CN103420820A - Production method of methylacrolein - Google Patents
Production method of methylacrolein Download PDFInfo
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- CN103420820A CN103420820A CN201210150517XA CN201210150517A CN103420820A CN 103420820 A CN103420820 A CN 103420820A CN 201210150517X A CN201210150517X A CN 201210150517XA CN 201210150517 A CN201210150517 A CN 201210150517A CN 103420820 A CN103420820 A CN 103420820A
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- butylene
- iso
- span
- trimethyl carbinol
- catalyzer
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Abstract
The invention relates to a production method of methylacrolein, and mainly solves the problems of poor reproducibility and low yield of the methylacrolein in the prior art. Through use of a technical scheme of the production method, the problems are well solved. The technical scheme is shown as follows: in a catalyst, at least one substance selected from SiO2 or Al2O3 is used as a carrier, the catalyst also contains an active component represented by the following general formula: Mo[12]Bi[a]Fe[b]Co[c]Ce[d]X[e]Y[f]Z[g]O[x], wherein X is at least one selected from the group consisting of W, V, Ni, Cr, Mn, Nb or Re, Y is at least one selected from the group consisting of Sn, Sr, Zn, Ti or Zr; Z is at least one selected from the group consisting of K, Rb, Na, Li, Tl or Cs. The production method can be used in industrial production of the methylacrolein.
Description
Technical field
The present invention relates to a kind of method of producing Methylacrylaldehyde.
Background technology
Methyl methacrylate (MMA) is a kind of important Organic Chemicals and Chemicals, mainly for the production of polymethylmethacrylate (synthetic glass, PMMA), polyvinyl chloride auxiliary agent A CR and as the second monomer of acrylic fiber production process, can also be for the production of coating, tackiness agent, lubricant, textile dyestuff etc.
The MMA conventional production methods is to take the Acetone cyanohydrin method that acetone and prussic acid is raw material, but this technique is used prussic acid and the sulfuric acid of high poison, highly corrosive, and a large amount of hydrogen sulfate ammonia of by-product, therefore require harsh and environment is produced to larger pressure production unit.After the last century the eighties, Japan catalyst, mitsubishi rayon and Asahi Kasei Corporation develop that to take iso-butylene/trimethyl carbinol in the hybrid C 4 cut be raw material MMA production technique processed in succession, because this process environments pollution is little, product cost is low, becomes very soon current world's second largest MMA production technique.In recent years, Britain Lucite company develops take the MMA production technique that ethene, methyl alcohol and CO be raw material, and had set up full scale plant in 2007 in Singapore.According to the said firm, claim: adopt this technique can the decrease raw materials cost.But its technology maturation and macroeconomic remain further to be checked.
Take iso-butylene or the trimethyl carbinol is that raw material three step oxidations produce the technique of methyl methacrylates and mainly comprise: one, and iso-butylene or trimethyl carbinol catalytic gas phase oxidation under molecular oxygen exists becomes Methylacrylaldehyde; Two, Methylacrylaldehyde catalytic gas phase oxidation under molecular oxygen exists becomes methacrylic acid; Three, methacrylic acid and methyl alcohol generation esterification generate methyl methacrylate.At present, the existing a large amount of reports of the patent of relevant iso-butylene or Oxidation of t-Butanol synthesize methyl acrylic aldehyde, nearly all patent all relates to Mo, Bi, Fe tri-dvielements, and they are the requisite components of catalyzer; And the improvement of catalyzer is mainly to carry out from activity and the stability aspect of catalyzer, as added transition metal to improve activity in active constituent, increases the single of product and receive; Add rare earth element to improve redox ability; Add the elements such as Fe, Co, Ni to suppress the distillation of Mo, the stabilizing catalyst activity component, improve the work-ing life of catalyzer etc.
Have a lot of patent reports for iso-butylene or trimethyl carbinol Selective Oxidation Methylacrylaldehyde:
Use the key component of the elements such as tellurium (Te), thallium (TI) as catalyzer in US Pat4250339, day disclosure special permission 57-72937 and CN1131059A, to improve the activity and selectivity of catalyzer, the loss but these materials are easy to disperse in the long-term operation process of catalyzer, thus the performance degradation of catalyzer caused.
US Pat5250485A proposes, by the composition of improvement catalyzer and their usage ratio and method for preparing catalyst, to improve iso-butylene or trimethyl carbinol transformation efficiency and target product yield.Isobutene conversion reaches 98.0%, Methylacrylaldehyde selectivity 85.3%, and methacrylic acid selectivity 4.5%, Methylacrylaldehyde and methacrylic acid are total recovery 85.0%, still not ideal enough.
JP Pat57-119837 is by adding macromolecular compound to control the catalyst surface structure, and for the Selective Oxidation of iso-butylene or the trimethyl carbinol, but still the problem that exists reactive behavior to reduce with the reaction times requires further improvement.
Summary of the invention
Technical problem to be solved by this invention is to have the problem that the Methylacrylaldehyde yield is lower in the reaction of iso-butylene or Preparation of Methacrolein by Oxidation of Tertiary Butyl Alcohol, and a kind of new iso-butylene or Preparation of Methacrolein by Oxidation of Tertiary Butyl Alcohol method are provided.The method is produced the methacrylic aldehyde reaction for iso-butylene or trimethyl carbinol selective oxidation, has advantages of that iso-butylene or trimethyl carbinol transformation efficiency are high, the Methylacrylaldehyde yield is high.
For solving the problems of the technologies described above, in the present invention, adopt technical scheme as follows: a kind of method of iso-butylene or trimethyl carbinol selective oxidation synthesize methyl acrylic aldehyde, take iso-butylene or the trimethyl carbinol and oxygen as raw material, the mol ratio of iso-butylene or the trimethyl carbinol and oxygen is 1:2～10, in temperature of reaction, it is 350～400 ℃, reaction pressure is 0.1～0.12 Mpa, and air speed is 800～1200 h
-1, the mol ratio of iso-butylene or the trimethyl carbinol and water is that under 1:1～4 conditions, raw material contacts with catalyzer, and reaction generates Methylacrylaldehyde, and wherein catalyzer used is to be selected from SiO
2Or Al
2O
3In at least one be carrier contain the active ingredient Mo by following general formula
12Bi
aFe
bCo
cCe
dX
eY
fZ
gO
x, in formula, the span of a is 0.05～6.0; The span of b is 0.05～8.5; The span of c is 0.05～15.0; The span of d is 0.01～9.0; The span of e is 0～5.0; The span of f is 0.05～15.0; The span of g is 0.01～5.0; X is at least one being selected from W, V, Ni, Cr, Mn, Nb or Re; Y is at least one being selected from Sn, Sr, Zn, Ti or Zr; Z is at least one being selected from K, Rb, Na, Li, Tl or Cs; A, b, c, d, e, f and g be the atom ratio of representative element bismuth, iron, cobalt, cerium, X, Y and Z respectively, and x meets the required Sauerstoffatom sum of other element valence, and in catalyzer, the consumption of carrier is catalyst weight 5～40%.
The solid content of catalyzer after oven dry is 25-75%.
In technique scheme, the mol ratio preferable range of iso-butylene or the trimethyl carbinol and oxygen is 1:2～5.
The preparation method of the catalyzer adopted in the inventive method is as follows:
A) ammonium molybdate of Kaolinite Preparation of Catalyst aequum is dissolved in water, then by Kaolinite Preparation of Catalyst, required carrier silicon sol, aluminum oxide or its mixture adds formation solution I;
B) metal salt solution of Kaolinite Preparation of Catalyst active ingredient aequum is dissolved in water and forms the solution II;
C) under agitation, the solution II is added in the solution I and forms catalyst pulp;
D) catalyst pulp is by dry, and making the solid content of catalyzer after oven dry is 25-75%, then obtains the catalyzer finished product through roasting.
In technique scheme, drying temperature is 70-100 ℃, and be 6-24 h time of drying.
The present invention finds this composite oxide catalysts of polycomponent for iso-butylene or Preparation of Methacrolein by Oxidation of Tertiary Butyl Alcohol, in catalyzer, the Ce component adds, the quantity of the active lattice oxygen species in the time of can obviously improving catalyst reaction, and lattice oxygen has important effect to the activity that improves catalyzer.The mensurable bonded atom of electronegativity attracts the ability of electronics, Bi
3+Pauling electronegativity value be 2.02, V
5+Pauling electronegativity value be 1.6, all than Mo
6+Pauling electronegativity value (2.35) little, the mobility of lattice oxygen that they produce in reaction is to Mo
6+Surface produce active sites or make its regeneration.And the Pauling electronegativity value of Ce is 1.12, electronegativity is less, and the lattice oxygen of its generation is also transferred to Mo
6+Surface produce activated sites, therefore can effectively improve the catalytic performance of catalyzer by adding Ce.Catalyzer of the present invention prepares the Methylacrylaldehyde reaction for iso-butylene or trimethyl carbinol selective oxidation, mol ratio at iso-butylene or the trimethyl carbinol and oxygen is 1:2～10, in temperature of reaction, be 350～400 ℃, reaction pressure is 0.1～0.12 Mpa, and air speed is 800～1200 h
-1The mol ratio of iso-butylene or the trimethyl carbinol and water is under 1:1～4 conditions, and its iso-butylene or trimethyl carbinol transformation efficiency can reach 98.5%, and Methylacrylaldehyde and methacrylic acid selectivity can reach 92.5%, product Methylacrylaldehyde and methacrylic acid yield can reach 91.1%, have obtained technique effect preferably.
Below by embodiment, the present invention is further elaborated.
Embodiment
[comparative example]
By 100 gram (NH
4)
6Mo
7O
244H
2O joins in the warm water of 70 ℃ of 100 grams, stirs and makes its whole dissolvings, adds the silicon sol of 63.2 grams 40% (wt.) to make material A.
By 38.5 gram Fe (NO
3)
39H
2O joins in 70 ℃ of hot water of 20 grams, adds 34.3 gram Bi (NO after stirring and dissolving again
3)
35H
2O, 41.2 gram Co (NO
3)
26H
2O, 25.1 gram Mn (NO
3)
2Solution (50%), 0.3 gram Zn (NO
3) 26H
2O, 0.5 gram CsNO
3Make material B after stirring and dissolving.
Solution B is added in solution A, form catalyst pulp, and stir aging 2 hours under 80 ℃, 70 ℃ of dry 6h of slurry, the slurry solid content is 25%, and then high-temperature roasting obtains the catalyzer finished product, and maturing temperature is 490 ℃.This catalyzer forms and preparation condition is listed in table 1, in the mol ratio of iso-butylene and oxygen, is 1:2; In temperature of reaction, it is 350 ℃; Reaction pressure is 0.1 Mpa; Air speed is 1000 h
-1The mol ratio of iso-butylene and water is to check and rate under the 1:2 condition, and it the results are shown in table 2.
[embodiment 1]
By 100 gram (NH
4)
6Mo
7O
244H
2O joins in the warm water of 70 ℃ of 100 grams, stirs and makes its whole dissolvings, adds silicon sol, 35.8 gram 20% aluminium colloidal sol and the 19.1 gram (NH of 89.4 grams 40% (wt.)
4)
6H
5[H
2(WO
4)
6] make material A.
By 38.5 gram Fe (NO
3)
39H
2O joins in 70 ℃ of hot water of 20 grams, adds 34.3 gram Bi (NO after stirring and dissolving again
3)
35H
2O, 41.2 gram Co (NO
3)
26H
2O, 6.1 gram Ce (NO
3)
36H
2O, 0.7 gram Zn (NO
3) 26H
2O, 0.3 gram CsNO
3Make material B after stirring and dissolving.
Solution B is added in solution A, form catalyst pulp, and stir aging 2 hours under 80 ℃, 80 ℃ of dry 12h of slurry, the slurry solid content is 50%, and then high-temperature roasting obtains the catalyzer finished product, and maturing temperature is 400 ℃～550 ℃.This catalyzer forms and preparation condition is listed in table 1, in the mol ratio of iso-butylene and oxygen, is 1:2; In temperature of reaction, it is 350 ℃; Reaction pressure is 0.1 Mpa; Air speed is 1000 h
-1The mol ratio of iso-butylene and water is to check and rate under the 1:2 condition, and it the results are shown in table 2.
[embodiment 2]
By 100 gram (NH
4)
6Mo
7O
244H
2O joins in the warm water of 70 ℃ of 100 grams, stirs and makes its whole dissolvings, adds silicon sol, 47.7 gram 20% aluminium colloidal sol and the 8.24 gram NH of 78.9 grams 40% (wt.)
4VO
3Make material A.
By 38.5 gram Fe (NO
3)
39H
2O joins in 70 ℃ of hot water of 20 grams, adds 34.3 gram Bi (NO after stirring and dissolving again
3)
35H
2O, 41.2 gram Co (NO
3)
26H
2O, 6.1 gram Ce (NO
3)
3, 0.7 gram Zn (NO
3) 26H
2O, 0.5 gram CsNO
3Make material B after stirring and dissolving.
Solution B is added in solution A, form catalyst pulp, and stir aging 2 hours under 80 ℃, 100 ℃ of dry 24h of slurry, slurry solid content 75%, then high-temperature roasting obtains the catalyzer finished product, and maturing temperature is 400 ℃～550 ℃.This catalyzer forms and preparation condition is listed in table 1, in the mol ratio of the trimethyl carbinol and oxygen, is 1:2; In temperature of reaction, it is 350 ℃; Reaction pressure is 0.1 Mpa; Air speed is 1000 h
-1The mol ratio of the trimethyl carbinol and water is to check and rate under the 1:2 condition, and it the results are shown in table 2.
[embodiment 3～11]
Make catalyzer by each step of implementing 2, concrete outcome is listed in table 1.Under the appreciation condition identical with embodiment 2, reaction result is listed in table 2.
[embodiment 12～21]
Under different reaction conditionss, the appraisal result of embodiment 1 catalyzer is listed in to table 3.
Table 1 catalyst weight forms and preparation condition
| ? | Catalyst weight forms | Solid content/g |
| Comparative example | Mo 12Bi 1.5Fe 2.0Co 3.0Mn 1.5Zn 0.02Cs 0.05+17%SiO 2 | 25 |
| Embodiment 1 | Mo 12Bi 1.5Fe 2.0Co 3.0Ce 0.3W 1.5Zn 0.05Gs 0.01+15% SiO 2+3%Al 2O 3 | 50 |
| Embodiment 2 | Mo 12Bi 1.5Fe 2.0Co 3.0Ce 0.3V 1.5Zn 0.05 Cs 0.05+19%SiO 2+4%Al 2O 3 | 75 |
| Embodiment 3 | Mo 12Bi 1.0Fe 3.0Co 3.0Ce 0.3Cr 1.5Sn 0.01Rb 0.08+19%SiO 2 | 50 |
| Embodiment 4 | Mo 12Bi 1.0Fe 2.0Co 3.0Ce 0.4Re 1.5Sn 0.08Cs 0.05+22%SiO 2 | 50 |
| Embodiment 5 | Mo 12Bi 1.0Fe 2.0Co 3.0Ce 0.4Ni 1.5Sn 0.05Cs 0.12+14%SiO 2 | 50 |
| Embodiment 6 | Mo 12Bi 1.0Fe 2.0Co 3.0Ce 0.4Nb 1.5Sn 0.03K 0.05+16%SiO 2+4%Al 2O 3 | 50 |
| Embodiment 7 | Mo 12Bi 0.5Fe 2.0Co 2.0Ce 0.5Mn 0.5Sr 0.05K 0.05+18%SiO 2+5%Al 2O 3 | 75 |
| Embodiment 8 | Mo 12Bi 0.5Fe 3.0Co 2.0Ce 0.5Mn 0.5Sr 0.60Cs 0.05+23%SiO 2 | 75 |
| Embodiment 9 | Mo 12Bi 0.5Fe 2.0Co 2.0Ce 0.5Mn 0.5Sr 0.03Cs 0.05+18%SiO 2 | 75 |
| Embodiment 10 | Mo 12Bi 0.5Fe 2.0Co 2.0Ce 0.5Mn 0.5Sr 0.10Cs 0.05+16%SiO 2+8%Al 2O 3 | 75 |
| Embodiment 11 | Mo 12Bi 0.5Fe 3.0Co 2.0Ce 0.5Mn 0.5Sr 0.05Rb 0.08+19%SiO 2+6%Al 2O 3 | 75 |
Table 2 evaluating catalyst result 1
Evaluating catalyst result 2 under table 3 differential responses condition
Claims (2)
1. the method for an iso-butylene or trimethyl carbinol selective oxidation synthesize methyl acrylic aldehyde, take iso-butylene or the trimethyl carbinol and oxygen as raw material, and the mol ratio of iso-butylene or the trimethyl carbinol and oxygen is 1:2～10, in temperature of reaction, is 350～400 ℃, reaction pressure is 0.1～0.12 Mpa, and air speed is 800～1200 h
-1, the mol ratio of iso-butylene or the trimethyl carbinol and water is that under 1:1～4 conditions, raw material contacts with catalyzer, and reaction generates Methylacrylaldehyde, and wherein catalyzer used is to be selected from SiO
2Or Al
2O
3In at least one be carrier contain the active ingredient Mo by following general formula
12Bi
aFe
bCo
cCe
dX
eY
fZ
gO
x, in formula, the span of a is 0.5～6.0; The span of b is 0.05～8.5; The span of c is 0.05～15.0; The span of d is 0.01～5.0; The span of e is 0～5.0; The span of f is 0.05～15.0; The span of g is 0.01～5.0; X is at least one being selected from W, V, Ni, Cr, Mn, Nb or Re; Y is at least one being selected from Sn, Sr, Zn, Ti or Zr; Z is at least one being selected from K, Rb, Na, Li, Tl or Cs; A, b, c, d, e, f and g be the atom ratio of representative element bismuth, iron, cobalt, cerium, X, Y and Z respectively, and x meets the required Sauerstoffatom sum of other element valence, and in catalyzer, the consumption of carrier is catalyst weight 5～40%.
2. according to the method for the described iso-butylene of claims 1 or trimethyl carbinol synthesize methyl acrylic aldehyde, the mol ratio that it is characterized in that iso-butylene or the trimethyl carbinol and oxygen is 1:2～5.
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| CN103420820B CN103420820B (en) | 2016-05-18 |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104801312A (en) * | 2015-03-17 | 2015-07-29 | 烟台大学 | Composite oxide catalyst and preparation method |
| CN105498795A (en) * | 2014-09-25 | 2016-04-20 | 中国石油化工股份有限公司 | Methacrylaldehyde catalyst and preparation method thereof |
| CN105503558A (en) * | 2014-09-25 | 2016-04-20 | 中国石油化工股份有限公司 | Synthesis method of methacrylaldehyde |
| CN106807394A (en) * | 2017-01-12 | 2017-06-09 | 南京氧簇科技有限公司 | A kind of catalyst of isobutylene oxidation synthesizing methyl methacrylaldehyde and preparation method thereof |
| JP2020171906A (en) * | 2019-04-15 | 2020-10-22 | 日本化薬株式会社 | Catalyst and production method of the same |
| CN115569650A (en) * | 2021-07-06 | 2023-01-06 | 惠生工程（中国）有限公司 | Catalyst for synthesizing unsaturated aldehyde and preparation method thereof |
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| CN1871201A (en) * | 2003-12-26 | 2006-11-29 | Lg化学株式会社 | Method of producing unsaturated aldehyde and/or unsaturated fatty acid |
| CN102091634A (en) * | 2010-12-13 | 2011-06-15 | 上海华谊丙烯酸有限公司 | Preparation method of catalyst used in reaction of preparing methylacrolein by selective oxidation of isobutene/tertiary butanol |
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Patent Citations (4)
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| CN1280036A (en) * | 1999-05-13 | 2001-01-17 | 株式会社日本触媒 | Catalyst for producing unsaturated aldehyde and unsaturated carboxylic acid and its use |
| CN1282630A (en) * | 1999-05-25 | 2001-02-07 | 株式会社日本触媒 | Compound oxide catalyst and method for preparing (methyl) propenal and (methgl) acrylic acid |
| CN1871201A (en) * | 2003-12-26 | 2006-11-29 | Lg化学株式会社 | Method of producing unsaturated aldehyde and/or unsaturated fatty acid |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105498795A (en) * | 2014-09-25 | 2016-04-20 | 中国石油化工股份有限公司 | Methacrylaldehyde catalyst and preparation method thereof |
| CN105503558A (en) * | 2014-09-25 | 2016-04-20 | 中国石油化工股份有限公司 | Synthesis method of methacrylaldehyde |
| CN104801312A (en) * | 2015-03-17 | 2015-07-29 | 烟台大学 | Composite oxide catalyst and preparation method |
| CN106807394A (en) * | 2017-01-12 | 2017-06-09 | 南京氧簇科技有限公司 | A kind of catalyst of isobutylene oxidation synthesizing methyl methacrylaldehyde and preparation method thereof |
| CN106807394B (en) * | 2017-01-12 | 2019-07-19 | 南京氧簇科技有限公司 | A kind of catalyst and preparation method thereof of isobutylene oxidation synthesizing methyl methacrylaldehyde |
| JP2020171906A (en) * | 2019-04-15 | 2020-10-22 | 日本化薬株式会社 | Catalyst and production method of the same |
| JP7209578B2 (en) | 2019-04-15 | 2023-01-20 | 日本化薬株式会社 | Catalyst and its manufacturing method |
| CN115569650A (en) * | 2021-07-06 | 2023-01-06 | 惠生工程（中国）有限公司 | Catalyst for synthesizing unsaturated aldehyde and preparation method thereof |
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