CN103739468A - Method of producing methylacrolein - Google Patents
Method of producing methylacrolein Download PDFInfo
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- CN103739468A CN103739468A CN201210393089.3A CN201210393089A CN103739468A CN 103739468 A CN103739468 A CN 103739468A CN 201210393089 A CN201210393089 A CN 201210393089A CN 103739468 A CN103739468 A CN 103739468A
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- methylacrylaldehyde
- butylene
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- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
- C07C45/34—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds
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- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/37—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups
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Abstract
The invention relates to a method of producing methylacrolein, mainly solving problems of the low yield and the low selectivity of the methylacrolein in the prior art. According to the technical scheme adopted by the method, at least one selected from SiO2 or Al2O3 is adopted as a carrier, and a catalyst comprises an active component having a general formula of Mo<12>Bi<a>Fe<b>Co<c>Sb<d>X<e>Y<f>Z<g>O<x>, wherein the X is at least one selected from W, V, Ni, Cr, Mn, Nb or Re; the Y is at least one selected form Sn, Sr, Zn, Ti or Zi; and the Z is at least one selected from K, Rb, Na, Li, Tl or Cs. By the technical scheme, the problems are solved and the method can be used in industrial production of the methylacrolein.
Description
Technical field
The present invention relates to a kind of manufacture Methylacrylaldehyde method.
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.
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 requires harsh and environment is produced to larger pressure production unit.After last century the eighties, Japan catalyst, mitsubishi rayon and Asahi Kasei Corporation develop that to take iso-butylene/trimethyl carbinol in 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 Nian Singapore.According to the said firm, claim: adopt this technique can significantly reduce raw materials cost.But its technology maturation and macroeconomic need further to be checked.
Take iso-butylene or the trimethyl carbinol is that raw material three steps 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, stabilizing catalyst activity component, improves the work-ing life of catalyzer etc.
For iso-butylene or trimethyl carbinol Selective Oxidation Methylacrylaldehyde, have a lot of patent reports:
In US Pat4250339, day disclosure special permission 57-72937 and CN1131059A, use the elements such as tellurium (Te), thallium (TI) as the key component of catalyzer, 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 improving the composition of 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 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 Methylacrylaldehyde yield is lower in the reaction of existing iso-butylene or Preparation of Methacrolein by Oxidation of Tertiary Butyl Alcohol, and a kind of new manufacture Methylacrylaldehyde method is provided.The method has advantages of iso-butylene or trimethyl carbinol transformation efficiency is high, selectivity good, Methylacrylaldehyde yield is high.
For solving the problems of the technologies described above, the technical scheme adopting in the present invention is as follows: a kind of manufacture Methylacrylaldehyde method, 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 hours
-1, the mol ratio of iso-butylene or the trimethyl carbinol and water is 1:(1～4) and under condition, raw material and catalyzer contact reacts generate Methylacrylaldehyde; Wherein catalyzer used is to be selected from SiO
2or Al
2o
3in at least one be carrier, and the active ingredient that contains following general formula: Mo
12bi
afe
bco
csb
dx
ey
fz
go
x;
In formula, a, b, c, d, e, f and g be the atom ratio of representative element bismuth, iron, cobalt, antimony, X, Y and Z respectively, and x meets the required Sauerstoffatom sum of other element valence;
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;
In catalyzer, the consumption of carrier is catalyst weight 5～40%.
In technique scheme, X preferred version is at least one being selected from W, V, Ni, Cr, Nb or Re.Y preferred version is at least one being selected from Sn, Sr or Zn.The value preferable range of a is 0.5～5.0; The value preferable range of b is 1.0～5.0; The value preferable range of c is 1.0～10.0; The value preferable range of d is 0.1～5.0; The value preferable range of e is 0.01～3.0; The value preferable range of f is 0.1～10.0; The value preferable range of g is 0.02～3.0.Temperature of reaction preferable range is 360～390 ℃.Air speed preferable range is 900～1100 hours
-1.The mol ratio preferable range of iso-butylene or the trimethyl carbinol and water is 1:(1.5～3.5), more preferably scope is 1:(2～3).The mol ratio preferable range of iso-butylene or the trimethyl carbinol and oxygen is 1:(2～8), more preferably scope is 1:(2.5～6).
The preparation method of the catalyzer adopting in the inventive method is as follows:
A) ammonium molybdate of Kaolinite Preparation of Catalyst aequum is dissolved in water, then the carrier silicon sol of Kaolinite Preparation of Catalyst aequum, aluminum oxide or its mixture is added and form solution I;
B) by Kaolinite Preparation of Catalyst, the metal salt solution of the active ingredient aequum except antimony component is dissolved in and in water, forms solution II;
C) under agitation, solution II is added and in solution I, form catalyst pulp I;
D) in slurry I, add the precipitation agent of aequum to obtain slurry II, precipitation agent is selected from least one in ammoniacal liquor, urea, quadrol, propylamine or trolamine, and the add-on of precipitation agent accounts for the 0.5-5% of catalyst weight.
E) slurry II is removed after most of moisture by oven dry, obtains catalyst precursor I, and the oxide compound of the antimony of Kaolinite Preparation of Catalyst aequum is added in catalyst precursor I and carries out mechanically mixing, forms catalyst precursor II.Catalyst precursor II obtains catalyzer finished product through extrusion moulding, roasting.
In the present invention, adding antimony compounds is to make the active of catalyzer for improving, added component S b, on the coordination unsaturated orbit of Sb5+ ion, be easy to carry out chemisorption and the insertion of lattice oxygen in π-allyl group of alkene, for catalyzed reaction provides lattice oxygen species, insert center, thereby more easily form the active ingredient of Methylacrylaldehyde.But the interpolation of antimony compounds is complicated and time-consuming in previous patent, therefore adopting the method for mechanically mixing is a kind of easy preparation method.Catalyzer of the present invention is prepared 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 hours
-1the mol ratio of iso-butylene or the trimethyl carbinol and water is 1:(1～4) under condition, its iso-butylene or trimethyl carbinol transformation efficiency can reach 98.5%, Methylacrylaldehyde and methacrylic acid selectivity can reach 92.5%, product Methylacrylaldehyde and methacrylic acid yield can reach 91.1%, have obtained good technique effect.
Below by embodiment, the present invention is further elaborated.
Embodiment
[comparative example]
By 100 grams of (NH
4)
6mo
7o
244H
2o joins in the warm water of 100 grams 70 ℃, stirs it is all dissolved, and adds the silicon sol of 103.7 gram 40% (wt.) to make material A.
By 38.5 grams of Fe (NO
3)
39H
2o joins in 70 ℃ of hot water of 20 grams, adds 34.3 grams of Bi (NO after stirring and dissolving again
3)
35H
2o, 41.2 grams of Co (NO
3)
26H
2o, 25.1 grams of Mn (NO
3)
2solution (50%), 2.1 grams of Er (NO
3)
36H
2o, 0.28 gram of Zn (NO
3)
26H
2o, 0.46 gram of CsNO
3after stirring and dissolving, make material B.
Solution B is under agitation added in solution A, form catalyst pulp, add 5.10 grams of ammoniacal liquor, and at 80 ℃, stir aging 2 hours, extrusion moulding after 120 ℃ of oven dry removal most of moisture of slurry, obtain the cylinder of φ 3.5x3.5mm, then high-temperature roasting obtains 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 hours
-1; The mol ratio of iso-butylene and water is to check and rate under 1:2 condition, and it the results are shown in table 2.
[embodiment 1]
By 100 grams of (NH
4)
6mo
7o
244H
2o joins in the warm water of 100 grams 70 ℃, stirs it is all dissolved, and adds the silicon sol of 89.4 gram 40% (wt.), 35.8 gram of 20% aluminium colloidal sol and 19.1 grams of (NH
4)
6h
5[H
2(WO
4)
6] make material A.
By 38.5 grams of Fe (NO
3)
39H
2o joins in 70 ℃ of hot water of 150 grams, adds 34.3 grams of Bi (NO after stirring and dissolving again
3)
35H
2o, 41.2 grams of Co (NO
3)
26H
2o, 2.1 grams of Er (NO
3)
33H
2o, 0.7 gram of Zn (NO
3)
26H
2o, 0.27 gram of CsNO
3after stirring and dissolving, make material B.
Solution B is under agitation added in solution A, form catalyst pulp, add 5.13 grams of ammoniacal liquor, and at 80 ℃, stir aging 2 hours, 120 ℃ of oven dry of slurry are removed after most of moisture, add 0.4 gram of antimonous oxide to carry out mechanically mixing, last extrusion moulding, obtain the cylinder of φ 3.5x3.5mm, then high-temperature roasting obtains 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 hours
-1; The mol ratio of iso-butylene and water is to check and rate under 1:2 condition, and it the results are shown in table 2.
[embodiment 2]
By 100 grams of (NH
4)
6mo
7o
244H
2o joins in the warm water of 100 grams 70 ℃, stirs it is all dissolved, and adds the silicon sol of 78.9 gram 40% (wt.), 47.7 gram of 20% aluminium colloidal sol and 8.24 grams of NH
4vO
3make material A.
By 38.5 grams of Fe (NO
3)
39H
2o joins in 70 ℃ of hot water of 150 grams, adds 34.3 grams of Bi (NO after stirring and dissolving again
3)
35H
2o, 41.2 grams of Co (NO
3)
26H
2o, 2.1 grams of Er (NO
3)
33H
2o, 0.7 gram of Zn (NO
3)
26H
2o, 0.27 gram of CsNO
3after stirring and dissolving, make material B.
Solution B and C are under agitation added in solution A, form catalyst pulp, add 5.60 grams, urea, and at 80 ℃, stir aging 2 hours, 100 ℃, slurry adds 0.4 gram of antimonous oxide to carry out mechanically mixing after drying and removing most of moisture, and last extrusion moulding obtains the cylinder of φ 3.5x3.5mm, then high-temperature roasting obtains 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 hours
-1; The mol ratio of the trimethyl carbinol and water is to check and rate under 1:2 condition, and it the results are shown in table 2.
[embodiment 3～11]
Each step by [embodiment 2] makes catalyzer, and 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
Table 2
Table 3
Claims (10)
1. manufacture Methylacrylaldehyde method for one kind, 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, be 350～400 ℃, reaction pressure is 0.1～0.12 MPa, and air speed is 800～1200 hours
-1, the mol ratio of iso-butylene or the trimethyl carbinol and water is 1:(1～4) and under condition, raw material and catalyzer contact reacts generate Methylacrylaldehyde; Wherein catalyzer used is to be selected from SiO
2or Al
2o
3in at least one be carrier, and the active ingredient that contains following general formula: Mo
12bi
afe
bco
csb
dx
ey
fz
go
x;
In formula, a, b, c, d, e, f and g be the atom ratio of representative element bismuth, iron, cobalt, antimony, X, Y and Z respectively, and x meets the required Sauerstoffatom sum of other element valence;
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;
In catalyzer, the consumption of carrier is catalyst weight 5～40%.
2. manufacture Methylacrylaldehyde method according to claim 1, is characterized in that X is at least one being selected from W, V, Ni, Cr, Nb or Re.
3. manufacture Methylacrylaldehyde method according to claim 1, is characterized in that Y is at least one being selected from Sn, Sr or Zn.
4. manufacture Methylacrylaldehyde method according to claim 1, the span that it is characterized in that a is 0.5～5.0; The span of b is 1.0～5.0; The span of c is 1.0～10.0; The span of d is 0.1～5.0; The span of e is 0.01～3.0; The span of f is 0.1～10.0; The span of g is 0.02～3.0.
5. manufacture Methylacrylaldehyde method according to claim 1, is characterized in that temperature of reaction is 360～390 ℃.
6. manufacture Methylacrylaldehyde method according to claim 1, is characterized in that air speed is 900～1100 hours
-1.
7. manufacture Methylacrylaldehyde method according to claim 1, the mol ratio that it is characterized in that iso-butylene or the trimethyl carbinol and water is 1:(1.5～3.5).
8. manufacture Methylacrylaldehyde method according to claim 7, the mol ratio that it is characterized in that iso-butylene or the trimethyl carbinol and water is 1:(2～3).
9. manufacture Methylacrylaldehyde method according to claim 1, the mol ratio that it is characterized in that iso-butylene or the trimethyl carbinol and oxygen is 1:(2～8).
10. manufacture Methylacrylaldehyde method according to claim 9, the mol ratio that it is characterized in that iso-butylene or the trimethyl carbinol and oxygen is 1:(2.5～6).
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105503558A (en) * | 2014-09-25 | 2016-04-20 | 中国石油化工股份有限公司 | Synthesis method of methacrylaldehyde |
| CN105498794A (en) * | 2014-09-25 | 2016-04-20 | 中国石油化工股份有限公司 | Methacrylaldehyde catalyst |
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| CN102371159A (en) * | 2010-08-23 | 2012-03-14 | 中国石油化工股份有限公司 | Catalyst for oxidizing isobutene of tert-butyl alcohol to prepare methy acraldehyde and preparation method thereof |
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| US4219670A (en) * | 1975-03-12 | 1980-08-26 | Mitsubishi Rayon Co., Ltd. | Process for producing unsaturated aldehydes and unsaturated carboxylic acids |
| CN1596149A (en) * | 2001-12-21 | 2005-03-16 | 旭化成化学株式会社 | Oxide catalyst composition |
| CN102371159A (en) * | 2010-08-23 | 2012-03-14 | 中国石油化工股份有限公司 | Catalyst for oxidizing isobutene of tert-butyl alcohol to prepare methy acraldehyde and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105503558A (en) * | 2014-09-25 | 2016-04-20 | 中国石油化工股份有限公司 | Synthesis method of methacrylaldehyde |
| CN105498794A (en) * | 2014-09-25 | 2016-04-20 | 中国石油化工股份有限公司 | Methacrylaldehyde catalyst |
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