG C roasting within 2-10 hour, obtain catalyst precursor 3；
I) by catalyst precursor 3 in the gaseous mixture comprising oxygen, steam and acrylic aldehyde at 360-420 DEG C process within 2-30 hour, obtain described catalyst.
In technique scheme, the value of a preferably ranges from 2.0～7.0；The value of b preferably ranges from 1.2～5.5；The value of c preferably ranges from 1.0～7.2；The value of d preferably ranges from 0.8～4.8；The value of e preferably ranges from 0.7～3.6.The preferred potassium of Z, X preferred elements tungsten.In step f) and/or step h), oxygenous atmosphere is preferably air.Step f) pre-calcination temperature is preferably 280 DEG C-330 DEG C；Step f) pre-firing times is preferably 4-6 hour.Step i) processes the time and is preferably 5-12 hour.With acrylic aldehyde preferred in the composition of the molar ratio computing described gaseous mixture of step i): oxygen: water=1:(1.2 ~ 1.8): (1 ~ 3)；More preferably acrylic aldehyde: oxygen: water=1:(1.4 ~ 1.6): (1.6 ~ 2.1).
In technique scheme, the condition of step e) spray drying is not the key point of the present invention, and those skilled in the art know how to control suitable condition for the purpose realizing that slurry is dried.Being illustrative only, the spray drying condition that the embodiment of the present invention adopts is: heating-up temperature is 200 DEG C-350 DEG C, and atomizing disk rotating speed is 1200-2500 rev/min.In step e) of the present invention, the granularity of powder catalyst presoma 1 is not the key of the present invention, and those skilled in the art are required to rationally determine its granularity according to step g) molding.But preferred size is 20～50 microns.
In technique scheme, at materialMiddle addition is selected from SiO2Or Al2O3At least one 10%-60% that amount is its total consumption in colloidal sol.
For solving the two of above-mentioned technical problem, technical scheme is as follows: the catalyst that the described preparation method of one of above-mentioned technical problem obtains.
For solving the three of above-mentioned technical problem, the technical solution used in the present invention is as follows: synthesis of conjugated carboxylic alkeneacid, with acrylic aldehyde, oxygen and water for raw material, and wherein acrylic aldehyde: oxygen: water (mol ratio) is 1:(1 ~ 2): (1 ~ 3)；Being 250～320 DEG C in reaction temperature, reaction pressure is 0.1 ~ 0.12MPa, and raw material volume air speed is 800 ~ 1400h-1When, raw material contacts with described catalyst, and reaction generates acrylic acid.
The catalyst using the present invention prepares acrylic acid for acrylic aldehyde selective oxidation, reaction temperature be 280 DEG C, raw material volume air speed be 1200 hours-1When, acrolein conversion rate is 99.2%, and acrylic acid selectivity is up to 99.5%, convenient formation in catalyst preparation process, catalytic mechanical intensity >=30N/cm, after 3000 hours, acrolein conversion rate is 99%, acrylic acid selectivity, up to 99.1%, achieves good technique effect.
Below by comparative example, the present invention is further elaborated with embodiment.
Detailed description of the invention
Comparative example 1
A) by 100 grams of (NH4)6Mo7O24·4H2O and 1.9 grams of KOH joins in the warm water of 100 grams 70 DEG C, and stirring makes it all dissolve, and material I made by the Ludox adding 64.4 grams of 40wt%；
B) in 50 grams of water, 25.8 grams of NH are added4VO3Form material II
C) by 28.5 grams of Fe (NO3)3·9H2O adds in 70 DEG C of hot water of 20 grams, adds 34.2 grams of Cu (NO after stirring and dissolving3)2·3H2O, 12.0 grams of Sr (NO3)2With 12.7 grams of (NH4)6H5[H2(WO4)6] stirring and dissolving makes material material III；
D) material II and III successively drips in material I under fast stirring, forms catalyst pulp, and stirs aging 2 hours at 80 DEG C；
E) spray drying (spray drying condition is: heating-up temperature is 300 DEG C, and atomizing disk rotating speed is 2000 revs/min) obtains powder catalyst presoma 1;
F) weigh 500 grams of catalyst precursors 1, add Ludox that 25 grams of concentration is 40wt% and the Alumina gel that 50 grams of concentration is 20wt% mediates extrusion molding, obtain the catalyst precursor 2 of φ 5 × 2 × 5mm；
G) then catalyst precursor 2 roasting in atmosphere being obtained catalyst precursor 3, sintering temperature is 430 DEG C, and roasting time is 5 hours；
The investigation appreciation condition of catalyst is:
Reactor: fixing sheet pipe reactor, internal diameter 25.4 millimeters, reactor length 3000 millimeters
Catalyst: 600 grams
Reaction temperature: 280 DEG C
Material molar ratio: acrylic aldehyde oxygen water vapour=1 1.5 1.7
Raw material volume air speed: 1200 hours-1
Sample analysis is carried out respectively after reaction carries out 4 hours and 3000 hours.Product is that 5% dilute hydrochloric acid absorbs by 0 DEG C of concentration, uses gas chromatographic analysis product.And calculate Carbon balance, when Carbon balance is valid data when (95～105) %.
Acrolein conversion rate, product yield and be optionally defined as:
The composition of catalyst and performance are listed in table 2.
Comparative example 2
A) by 100 grams of (NH4)6Mo7O24·4H2O and 1.9 grams of KOH joins in the warm water of 100 grams 70 DEG C, and stirring makes it all dissolve, and material I made by the Ludox adding 64.4 grams of 40wt%；
B) in 50 grams of water, 25.8 grams of NH are added4VO3Form material II
C) by 28.5 grams of Fe (NO3)3·9H2O adds in 70 DEG C of hot water of 20 grams, adds 34.2 grams of Cu (NO after stirring and dissolving3)2·3H2O, 12.0 grams of Sr (NO3)2With 12.7 grams of (NH4)6H5[H2(WO4)6] stirring and dissolving makes material material III；
D) material II and III successively drips in material I under fast stirring, forms catalyst pulp, and stirs aging 2 hours at 80 DEG C；
E) spray drying (spray drying condition is: heating-up temperature is 300 DEG C, and atomizing disk rotating speed is 2000 revs/min) obtains powder catalyst presoma 1;
F) by catalyst precursor 1 300 DEG C of preroast 5 hours in atmosphere；
G) weigh the catalyst precursor 1 after 500 grams of preroast, add Ludox that 25 grams of concentration is 40wt% and the Alumina gel that 50 grams of concentration is 20wt% mediates extrusion molding, obtain the catalyst precursor 2 of φ 5 × 2 × 5mm；
H) then catalyst precursor 2 roasting in atmosphere being obtained catalyst precursor 3, sintering temperature is 430 DEG C, and roasting time is 5 hours；
Main catalyst preparation process condition is listed in table 1.
The composition of catalyst and performance, with comparative example 1, are listed in table 2 by the evaluation methodology of catalyst.
Comparative example 3
A) by 100 grams of (NH4)6Mo7O24·4H2O and 1.9 grams of KOH joins in the warm water of 100 grams 70 DEG C, and stirring makes it all dissolve, and material I made by the Ludox adding 64.4 grams of 40wt%；
B) in 50 grams of water, 25.8 grams of NH are added4VO3Form material II
C) by 28.5 grams of Fe (NO3)3·9H2O adds in 70 DEG C of hot water of 20 grams, adds 34.2 grams of Cu (NO after stirring and dissolving3)2·3H2O, 12.0 grams of Sr (NO3)2With 12.7 grams of (NH4)6H5[H2(WO4)6] stirring and dissolving makes material material III；
D) material II and III successively drips in material I under fast stirring, forms catalyst pulp, and stirs aging 2 hours at 80 DEG C；
E) spray drying (spray drying condition is: heating-up temperature is 300 DEG C, and atomizing disk rotating speed is 2000 revs/min) obtains powder catalyst presoma 1;
F) weigh 500 grams of catalyst precursors 1, add Ludox that 25 grams of concentration is 40wt% and the Alumina gel that 50 grams of concentration is 20wt% mediates extrusion molding, obtain the catalyst precursor 2 of φ 5 × 2 × 5mm；
G) then catalyst precursor 2 roasting in atmosphere being obtained catalyst precursor 3, sintering temperature is 430 DEG C, and roasting time is 5 hours；
H) by catalyst precursor 3 in the gaseous mixture comprising air (namely oxygen is provided), steam and acrylic aldehyde by air at 390 DEG C process within 12 hours, obtain described finished catalyst, wherein acrylic aldehyde: oxygen: steam mol ratio=1:1.5:1.8.Main catalyst preparation process condition is listed in table 1.
The composition of catalyst and performance, with comparative example 1, are listed in table 2 by the evaluation methodology of catalyst.
Embodiment 1
A) by 100 grams of (NH4)6Mo7O24·4H2O and 1.9 grams of KOH joins in the warm water of 100 grams 70 DEG C, and stirring makes it all dissolve, and material I made by the Ludox adding 64.4 grams of 40wt%；
B) in 50 grams of water, 25.8 grams of NH are added4VO3Form material II
C) by 28.5 grams of Fe (NO3)3·9H2O adds in 70 DEG C of hot water of 20 grams, adds 34.2 grams of Cu (NO after stirring and dissolving3)2·3H2O, 12.0 grams of Sr (NO3)2With 12.7 grams of (NH4)6H5[H2(WO4)6] stirring and dissolving makes material material III；
D) material II and III successively drips in material I under fast stirring, forms catalyst pulp, and stirs aging 2 hours at 80 DEG C；
E) spray drying (spray drying condition is: heating-up temperature is 300 DEG C, and atomizing disk rotating speed is 2000 revs/min) obtains powder catalyst presoma 1;
F) by catalyst precursor 1 300 DEG C of preroast 5 hours in atmosphere；
G) weigh the catalyst precursor 1 after 500 grams of preroast, add Ludox that 25 grams of concentration is 40wt% and the Alumina gel that 50 grams of concentration is 20wt% mediates extrusion molding, obtain the catalyst precursor 2 of φ 5 × 2 × 5mm；
H) then catalyst precursor 2 roasting in atmosphere being obtained catalyst precursor 3, sintering temperature is 430 DEG C, and roasting time is 5 hours；
I) by catalyst precursor 3 in the gaseous mixture comprising air (namely oxygen is provided), steam and acrylic aldehyde by air at 390 DEG C process within 12 hours, obtain described finished catalyst, wherein acrylic aldehyde: oxygen: steam mol ratio=1:1.5:1.8.Main catalyst preparation process condition is listed in table 1.
The composition of catalyst and performance, with comparative example 1, are listed in table 2 by the evaluation methodology of catalyst.
Embodiment 2
Except step f) pre-calcination temperature, pre-firing times, step i) acrylic aldehyde: oxygen: except steam mol ratio, treatment temperature and process time changes, other preparation technology is identical with embodiment 1.Main catalyst preparation process condition is listed in table 1.
The composition of catalyst and performance, with comparative example 1, are listed in table 2 by the evaluation methodology of catalyst.
Embodiment 3
Except step f) pre-calcination temperature, pre-firing times, step i) acrylic aldehyde: oxygen: except steam mol ratio, treatment temperature and process time changes, other preparation technology is identical with embodiment 1.Main catalyst preparation process condition is listed in table 1.The composition of catalyst and performance, with comparative example 1, are listed in table 2 by the evaluation methodology of catalyst.
Embodiment 4
Replacing except step i) purity oxygen providing except oxygen with air, other is all identical with embodiment 1.Main catalyst preparation process condition is listed in table 1.
The composition of catalyst and performance, with comparative example 1, are listed in table 2 by the evaluation methodology of catalyst.
Embodiment 5
A) by 100 grams of (NH4)6Mo7O24·4H2O and 2.66 grams of KOH joins in the warm water of 100 grams 70 DEG C, and stirring makes it all dissolve, and the Ludox adding 64.4 grams of 40wt% obtains material I；
B) in 50 grams of water, 18.7 grams of NH are added4VO3Form material II；
C) by 20.6 grams of Bi (NO3)3.5H2O adds in 70 DEG C of hot water of 20 grams, adds 31.9 grams of Cu (NO after stirring and dissolving3)2·3H2O, 32.8 grams of Ce (NO3)3.6H2O, 13.2 grams of CsNO3With 16.5 grams of (NH4)6H5[H2(WO4)6] form material III after stirring and dissolving；
D) material II and III is successively dripped in material I under fast stirring, form catalyst pulp, and at 80 DEG C, stir aging 2 hours；
E) spray drying (spray drying condition is: heating-up temperature is 300 DEG C, and atomizing disk rotating speed is 2000 revs/min) obtains catalyst precursor 1；
F) catalyst precursor 1 is put in converter and is carried out preroast, roasting time 5 hours in 300 DEG C in air atmosphere；
G) 500 grams of catalyst precursors 1 after preroast are weighed, the Alumina gel 50 grams adding concentration to be the Ludox 25 grams of 40wt%, concentration be 20wt% mediates extrusion molding, obtain φ 5 × 2 × 5mm(external diameter 5mm, internal diameter 2mm, high 5mm) the catalyst precursor 2 of Raschig ring shape；
H) calcined catalyst presoma 2 obtains catalyst precarsor 3, and sintering temperature is 430 DEG C, and roasting time is 5 hours；
I) catalyst precarsor 3 carries out processing 12 hours in 390 DEG C in the gaseous mixture of air, steam and acrylic aldehyde, and wherein the mol ratio of acrylic aldehyde, oxygen and steam is 1:1.5:1.8.
Main catalyst preparation process condition is listed in table 1.
The composition of catalyst and performance, with comparative example 1, are listed in table 2 by the evaluation methodology of catalyst.
Embodiment 6
A) by 100 grams of (NH4)6Mo7O24·4H2O and 2.66 grams of KOH joins in the warm water of 100 grams 70 DEG C, and stirring makes it all dissolve, and adds the Ludox that 64.4 grams of concentration is 40wt% and obtains material I；
B) in 50 grams of water, 22 grams of NH are added4VO3Form material II；
C) by 17.1 grams of Fe (NO3)3.9H2O adds in 70 DEG C of hot water of 20 grams, adds 44.4 grams of Cu (NO after stirring and dissolving3)2·3H2O, 32.8 grams of Ce (NO3)3.6H2O, 3.37 grams of RbOH and 25.4 grams of (NH4)6H5[H2(WO4)6] make material III after stirring and dissolving；
D) material II and III is successively dripped in material I under fast stirring, form catalyst pulp, and at 80 DEG C, stir aging 2 hours；
E) spray drying (spray drying condition is: heating-up temperature is 300 DEG C, and atomizing disk rotating speed is 2000 revs/min) catalyst precursor 1；
F) catalyst precursor 1 is put in converter and carry out preroast, roasting time 5 hours in 300 DEG C in air atmosphere；
G) 500 grams of catalyst precursors 1 after preroast are weighed, the Alumina gel 50 grams adding concentration to be the Ludox 25 grams of 40wt%, concentration be 20wt% mediates extrusion molding, obtain φ 5 × 2 × 5mm(external diameter 5mm, internal diameter 2mm, high 5mm) the catalyst precursor 2 of Raschig ring；
H) then calcined catalyst presoma 2 obtains catalyst precursor 3, and sintering temperature is 430 DEG C, and roasting time is 5 hours；
I) catalyst precursor 3 carries out processing 12 hours in 390 DEG C in the gaseous mixture of air, steam and acrylic aldehyde；Wherein the mol ratio of acrylic aldehyde, oxygen and steam is 1:1.5:1.8.
Main catalyst preparation process condition is listed in table 1.
The composition of catalyst and performance, with comparative example 1, are listed in table 2 by the evaluation methodology of catalyst.
Embodiment 7
A) by 100 grams of (NH4)6Mo7O24·4H2O and 9.6 grams of Ca (NO3)2.4H2O joins in the warm water of 100 grams 70 DEG C, and stirring makes it all dissolve, and adds the Ludox that 64.4 grams of concentration is 40wt% and obtains material I；
B) in 50 grams of water, 23.1 grams of NH are added4VO3Form material II；
C) by 24.9 grams of Ni (NO3)2.6H2O adds in 70 DEG C of hot water of 20 grams, adds 44.4 grams of Cu (NO after stirring and dissolving3)2·3H2O, 22.9 grams of Cr (NO3)3.9H2O, 11.9 grams of CsNO3Material III is made after stirring and dissolving；
D) material II and III is successively dripped in material I under fast stirring, form catalyst pulp, and at 80 DEG C, stir aging 2 hours；
E) spray drying (spray drying condition is: heating-up temperature is 300 DEG C, and atomizing disk rotating speed is 2000 revs/min) catalyst precursor 1；
F) catalyst precursor 1 is put in converter and carry out preroast, roasting time 5 hours in 300 DEG C in air atmosphere；
G) 500 grams of catalyst precursors 1 after preroast are weighed, the Alumina gel 50 grams adding concentration to be the Ludox 25 grams of 40wt%, concentration be 20wt% mediates extrusion molding, obtain φ 5 × 2 × 5mm(external diameter 5mm, internal diameter 2mm, high 5mm) the catalyst precursor 2 of Raschig ring shape；
H) then calcined catalyst presoma 2 obtains catalyst precursor 3, and sintering temperature is 430 DEG C, and roasting time is 5 hours；
I) catalyst precursor 3 carries out processing 12 hours in 390 DEG C in the gaseous mixture of air, steam and acrylic aldehyde；Wherein the mol ratio of acrylic aldehyde, oxygen and steam is 1:1.5:1.8.
Main catalyst preparation process condition is listed in table 1.
The composition of catalyst and performance, with comparative example 1, are listed in table 2 by the evaluation methodology of catalyst.
Experiment finds that step f) and step i) have synergism, and selectivity of catalyst is substantially increased, for instance comparative example 2 from table 1 and table 2, comparative example 3 and embodiment 1 data on year-on-year basis can be seen that.It addition, the oxygenous gas of step i) adopts air to be better than adopting purity oxygen.
Table 1, shaping of catalyst process conditions
Table 2, comparative example, embodiment investigate result
Claims (9)
1. a preparation method for acrylic acid catalyst, described catalyst is with selected from SiO2、Al2O3In at least one be carrier, active constituent is by following general formula:
Mo12VaCubXcYdZeOx
In formula, X is at least one in W, Cr, Sn；
Y is at least one in Fe, Bi, Co, Ni, Sb, Ce, La, Zr or Sr；
Z is at least one in alkali metal or alkaline-earth metal；
The span of a is 1.0～10.0；
The span of b is 0.5～8.0；
The span of c is 0.8～11.0；
The span of d is 0.5～6.0；
The span of e is 0.5～5.0；
X meets the oxygen atom sum needed for other element valence；
In catalyst, the consumption of carrier is the 5～60% of catalyst weight, comprises the steps:
A) hydroxide of the desired amount of ammonium molybdate and Z is dispersed in water, is subsequently adding the desired amount of carrier and obtains material I；
B) will provide for the ammonium metavanadate of aequum V to be dissolved in water and form material II；
C) will provide for the copper nitrate of aequum Cu and X slaine and Y dissolving metal salts in water, form material III；
D) under agitation, material II and material III is separately added into material I and forms catalyst pulp；
E) catalyst pulp obtains powder catalyst presoma 1 by precipitation, dry, pulverizing or spray drying；
F) catalyst precursor 1 in oxygenous atmosphere at 240-360 DEG C preroast 2-8 hour；
G) add selected from SiO in the catalyst precursor 1 after roasting2Or Al2O3At least one inorganic binder in colloidal sol obtains catalyst precursor 2 through mediating extrusion molding；
H) by catalyst precursor 2 in oxygenous atmosphere in 350-450 DEG C roasting within 2-10 hour, obtain catalyst precursor 3；
I) by catalyst precursor 3 in the gaseous mixture comprising oxygen, steam and acrylic aldehyde at 360-420 DEG C process within 2-30 hour, obtain described catalyst, with acrylic aldehyde in the composition of gaseous mixture described in molar ratio computing: oxygen: water=1:(1.2～1.8): (1～3).
2. preparation method according to claim 1, it is characterised in that the span of a is 2.0～7.0；The span of b is 1.2～5.5；The span of c is 1.0～7.2；The span of d is 0.8～4.8；The span of e is 0.7～3.6.
3. preparation method according to claim 1, it is characterised in that Z is potassium, X is tungsten.
4. preparation method according to claim 1, it is characterised in that step f) and/or atmosphere oxygenous in step h) are air.
5. preparation method according to claim 1, it is characterised in that step f) pre-calcination temperature is 280 DEG C-330 DEG C.
6. preparation method according to claim 1, it is characterised in that step f) pre-firing times is 4-6 hour.
7. preparation method according to claim 1, it is characterised in that with acrylic aldehyde in the composition of the molar ratio computing described gaseous mixture of step i): oxygen: water=1:(1.4～1.6): (1.6～2.1).
8. the catalyst that preparation method described in any one of claim 1 to 7 obtains.
9. synthesis of conjugated carboxylic alkeneacid, with acrylic aldehyde, oxygen and water for raw material, wherein with molar ratio computing acrylic aldehyde: oxygen: water is 1 (1～2) (1～3)；Being 250～320 DEG C in reaction temperature, reaction pressure is 0.1～0.12MPa, and raw material volume air speed is 800～1400h-1When, raw material contacts with catalyst described in claim 8, and reaction generates acrylic acid.
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| CN102039141A (en) * | 2009-10-13 | 2011-05-04 | 中国石油化工股份有限公司 | Catalyst for preparing unsaturated acid from unsaturated aldehyde by oxidization and preparation method of catalyst |
| CN102371158A (en) * | 2010-08-23 | 2012-03-14 | 中国石油化工股份有限公司 | Catalyst of acrylic acid prepared by oxidation process and its preparation method |
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| CN102039141A (en) * | 2009-10-13 | 2011-05-04 | 中国石油化工股份有限公司 | Catalyst for preparing unsaturated acid from unsaturated aldehyde by oxidization and preparation method of catalyst |
| CN102371158A (en) * | 2010-08-23 | 2012-03-14 | 中国石油化工股份有限公司 | Catalyst of acrylic acid prepared by oxidation process and its preparation method |
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