CN103772171A - Method for preparing methylacrolein through oxidization of isobutene or tert-butyl alcohol - Google Patents
Method for preparing methylacrolein through oxidization of isobutene or tert-butyl alcohol Download PDFInfo
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- CN103772171A CN103772171A CN201210393291.6A CN201210393291A CN103772171A CN 103772171 A CN103772171 A CN 103772171A CN 201210393291 A CN201210393291 A CN 201210393291A CN 103772171 A CN103772171 A CN 103772171A
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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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- C07C45/32—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 invention relates to a method for preparing methylacrolein through oxidization of isobutene or tert-butyl alcohol, and mainly solves the problems that methylacrolein is not high in yield and not high in selectivity in the prior art. At least one of SiO2 or Al2O3 is selected as a carrier, and an active ingredient with the following general formula of Mo12BiaFebCocSbdCeeXfYgZhOx is contained, wherein X is at least one selected from W, V, Ni, Cr, Mn, Nb or Re; Y is at least one selected from Sn, Sr, Zn, Ti or Zr; and Z is at least one selected from K, Rb, Na, Li, Tl or Cs. Through adopting the above technical scheme, the problems in the prior art are well solved, and the method can be used in industrial production of methylacrolein.
Description
Technical field
The present invention relates to a kind of iso-butylene or Preparation of Methacrolein by Oxidation of Tertiary Butyl Alcohol 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 the Acetone cyanohydrin method take acetone and prussic acid as raw material, but this technique is used prussic acid and the sulfuric acid of high poison, highly corrosive, and therefore a large amount of hydrogen sulfate ammonia of by-product require harsh and environment is produced to larger pressure production unit.After last century the eighties, Japan's catalyst, mitsubishi rayon and Asahi Kasei Corporation develop in succession take iso-butylene/trimethyl carbinol in hybrid C 4 cut as raw material MMA production technique processed, 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, Lucite company of Britain developed the MMA production technique take ethene, methyl alcohol and CO as raw material, and had set up full scale plant in 2007 in Singapore.Claim according to the said firm: adopt this technique can significantly reduce raw materials cost.But its technology maturation and macroeconomic need further to be checked.
The technique of producing methyl methacrylates as raw material three steps oxidations take iso-butylene or the trimethyl carbinol mainly comprises: 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, about the existing a large amount of reports of patent of 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.
Have a lot of patent reports for iso-butylene or trimethyl carbinol Selective Oxidation Methylacrylaldehyde:
In US Pat4250339, day disclosure special permission 57 ~ 72937 and CN1131059A, use the key component of the element such as tellurium (Te), thallium (TI) as 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 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 are 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 iso-butylene or Preparation of Methacrolein by Oxidation of Tertiary Butyl Alcohol method are 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 solution used in the present invention is as follows: a kind of iso-butylene or Preparation of Methacrolein by Oxidation of Tertiary Butyl Alcohol 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), it is 350～400 ℃ in temperature of reaction, 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; Catalyzer used is to be selected from SiO
2or Al
2o
3in at least one be carrier, and the active ingredient Mo that contains following general formula
12bi
afe
bco
csb
dce
ex
fy
gz
ho
x;
In formula, a, b, c, d, e, f, g and h be the atom ratio of representative element bismuth, iron, cobalt, antimony, erbium, 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; The span of h is 0.01～3.0;
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 catalyst preparation process, add at least one expanding agent being selected from urea, oxalic acid, glass fibre element or polyvinyl alcohol, the add-on of expanding agent accounts for 0.5 ~ 5% of catalyst weight.
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; The span of h is preferably 0.05～2.5.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).The mol ratio preferable range of iso-butylene or the trimethyl carbinol and oxygen is 1:(2～8).In catalyzer, the consumption preferable range of carrier is catalyst weight 10～30%.The add-on preferable range of expanding agent is to account for 1 ~ 3.5% of catalyst weight.
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) by the oxide dissolution of the antimony of Kaolinite Preparation of Catalyst aequum in hydrochloric acid, form solution III;
D) under agitation, solution II and solution III are added and in solution I, form catalyst pulp I;
E) in slurry I, add the expanding agent of aequum to obtain slurry II, expanding agent is selected from least one in urea, oxalic acid, glass fibre element or polyvinyl alcohol;
F) slurry II by spray shaping or evaporation most of moisture after extrusion moulding obtain catalyst precursor, catalyst precursor obtains catalyzer finished product by roasting.
The present invention is owing to having added component S b, Sb in catalyzer
5+on the coordination unsaturated orbit of ion, be easy to carry out chemisorption and the insertion of lattice oxygen in π ~ allyl group of alkene, insert center for catalyzed reaction provides lattice oxygen species, thereby more easily form the active ingredient of Methylacrylaldehyde.Catalyzer in the present invention is prepared Methylacrylaldehyde reaction for iso-butylene or trimethyl carbinol selective oxidation, be 1:(2～10 in the mol ratio of iso-butylene or the trimethyl carbinol and oxygen), be 350～400 ℃ in temperature of reaction, 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%), 1.88 grams of Ce (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 respectively in solution A, form catalyst pulp, 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 composition and preparation condition are listed in table 1, are 1:2 in the mol ratio of iso-butylene and oxygen; It is 350 ℃ in temperature of reaction; 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, 1.88 grams of Ce (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.
2.1 grams of antimonous oxides are dissolved in the diluted hydrochloric acid aqueous solution of 30 gram of 10% quality, obtain solution C.Solution B and C are under agitation added respectively in solution A, form catalyst pulp, add 5.13 grams, urea, 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 400～550 ℃.This catalyzer composition and preparation condition are listed in table 1, are 1:2 in the mol ratio of iso-butylene and oxygen; It is 350 ℃ in temperature of reaction; Reaction pressure is 0.1 MPa; Air speed be 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 Ce (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.
2.1 grams of antimonous oxides are dissolved in the diluted hydrochloric acid aqueous solution of 30 gram of 10% quality, obtain solution C.Solution B and C are under agitation added respectively in solution A, form catalyst pulp, add 5.60 grams of oxalic acid, and at 80 ℃, stir aging 2 hours, extrusion moulding after 100 ℃ 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 400～550 ℃.This catalyzer composition and preparation condition are listed in table 1, are 1:2 in the mol ratio of the trimethyl carbinol and oxygen; It is 350 ℃ in temperature of reaction; Reaction pressure is 0.1MPa; Air speed be 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]
Make catalyzer by each step of [embodiment 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
Table 2
Table 3
Claims (10)
1. an iso-butylene or Preparation of Methacrolein by Oxidation of Tertiary Butyl Alcohol 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), it is 350～400 ℃ in temperature of reaction, 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; Catalyzer used is to be selected from SiO
2or Al
2o
3in at least one be carrier, and the active ingredient Mo that contains following general formula
12bi
afe
bco
csb
dce
ex
fy
gz
ho
x;
In formula, a, b, c, d, e, f, g and h be the atom ratio of representative element bismuth, iron, cobalt, antimony, erbium, 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; The span of h is 0.01～3.0;
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 catalyst preparation process, add at least one expanding agent being selected from urea, oxalic acid, glass fibre element or polyvinyl alcohol, the add-on of expanding agent accounts for 0.5 ~ 5% of catalyst weight.
2. iso-butylene according to claim 1 or Preparation of Methacrolein by Oxidation of Tertiary Butyl Alcohol method, is characterized in that X is at least one being selected from W, V, Ni, Cr, Nb or Re.
3. iso-butylene according to claim 1 or Preparation of Methacrolein by Oxidation of Tertiary Butyl Alcohol method, is characterized in that Y is at least one being selected from Sn, Sr or Zn.
4. iso-butylene according to claim 1 or Preparation of Methacrolein by Oxidation of Tertiary Butyl Alcohol method, 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; The span of h is 0.05～2.5.
5. iso-butylene according to claim 1 or Preparation of Methacrolein by Oxidation of Tertiary Butyl Alcohol method, is characterized in that temperature of reaction is 360～390 ℃.
6. iso-butylene according to claim 1 or Preparation of Methacrolein by Oxidation of Tertiary Butyl Alcohol method, is characterized in that air speed is 900～1100 hours
-1.
7. iso-butylene according to claim 1 or Preparation of Methacrolein by Oxidation of Tertiary Butyl Alcohol method, the mol ratio that it is characterized in that iso-butylene or the trimethyl carbinol and water is 1:(1.5～3.5).
8. iso-butylene according to claim 1 or Preparation of Methacrolein by Oxidation of Tertiary Butyl Alcohol method, the mol ratio that it is characterized in that iso-butylene or the trimethyl carbinol and oxygen is 1:(2～8).
9. iso-butylene according to claim 1 or Preparation of Methacrolein by Oxidation of Tertiary Butyl Alcohol method, the consumption that it is characterized in that carrier in catalyzer is catalyst weight 10～30%.
10. iso-butylene according to claim 1 or Preparation of Methacrolein by Oxidation of Tertiary Butyl Alcohol method, is characterized in that the add-on of expanding agent accounts for 1 ~ 3.5% of catalyst weight.
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| CN112675866A (en) * | 2020-12-24 | 2021-04-20 | 烟台大学 | Composite metal oxide catalyst, preparation method and application thereof |
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| CN112675866A (en) * | 2020-12-24 | 2021-04-20 | 烟台大学 | Composite metal oxide catalyst, preparation method and application thereof |
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