CN103521234A - Catalyst for preparing acrylic acid through acrolein oxidation and preparation method thereof - Google Patents
Catalyst for preparing acrylic acid through acrolein oxidation and preparation method thereof Download PDFInfo
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- CN103521234A CN103521234A CN201210225849.XA CN201210225849A CN103521234A CN 103521234 A CN103521234 A CN 103521234A CN 201210225849 A CN201210225849 A CN 201210225849A CN 103521234 A CN103521234 A CN 103521234A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 50
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 title claims abstract description 36
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 title claims abstract description 32
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 17
- 230000003647 oxidation Effects 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 6
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 5
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 5
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 5
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 5
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 5
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 5
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 5
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 5
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 5
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 3
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 3
- 229910052718 tin Inorganic materials 0.000 claims abstract description 3
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 12
- 239000003377 acid catalyst Substances 0.000 claims description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- 238000009826 distribution Methods 0.000 claims description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims description 5
- 239000011148 porous material Substances 0.000 claims description 5
- 229910052720 vanadium Inorganic materials 0.000 claims description 5
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 4
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 4
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 claims description 4
- 238000001125 extrusion Methods 0.000 claims description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 4
- 235000021355 Stearic acid Nutrition 0.000 claims description 3
- 239000000470 constituent Substances 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 3
- 239000008117 stearic acid Substances 0.000 claims description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims description 2
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 claims description 2
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- 244000275012 Sesbania cannabina Species 0.000 claims description 2
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 2
- 229920002472 Starch Polymers 0.000 claims description 2
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 2
- 239000011609 ammonium molybdate Substances 0.000 claims description 2
- 229940010552 ammonium molybdate Drugs 0.000 claims description 2
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 2
- 229940116318 copper carbonate Drugs 0.000 claims description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims description 2
- 239000001863 hydroxypropyl cellulose Substances 0.000 claims description 2
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 2
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 2
- 239000008107 starch Substances 0.000 claims description 2
- 235000019698 starch Nutrition 0.000 claims description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract 1
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000000377 silicon dioxide Substances 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 15
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 230000000694 effects Effects 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 description 2
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a catalyst for preparing acrylic acid through acrolein oxidation and a preparation method thereof, which are mainly used for solving the problems of relatively low acrylic acid selectivity and low yield in the prior art. The catalyst provided by the invention takes at least one of SiO2, Al2O3 and TiO2 as a carrier and comprises an active component shown by the general formula: Mo12VaCubXcYdZeOx, wherein X is at least one of W, Cr, Sn and Nb; Y is at least one of Fe, Bi, Co, Ni, Sb, Ce, La, Zr and Sr; Z is at least one of alkali metal and alkaline-earth metal. By adopting the technical scheme, the problems are better solved, and the catalyst can be applied to the industrial production for producing acrylic acid through acrolein oxidation.
Description
Technical field
The present invention relates to a kind ofly by acrolein oxidation, prepare acrylic acid Catalysts and its preparation method.
Background technology
It is important chemical process that a, b unsaturated aldehyde and unsaturated acids are prepared in the selective oxidation of alkene, the catalyst that wherein contains Mo, V by a kind of active component of the acrylic acid production and application of methacrylaldehyde system.The improvement of catalyst is mainly that carry out activity from catalyst, selective and stability aspect, as added transition metal to improve activity in active constituent, increases the single of product and receives; Add rare earth element to 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 of catalyst etc.
For methacrylaldehyde selective oxidation, have a lot of patent reports:
US Pat7220698B2, by adding a kind of catalyst poison of trace in catalyst preparation process, controls catalyst reaction bed focus, suppresses the thermal degradation of catalyst, improves catalyst stability.Acrolein conversion rate reaches 98.8%, and keeps for a long time stable.US Pat7378367B2 has introduced 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.US Pat7456129B2 improves catalyst performance, acrolein conversion rate 98.9%, acrylic acid selective 95.1% by controlling carrier acid strength.
CN1183088C introduces a kind of method for preparing catalyst, and by selecting specific raw materials, acrolein conversion rate is up to 99.6%, and acrylic acid is selectively up to 96.0%, and acrylic acid yield is up to 95.2%.
In sum, in existing document, all there is the selective low and lower problem of acrylic acid yield of acrylic acid.The pore passage structure of preformed catalyst, pore-size distribution etc. also have a certain impact to catalytic performance in addition.Existing patent does not all relate to this problem.In this patent, will relate to this problem.
Summary of the invention
One of technical problem to be solved by this invention is the selective lower and lower problem of acrylic acid yield of acrylic acid in prior art, provides a kind of new prepared by acrolein oxidation acrylic acid catalyst.This catalyst is produced acrylic acid reaction for methacrylaldehyde selective oxidation, has advantages of that the selective height of acrylic acid and acrylic acid yield are high.Two of technical problem to be solved by this invention is to provide the corresponding preparation method of a kind of catalyst used with one of technical solution problem.
For one of solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind ofly by acrolein oxidation, prepare acrylic acid catalyst, to be selected from SiO
2, Al
2o
3or TiO
2in at least one be carrier, active constituent is by following general formula:
Mo
12V
aCu
bX
cY
dZ
eO
x
In formula, X is at least one being selected from W, Cr, Sn or Nb;
Y is at least one being selected from Fe, Bi, Co, Ni, Sb, Ce, La, Zr or Sr;
Z is at least one being selected from 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 required oxygen atom sum of other element valence;
In catalyst, the consumption of carrier is catalyst weight 5～40%; The pore size distribution of catalyst is as follows: 3-is less than 20nm and accounts for 8-15%, and 20-is less than 70nm and accounts for 45-60%, and 70-210nm accounts for 30-45%.
In technique scheme, the value preferable range of a is 2.0～7.0; The value preferable range of b is 1.2～5.5; The value preferable range of c is 1.0～7.2; The value preferable range of d is 0.8～4.8; The span of e is 0.7～3.6.
For solve the problems of the technologies described above two, the technical solution used in the present invention is as follows: a kind of preparation method who is prepared acrylic acid catalyst by acrolein oxidation, comprises the following steps:
A) oxide that is selected from Mo, V, Cu, Fe, Bi, Co, Ni, Sb, Ce, La, Zr or Sr of aequum or salt are evenly mixed to get to mixture 1;
B) by the ammonium tungstate of aequum and be selected from alkali metal or the hydroxide of alkaline-earth metal or at least one in oxide, wiring solution-forming 1;
C) mixture 1 and solution 1 are mixed to get to mixture 2 mutually;
D) to the SiO that is selected from that adds aequum in mixture 2
2, Al
2o
3or TiO
2in at least one carrier and be selected from least one in sesbania powder, ethylene glycol, carboxymethyl cellulose, hydroxyethylcellulose, hydroxypropyl cellulose, sodium carboxymethylcellulose, starch, stearic acid or polyvinyl alcohol, obtain mixture 3;
E), by mixture 3 extrusions, after being dried, by 350-600 ℃ of roasting, obtain required catalyst.
In technique scheme, in catalyst preparation process, the addition preferred version of auxiliary compound is the 2-10% that accounts for catalyst weight.Wherein, molybdenum source preferred version is from ammonium molybdate, and copper source preferred version is from copper nitrate or basic copper carbonate, and vanadium source preferred version is from ammonium metavanadate, and other are all from nitrate.
The present invention is owing to having added auxiliary compound in catalyst preparation process, this compound demonstrates good cementation in shaping of catalyst process, thereby in Roasting Decomposition process subsequently, has affected reactivity worth and intensity that the physical parameters such as catalyst metals redox condition and catalyst specific surface area of finished products, pore size distribution have improved catalyst.Owing to having formed special pore size distribution structure, make reactant be easy to absorption, simultaneous reactions product is easy to desorption, and deep oxidation reaction is subject to certain inhibition, thereby has improved acrylic acid selective and yield.Using catalyst of the present invention to prepare acrylic acid for methacrylaldehyde selective oxidation, is that 280 ℃, reaction velocity are 1400 hours in reaction temperature
-1condition under, its acrolein conversion rate can reach 99.0%, acrylic acid selectively can reach 99.1%, product acrylic acid yield can reach 98.1%, yield has improved at least 0.5 percentage point than prior art, has obtained good technique effect.
In the embodiment providing below, to the investigation appreciation condition of catalyst, be:
Reactor: fixed bed reactors, 25.4 millimeters of internal diameters, 750 millimeters of reactor length
Catalyst filling amount: 150 grams
Reaction temperature: 280 ℃
Reaction time: 4 hours
Raw material ratio: methacrylaldehyde/air/water steam=15.8/50.9/33.3
Reaction velocity: 1400 hours
-1
Product absorbs with 0 ℃ of diluted acid, uses gas chromatographic analysis product.And calculate Carbon balance, when Carbon balance is valid data during at (95～105) %.
Acrolein conversion rate, product yield and be optionally defined as:
Below by embodiment, the present invention is further elaborated.
The specific embodiment
[comparative example 1]
Take 450 grams of ammonium molybdates, 116.2 grams of ammonium metavanadates, 140.9 grams of basic copper carbonates, 15 grams of stearic acid, 76.3 grams of iron oxide, 30.5 grams of strontium oxide strontias, add in kneader and mediate 1 hour, add again ammonium tungstate (57.3 grams) solution after dissolving, potassium hydroxide (10.7 grams) solution, mediate 30 minutes, add again 147.3 grams of Ludox (40wt%), continue to mediate, when thing to be mixed reaches certain humidity and hardness, take out and put into the cylinder that banded extruder extrusion molding obtains φ 3.5x3.5mm, then high-temperature roasting obtains catalyst finished product, sintering temperature is 430 ℃, by above-mentioned examination condition, reaction appraisal result is listed in table 2.Comparative example 2 makes catalyst by the step of comparative example 1, does not just add auxiliary compound.
[embodiment 1]
Take 450 grams of ammonium molybdates, 84 grams of ammonium metavanadates, 131.5 grams of basic copper carbonates, 58.5 grams of cerium oxide, 34 grams of zirconias, 18 grams of ethylene glycol, putting into kneader mediates 1 hour, add again ammonium tungstate (74.5 grams) solution after dissolving, potassium hydroxide (15 grams) solution, cesium hydroxide (8.2 grams) solution, mediate 30 minutes, add again 183 grams of Ludox (40wt%), continue to mediate, when thing to be mixed reaches certain humidity and hardness, take out and put into the cylinder that banded extruder extrusion molding obtains φ 3.5x3.5mm, then high-temperature roasting obtains catalyst finished product, sintering temperature is 430 ℃.
[embodiment 2～11]
Each step by embodiment 1 makes catalyst, just changes catalyst preparation condition and adds kind and the consumption of auxiliary compound, and concrete outcome is listed in table 1, and under above-mentioned identical appreciation condition, reaction appraisal result is listed in table 2.The pore-size distribution of each catalyst is listed in table 3.
Table 1 catalyst
Table 2 catalyst is investigated result
| ? | Acrylic acid yield (%) | Acrylic acid selective (%) | Acrolein conversion rate (%) | Catalyst strength |
| Comparative example 1 | 97.1 | 98.0 | 99.1 | Good |
| Comparative example 2 | 95.8 | 98.0 | 97.8 | Generally |
| Embodiment 1 | 97.4 | 98.9 | 98.5 | Generally |
| Embodiment 2 | 97.3 | 98.7 | 98.6 | Poor |
| Embodiment 3 | 97.7 | 98.5 | 99.2 | Poor |
| Embodiment 4 | 98.1 | 99.1 | 99 | Good |
| Embodiment 5 | 96.3 | 97.5 | 98.8 | Poor |
| Embodiment 6 | 96.4 | 96.8 | 99.6 | Poor |
| Embodiment 7 | 96.6 | 98.2 | 98.4 | Good |
| Embodiment 8 | 96.7 | 97.7 | 99.0 | Poor |
| Embodiment 9 | 97.9 | 99.4 | 98.5 | Generally |
| Embodiment 10 | 97.9 | 99.1 | 98.8 | Good |
| Embodiment 11 | 97.2 | 98.9 | 98.3 | Good |
Table 3 catalyst aperture distributes
| ? | 3-is less than 20nm (%) | 20-is less than 70nm (%) | 70-210nm(%) |
| Comparative example 1 | 12 | 50 | 38 |
| Comparative example 2 | 20 | 65 | 15 |
| Embodiment 1 | 11 | 48 | 41 |
| Embodiment 2 | 11.5 | 49 | 39.5 |
| Embodiment 3 | 15 | 52 | 33 |
| Embodiment 4 | 13.5 | 46 | 41.5 |
| Embodiment 5 | 14 | 55 | 31 |
| Embodiment 6 | 14.8 | 53 | 32.2 |
| Embodiment 7 | 12 | 58 | 30 |
| Embodiment 8 | 12 | 56 | 32 |
| Embodiment 9 | 10 | 45 | 45 |
| Embodiment 10 | 9 | 49 | 42 |
| Embodiment 11 | 8 | 60 | 32 |
Claims (4)
1. by acrolein oxidation, prepare an acrylic acid catalyst, to be selected from SiO
2, Al
2o
3or TiO
2in at least one be carrier, active constituent is by following general formula:
Mo
12V
aCu
bX
cY
dZ
eO
x
In formula, X is at least one being selected from W, Cr, Sn or Nb;
Y is at least one being selected from Fe, Bi, Co, Ni, Sb, Ce, La, Zr or Sr;
Z is at least one being selected from 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 required oxygen atom sum of other element valence;
In catalyst, the consumption of carrier is catalyst weight 5～40%;
The pore size distribution of catalyst is as follows: 3-is less than 20nm and accounts for 8-15%, and 20-is less than 70nm and accounts for 45-60%, and 70-210nm accounts for 30-45%.
2. according to claim 1 by prepared by acrolein oxidation acrylic acid catalyst, the span that it is characterized in that 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. the preparation method by prepared by acrolein oxidation acrylic acid catalyst claimed in claim 1, comprises the following steps:
A) oxide that is selected from Mo, V, Cu, Fe, Bi, Co, Ni, Sb, Ce, La, Zr or Sr of aequum or salt are evenly mixed to get to mixture 1;
B) by the ammonium tungstate of aequum and be selected from alkali metal or the hydroxide of alkaline-earth metal or at least one in oxide, wiring solution-forming 1;
C) mixture 1 and solution 1 are mixed to get to mixture 2 mutually;
D) to the SiO that is selected from that adds aequum in mixture 2
2, Al
2o
3or TiO
2in at least one carrier and be selected from least one in sesbania powder, ethylene glycol, carboxymethyl cellulose, hydroxyethylcellulose, hydroxypropyl cellulose, sodium carboxymethylcellulose, starch, stearic acid or polyvinyl alcohol, obtain mixture 3;
E), by mixture 3 extrusions, after being dried, by 350-600 ℃ of roasting, obtain required catalyst.
4. according to preparing the preparation method of acrylic acid catalyst by acrolein oxidation described in claims 3, it is characterized in that the addition of auxiliary compound in catalyst preparation process accounts for the 2-10% of catalyst weight; Wherein, molybdenum source is from ammonium molybdate, and copper source is from copper nitrate or basic copper carbonate, and vanadium source is from ammonium metavanadate, and other are all from nitrate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210225849.XA CN103521234A (en) | 2012-07-03 | 2012-07-03 | Catalyst for preparing acrylic acid through acrolein oxidation and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210225849.XA CN103521234A (en) | 2012-07-03 | 2012-07-03 | Catalyst for preparing acrylic acid through acrolein oxidation and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103521234A true CN103521234A (en) | 2014-01-22 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210225849.XA Pending CN103521234A (en) | 2012-07-03 | 2012-07-03 | Catalyst for preparing acrylic acid through acrolein oxidation and preparation method thereof |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104923247A (en) * | 2014-03-17 | 2015-09-23 | 中国石油化工股份有限公司 | Catalyst for synthesis of acrylic acid from acraldehyde |
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| CN105080558A (en) * | 2014-05-14 | 2015-11-25 | 中国石油化工股份有限公司 | Catalyst for acrylic acid synthesis and preparation method thereof |
| CN107282069A (en) * | 2016-04-13 | 2017-10-24 | 中国石油化工股份有限公司 | Acrolein oxidation generates the catalyst of acrylic acid |
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| CN102451702A (en) * | 2010-10-21 | 2012-05-16 | 中国石油化工股份有限公司 | Catalyst for preparing acrylic acid by acrolein oxidation and preparation method thereof |
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| CN103769149A (en) * | 2012-10-25 | 2014-05-07 | 中国石油化工股份有限公司 | Catalyst for preparing propenoic acid through oxidation of propenal, as well as preparation and application of catalyst |
| CN104923247A (en) * | 2014-03-17 | 2015-09-23 | 中国石油化工股份有限公司 | Catalyst for synthesis of acrylic acid from acraldehyde |
| CN104923245A (en) * | 2014-03-17 | 2015-09-23 | 中国石油化工股份有限公司 | Acrylic acid catalyst and synthesis method of acrylic acid |
| CN104923247B (en) * | 2014-03-17 | 2018-06-08 | 中国石油化工股份有限公司 | By the catalyst of methacrylaldehyde acrylic acid synthesizing |
| CN104923245B (en) * | 2014-03-17 | 2018-01-09 | 中国石油化工股份有限公司 | Acrylic acid catalyst and acrylic acid synthetic method |
| CN105080558B (en) * | 2014-05-14 | 2017-10-27 | 中国石油化工股份有限公司 | Acrylic acid catalyst and preparation method thereof |
| CN105080558A (en) * | 2014-05-14 | 2015-11-25 | 中国石油化工股份有限公司 | Catalyst for acrylic acid synthesis and preparation method thereof |
| CN107282059A (en) * | 2016-04-13 | 2017-10-24 | 中国石油化工股份有限公司 | Produce the catalyst of acrylic acid |
| CN107282069A (en) * | 2016-04-13 | 2017-10-24 | 中国石油化工股份有限公司 | Acrolein oxidation generates the catalyst of acrylic acid |
| CN107282059B (en) * | 2016-04-13 | 2020-08-07 | 中国石油化工股份有限公司 | Catalyst for producing acrylic acid |
| CN115475623A (en) * | 2021-06-16 | 2022-12-16 | 中国石油化工股份有限公司 | Catalyst for preparing acrolein by selective oxidation of propylene and preparation method and application thereof |
| CN115487817A (en) * | 2021-06-18 | 2022-12-20 | 中国石油化工股份有限公司 | Catalyst for acrylic acid synthesis and preparation method thereof, molded catalyst for acrylic acid synthesis and preparation method thereof, and acrylic acid synthesis method |
| CN115487817B (en) * | 2021-06-18 | 2024-01-26 | 中国石油化工股份有限公司 | Catalyst for acrylic acid synthesis, preparation method thereof, molding catalyst for acrylic acid synthesis, preparation method thereof and acrylic acid synthesis method |
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