CN103772171B - Isobutene. or Preparation of Methacrolein by Oxidation of Tertiary Butyl Alcohol method - Google Patents
Isobutene. or Preparation of Methacrolein by Oxidation of Tertiary Butyl Alcohol method Download PDFInfo
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- CN103772171B CN103772171B CN201210393291.6A CN201210393291A CN103772171B CN 103772171 B CN103772171 B CN 103772171B CN 201210393291 A CN201210393291 A CN 201210393291A CN 103772171 B CN103772171 B CN 103772171B
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- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- 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
- C07C45/35—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 in propene or isobutene
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- B01J23/88—Molybdenum
- B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
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- B01J23/88—Molybdenum
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- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- C07C—ACYCLIC OR CARBOCYCLIC 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
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Abstract
The present invention relates to a kind of isobutene. or Preparation of Methacrolein by Oxidation of Tertiary Butyl Alcohol method, mainly solve the problem that methylacrolein yield and selectivity in prior art are the highest.The present invention is by using with selected from SiO2Or Al2O3In at least one be carrier, and containing active component Mo of general formula12BiaFebCocSbdCeeXfYgZhOx, wherein X is at least one in W, V, Ni, Cr, Mn, Nb or Re；Y is at least one in Sn, Sr, Zn, Ti or Zr；Z is that the technical scheme of at least one in K, Rb, Na, Li, Tl or Cs preferably solves this problem, can be used in the commercial production of methylacrolein.
Description
Technical field
The present invention relates to a kind of isobutene. or Preparation of Methacrolein by Oxidation of Tertiary Butyl Alcohol method.
Background technology
Methyl methacrylate (MMA) is a kind of important Organic Chemicals and chemical products, mainly for the production of poly-
Methyl methacrylate (lucite, PMMA), polrvinyl chloride auxiliary agent A CR and the second comonomer as acrylic fiber production process, it is also possible to
For producing coating, binding agent, lubricant, textile dyestuff etc..
MMA conventional production methods is the Acetone cyanohydrin method as raw material with acetone and hydrocyanic acid, but this technique uses high malicious, high
Corrosive hydrocyanic acid and sulphuric acid, by-product a large amount of hydrogen sulfate ammonia, therefore harsh and bigger to environment generation to producing equipment requirements
Pressure.After last century the eighties, Japan's catalyst, mitsubishi rayon and Asahi Kasei Corporation develop to mix C 4 fraction in succession
Middle isobutene ./tert-butyl alcohol is raw material MMA production technology, and owing to this process environments pollutes little, product cost is low, is quickly become mesh
Front world's second largest MMA production technology.In recent years, Britain Lucite company developed the MMA with ethylene, methanol and CO as raw material
Production technology, and established commercial plant in 2007 in Singapore.Claim according to the said firm: use this technique to be greatly lowered
Cost of material.But its technology maturation and macroeconomic need to be checked further.
It is that the oxidation of raw material three step produces the technique of methyl methacrylate and specifically includes that one with isobutene. or the tert-butyl alcohol, different
Butylene or tert-butyl alcohol catalytic gas phase oxidation in the presence of molecular oxygen becomes methylacrolein；Two, methylacrolein exists at molecular oxygen
Lower gas phase is catalytically oxidized to methacrylic acid；Three, methacrylic acid generates methyl methacrylate with methanol generation esterification.
At present, the patent about isobutene. or Oxidation of t-Butanol synthesizing methyl acrylic aldehyde is reported the most in a large number, and nearly all patent all relates to
And to Mo, Bi, Fe tri-dvielement, they are the requisite components of catalyst；And the improvement of catalyst is mainly from catalyst
Activity and stability aspect carry out, as added transition metal in active constituent improving activity, the list receipts of increase product；
Add rare earth element and improve redox ability；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.
For isobutene. or tert-butyl alcohol Selective Oxidation methylacrolein a lot of patent reports:
US Pat4250339, Japan Kokai 57 ~ 72937 and CN1131059A use the units such as tellurium (Te), thallium (TI)
Element is as the key component of catalyst, and to improve the activity and selectivity of catalyst, but these materials are in the long-term fortune of catalyst
It is prone to loss of dispersing during Zhuaning, thus causes the performance degradation of catalyst.
US Pat5250485A proposes the composition by improving catalyst and their usage ratio and catalyst preparation side
Method, improves isobutene. or tert-butyl alcohol conversion ratio and target product yield.Isobutene conversion reaches 98.0%, methylacrolein
Selectivity 85.3%, Methacrylic acid selectivity 4.5%, methylacrolein and methacrylic acid are total recovery 85.0%, manage the most not
Think.
JP Pat57 ~ 119837 control catalyst surface structure by adding macromolecular compound, for isobutene. or
The Selective Oxidation of the tert-butyl alcohol, but still suffer from the problem that reactivity reduces with the response time, require further improvement.
Summary of the invention
The technical problem to be solved is in the reaction of existing isobutene. or Preparation of Methacrolein by Oxidation of Tertiary Butyl Alcohol
There is the problem that methylacrolein yield is relatively low, it is provided that a kind of new isobutene. or Preparation of Methacrolein by Oxidation of Tertiary Butyl Alcohol method.
The method has the advantage that isobutene. or tert-butyl alcohol conversion ratio are high, selectivity is good, methylacrolein yield is high.
For solving above-mentioned technical problem, the technical solution used in the present invention is as follows: a kind of isobutene. or Oxidation of t-Butanol system
Methylacrolein method, with isobutene. or the tert-butyl alcohol and oxygen as raw material, the mol ratio of isobutene. or the tert-butyl alcohol and oxygen be 1:(2～
10), being 350～400 DEG C in reaction temperature, reaction pressure is 0.1～0.12 MPa, and air speed is 800～1200 hours-1, isobutyl
The mol ratio of alkene or the tert-butyl alcohol and water is 1:(1～4) under the conditions of, raw material generates methylacrolein with catalyst haptoreaction；Institute
Catalyst with selected from SiO2Or Al2O3In at least one be carrier, and containing the active component of general formula
Mo12BiaFebCocSbdCeeXfYgZhOx；
In formula, a, b, c, d, e, f, g and h representative element bismuth, ferrum, cobalt, antimony, erbium, the atom ratio of X, Y and Z respectively, x is
Meet the oxygen atom sum needed for 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 be 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；G takes
Value scope is 0.01～5.0；The span of h is 0.01～3.0；
X is at least one in W, V, Ni, Cr, Mn, Nb or Re；
Y is at least one in Sn, Sr, Zn, Ti or Zr；
Z is at least one in K, Rb, Na, Li, Tl or Cs；
In catalyst, the consumption of carrier is the 5～40% of catalyst weight；
At least one in carbamide, oxalic acid, glass fibre element or polyvinyl alcohol is added in catalyst preparation process
Expanding agent, the addition of expanding agent accounts for the 0.5 ~ 5% of catalyst weight.
In technique scheme, X preferred version is at least one in W, V, Ni, Cr, Nb or Re.Y preferred version
For at least one in Sn, Sr or Zn.The preferred scope of value of a is 0.5～5.0；The preferred scope of value of b be 1.0～
5.0；The preferred scope of value of c is 1.0～10.0；The preferred scope of value of d is 0.1～5.0；The preferred scope of value of e is
0.01～3.0；The preferred scope of value of f is 0.1～10.0；The preferred scope of value of g is 0.02～3.0；The span of h is excellent
Elect 0.05～2.5 as.The preferred scope of reaction temperature is 360～390 DEG C.The preferred scope of air speed is 900～1100 hours-1.Isobutyl
The preferred scope of mol ratio of alkene or the tert-butyl alcohol and water is 1:(1.5～3.5).The preferred model of mol ratio of isobutene. or the tert-butyl alcohol and oxygen
Enclose for 1:(2～8).In catalyst, the preferred scope of the consumption of carrier is the 10～30% of catalyst weight.The addition of expanding agent is excellent
Selecting scope is account for catalyst weight 1 ~ 3.5%.
The preparation method of the catalyst used in the inventive method is as follows:
A) it is dissolved in water preparing the desired amount of ammonium molybdate of catalyst, then will prepare catalyst the desired amount of carrier silicon
Colloidal sol, aluminium oxide or its mixture add formation solution I；
B) by prepare the catalyst the desired amount of metal salt solution of the active component in addition to antimony component be dissolved in water formation molten
Liquid II;
C) oxide preparing the desired amount of antimony of catalyst is dissolved in hydrochloric acid, forms solution III；
D) under agitation, solution II and solution III are added formation catalyst pulp I in solution I；
E) adding the desired amount of expanding agent in slurry I and obtain slurry II, expanding agent is selected from carbamide, oxalic acid, glass fibre element
Or at least one in polyvinyl alcohol;
F) slurry II obtains catalyst precarsor, before catalyst by extrusion molding after spray shaping or evaporation most of moisture
Body obtains finished catalyst by roasting.
Due to the fact that and add component Sb in the catalyst, Sb5+It is prone to carry out alkene on the coordination unsaturation track of ion
The chemisorbed of hydrocarbon and Lattice Oxygen insertion in π ~ pi-allyl, provide Lattice Oxygen species to insert center for catalytic reaction, thus
It is more likely formed the active component of methylacrolein.Catalyst in the present invention prepares first for isobutene. or tert-butyl alcohol selective oxidation
In base acrolein reaction, the mol ratio at isobutene. or the tert-butyl alcohol and oxygen is 1:(2～10), it is 350～400 in reaction temperature
DEG C, reaction pressure is 0.1～0.12 MPa, and air speed is 800～1200 hours-1, isobutene. or the tert-butyl alcohol with the mol ratio of water are
1:(1～4) under the conditions of, its isobutene. or tert-butyl alcohol conversion ratio are up to 98.5%, and methylacrolein and Methacrylic acid selectivity can
Reaching 92.5%, product methylacrolein and methacrylic acid yield, up to 91.1%, achieve preferable technique effect.
Below by embodiment, the present invention is further elaborated.
Detailed description of the invention
[comparative example]
By 100 grams of (NH4)6Mo7O24·4H2O joins in the warm water of 100 grams 70 DEG C, and stirring makes it all dissolve, and adds
Material A made by the Ludox entering 103.7 gram 40% (wt.).
By 38.5 grams of Fe (NO3)3·9H2O joins in 70 DEG C of hot water of 20 grams, adds 34.3 grams after stirring and dissolving
Bi(NO3)3·5H2O, 41.2 grams of Co (NO3)2·6H2O, 25.1 grams of Mn (NO3)2Solution (50%), 1.88 grams of Ce (NO3)3·
6H2O, 0.28 gram of Zn (NO3)2·6H2O, 0.46 gram of CsNO3Material B is made after stirring and dissolving.
Solution B is separately added with agitation in solution A, forms catalyst pulp, and stir aging 2 little at 80 DEG C
Time, 120 DEG C of slurry is dried and is removed extrusion molding after most of moisture, obtains the cylinder of φ 3.5x3.5mm, then high temperature roasting
Burning obtains finished catalyst, and sintering temperature is 490 DEG C.This catalyst composition and preparation condition are listed in table 1, at isobutene. and oxygen
Mol ratio is 1:2；It it is 350 DEG C in reaction temperature；Reaction pressure is 0.1 MPa;Air speed is 1000 hours-1；Isobutene. and water
Mol ratio be to check and rate under the conditions of 1:2, its result is listed in table 2.
[embodiment 1]
By 100 grams of (NH4)6Mo7O24·4H2O joins in the warm water of 100 grams 70 DEG C, and stirring makes it all dissolve, and adds
Enter the Ludox of 89.4 gram 40% (wt.), 35.8 gram of 20% Alumina gel and 19.1 grams of (NH4)6H5[H2(WO4)6] make material A.
By 38.5 grams of Fe (NO3)3·9H2O joins in 70 DEG C of hot water of 150 grams, adds 34.3 grams after stirring and dissolving
Bi(NO3)3·5H2O, 41.2 grams of Co (NO3)2·6H2O, 1.88 grams of Ce (NO3)3·3H2O, 0.7 gram of Zn (NO3)2·6H2O、
0.27 gram of CsNO3Material B is made after stirring and dissolving.
2.1 grams of antimony oxides are dissolved in the diluted hydrochloric acid aqueous solution of 30 gram of 10% mass, obtain solution C.By solution B and C
It is separately added with agitation in solution A, forms catalyst pulp, add 5.13 grams of carbamide, and stir aging 2 little at 80 DEG C
Time, 120 DEG C of slurry is dried and is removed extrusion molding after most of moisture, obtains the cylinder of φ 3.5x3.5mm, then high temperature roasting
Burning obtains finished catalyst, and sintering temperature is 400～550 DEG C.This catalyst composition and preparation condition are listed in table 1, at isobutene.
It is 1:2 with the mol ratio of oxygen；It it is 350 DEG C in reaction temperature；Reaction pressure is 0.1 MPa;Air speed is 1000 hours-1；Isobutyl
The mol ratio of alkene and water is examination under the conditions of 1:2, and its result is listed in table 2.
[embodiment 2]
By 100 grams of (NH4)6Mo7O24·4H2O joins in the warm water of 100 grams 70 DEG C, and stirring makes it all dissolve, and adds
Enter the Ludox of 78.9 gram 40% (wt.), 47.7 gram of 20% Alumina gel and 8.24 grams of NH4VO3Make material A.
By 38.5 grams of Fe (NO3)3·9H2O joins in 70 DEG C of hot water of 150 grams, adds 34.3 grams after stirring and dissolving
Bi(NO3)3·5H2O, 41.2 grams of Co (NO3)2·6H2O, 2.1 grams of Ce (NO3)3·3H2O, 0.7 gram of Zn (NO3)2·6H2O、0.27
Gram CsNO3Material B is made after stirring and dissolving.
2.1 grams of antimony oxides are dissolved in the diluted hydrochloric acid aqueous solution of 30 gram of 10% mass, obtain solution C.By solution B and C
It is separately added with agitation in solution A, forms catalyst pulp, add oxalic acid 5.60 grams, and stir aging 2 little at 80 DEG C
Time, 100 DEG C of slurry is dried and is removed extrusion molding after most of moisture, obtains the cylinder of φ 3.5x3.5mm, then high temperature roasting
Burning obtains finished catalyst, and sintering temperature is 400～550 DEG C.This catalyst composition and preparation condition are listed in table 1, at the tert-butyl alcohol
It is 1:2 with the mol ratio of oxygen；It it is 350 DEG C in reaction temperature；Reaction pressure is 0.1MPa;Air speed is 1000 hours-1；The tert-butyl alcohol
Being to check and rate under the conditions of 1:2 with the mol ratio of water, its result is listed in table 2.
[embodiment 3～11]
Preparing catalyst by each step of [embodiment 2], concrete outcome is listed in table 1.With [embodiment 2] identical commenting
Under the conditions of valency, reaction result is listed in table 2.
[embodiment 12～21]
Under different reaction conditions, the appraisal result of [embodiment 1] catalyst is listed in table 3.
Table 1
Table 2
Table 3
Claims (7)
1. isobutene. or a Preparation of Methacrolein by Oxidation of Tertiary Butyl Alcohol method, with isobutene. or the tert-butyl alcohol and oxygen as raw material, isobutyl
Alkene or the tert-butyl alcohol are 1:(2～8 with the mol ratio of oxygen), be 350～400 DEG C in reaction temperature, reaction pressure be 0.1～
0.12MPa, air speed is 800～1200 hours-1, the mol ratio of isobutene. or the tert-butyl alcohol and water is 1:(1.5～3.5) under the conditions of,
Raw material generates methylacrolein with catalyst haptoreaction；Catalyst used is with selected from SiO2Or Al2O3In at least one be
Carrier, and active component Mo containing general formula12BiaFebCocSbdCeeXfYgZhOx；
In formula, a, b, c, d, e, f, g and h representative element bismuth, ferrum, cobalt, antimony, cerium, the atom ratio of X, Y and Z respectively, x is satisfied
Oxygen atom sum needed for other element valence；
The span of a is 0.5～5.0；The span of b is 1.0～5.0；The span of c is 1.0～10.0；D takes
Value scope 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；The span of h is 0.05～2.5；
X is at least one in W, V, Ni, Cr, Mn, Nb or Re；
Y is at least one in Sn, Sr, Zn, Ti or Zr；
Z is at least one in K, Rb, Na, Li, Tl or Cs；
In catalyst, the consumption of carrier is the 5～40% of catalyst weight；
At least one reaming in carbamide, oxalic acid, glass fibre element or polyvinyl alcohol is added in catalyst preparation process
Agent, the addition of expanding agent accounts for the 0.5～5% of catalyst weight.
Isobutene. the most according to claim 1 or Preparation of Methacrolein by Oxidation of Tertiary Butyl Alcohol method, it is characterised in that X is for being selected from
At least one in W, V, Ni, Cr, Nb or Re.
Isobutene. the most according to claim 1 or Preparation of Methacrolein by Oxidation of Tertiary Butyl Alcohol method, it is characterised in that Y is for being selected from
At least one in Sn, Sr or Zn.
Isobutene. the most according to claim 1 or Preparation of Methacrolein by Oxidation of Tertiary Butyl Alcohol method, it is characterised in that reaction temperature
Degree is 360～390 DEG C.
Isobutene. the most according to claim 1 or Preparation of Methacrolein by Oxidation of Tertiary Butyl Alcohol method, it is characterised in that air speed is
900～1100 hours-1。
Isobutene. the most according to claim 1 or Preparation of Methacrolein by Oxidation of Tertiary Butyl Alcohol method, it is characterised in that catalyst
The consumption of middle carrier is the 10～30% of catalyst weight.
Isobutene. the most according to claim 1 or Preparation of Methacrolein by Oxidation of Tertiary Butyl Alcohol method, it is characterised in that expanding agent
Addition account for the 1～3.5% of catalyst weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210393291.6A CN103772171B (en) | 2012-10-17 | 2012-10-17 | Isobutene. or Preparation of Methacrolein by Oxidation of Tertiary Butyl Alcohol method |
Applications Claiming Priority (1)
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| 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 |
| SG11201703339UA (en) * | 2014-10-31 | 2017-05-30 | Rohm & Haas | Oxidative esterification process for making methyl methacrylate |
| CN106977400A (en) * | 2017-05-08 | 2017-07-25 | 安徽海德石油化工有限公司 | The method that a kind of utilization refinery C-4-fraction produces methyl methacrylate |
| CN110420643A (en) * | 2019-08-16 | 2019-11-08 | 中国科学院过程工程研究所 | A kind of preparation method and applications of eggshell type composite metal catalyst |
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| 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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| 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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