CN100453177C - Catalyst for producing methyl-acrylate from methyl-acrolein and its production - Google Patents
Catalyst for producing methyl-acrylate from methyl-acrolein and its production Download PDFInfo
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- CN100453177C CN100453177C CNB2006100804179A CN200610080417A CN100453177C CN 100453177 C CN100453177 C CN 100453177C CN B2006100804179 A CNB2006100804179 A CN B2006100804179A CN 200610080417 A CN200610080417 A CN 200610080417A CN 100453177 C CN100453177 C CN 100453177C
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Abstract
The invention is concerned with the activator of polymethyl methacrylate and the preparation method that makes by methyl propenal directly, which is heteropolyacids catalyst with Keggin structure character. The transforming rate of the activator MAL is over 95%, which can maintain the selection of MMA to be over 90%, the stability of the activator is good; the feedback rate is higher than the reaction that the activator is Pd, the activator is fit for fixing bed reactor, the touching time is 20 to 28second, but, the Pd activator is fit for batch reactor, the reacting time is several hours.
Description
Technical field:
The present invention relates to a kind of Catalysts and its preparation method of directly producing methyl methacrylate by MAL.
Background technology:
Methyl methacrylate (MMA) is a kind of important Organic Chemicals, is mainly used in the production of lucite (PMMA), also be used for the manufacturing of polyvinyl chloride auxiliary agent A CR and as second monomer applications in acrylic fiber production process.In addition, application is widely also arranged in fields such as coating, weaving, bonding agents.As a kind of chemical products, can directly apply to leather, weaving, papermaking, floor polishing, unsaturated-resin modification, higher alkyl methacrylate class, also can be used as many industries such as plasticizer of timber size, printing and dyeing assistant and plastics.
The method of synthetic MMA mainly was acetone cyanohydrin method (an ACH method) in the past.The raw material that adopts in this method production process contains cyanide, and is bigger to human body harm, also exists shortcomings such as contaminated environment, equipment corrosion are serious.Nineteen eighty-two Japan catalyst chemical company and mitsubishi rayon have realized with the isobutene being the C of representative
4Derivative is the industrialization that raw material is produced MMA.C
4Technology must be through isobutene/tert-butyl alcohol-MAL (MAL)-methacrylic acid (MAA)-MMA three-step reaction, and this technology successfully realizes industrialization.Develop the two-step reaction of isobutene/tert-butyl alcohol-MAL-MMA afterwards again, be called direct methyl method.Directly the methyl method has been simplified the MAL oxidizing process and has been separated the equipment of intermediate, and makes reaction realize coupling, helps the carrying out that react on thermodynamics, meets the Atom economy reaction, can realize the greenization production of MMA.
The patent that relates to the synthetic MMA of MAL oxidative esterification is divided into two classes: a class is the catalyst of the synthetic MMA of MAL direct oxidation esterification, and another kind of is the synthetic MAA catalyst of MAL oxidation, and then the synthetic MMA of esterification.Last class is carried on CaCO with palladium (Pd)
3As catalyst, oxidative esterification reaction takes place and generates MMA in molecular oxygen, methyl alcohol and MAL, scheme as described in saying as patents such as CN 1485133A, US3772381, JP-B-57-35856, JP-A-57-50545, JP-A-61-243044, JP-B-61-60820, JP-B-62-7902, JP-A-5-148148, JP-A-61-243044, JP-B-57-35860, JP-B-57-19090, USP5892102, EP0972579A.But there is the problem that activity is low, the reaction time is long in such catalyst, and Pd belongs to noble metal, and the Catalyst Production cost is very high, and exploitation is made troubles to large-scale industrialization.Back-class with oxidative esterification be divided into two the step carry out, earlier MAL is oxidized to MAA, main is the catalyst of the Keggin type heteropoly compound of main component with P, Mo and V, its gegenion is based on alkali metal ion, as JP57-171443, CN1483014A and CN1273232A, but this solid catalyst exists poor heat stability, mechanical strength is low, service life is short, the defectives such as poor selectivity of generation MAA; Again MAA and methyl alcohol are obtained MMA under the effect of catalyst such as acidic cationic resin, the employing acidic resins are catalyst, as the clear 59-65041 of Ri Tekai, 54-81213,58-159442 and CN1052848A.
Summary of the invention:
The purpose of this invention is to provide a kind of Catalysts and its preparation method of directly producing methyl methacrylate by MAL.Be a kind of heteropolyacid salt catalyst, under the situation that improves catalyst selectivity and heat endurance, reduce cost, improve the service life of catalyst.
The invention provides and a kind ofly directly produce the catalyst of methyl methacrylate by MAL, be a kind of heteropolyacid catalyst with Keggin architectural feature, it is composed as follows:
H
aPMo
bV
cCs
dX
eY
fZ
gO
i
H, P, Mo, V, Cs, O represent hydrogen, phosphorus, molybdenum, vanadium, caesium and oxygen respectively, X represents to be selected from least a element in sodium, potassium, the rubidium, Y represents at least a element in chosen from Fe, copper, zinc, chromium, magnesium, cobalt, manganese, barium, gallium, cerium, the lanthanum, and Z represents to be selected from least a element in antimony, bismuth, arsenic, germanium, zirconium, tellurium, silver, selenium, silicon, tungsten, the boron.A, b, c, d, e, f, g, i represent each atoms of elements ratio respectively, when a=0.05～5, b=8～11, c=1～4, d=0.01～2, e=0.01～2, f=0.01～1, g=0.01～1, b+c=12 wherein, i is the atom ratio that satisfies the needed oxygen of valence of above-mentioned each component.
The present invention also provides a kind of and has directly produced the Preparation of catalysts method of methyl methacrylate by MAL, and concrete grammar and step are: earlier with the H of 80～120 mass parts
aPMo
bV
cO
i20～35H
2O is water-soluble, a=0.05～5 wherein, and b=8～11, c=1～4, i is the atom ratio that satisfies the needed oxygen of valence of above-mentioned each component, adds 4～8 parts CsNO
3Nitrate or oxide with the Z element of the nitrate of the Y element of the nitrate of the X element of 0.5～2 mass parts or oxide, 1～2 mass parts or oxide, 1～2 mass parts mix; The quinoline of getting 10～50 parts is dissolved in rare nitric acid, and above-mentioned two kinds of solution are mixed, stir, mix the back under 80～130 ℃ with mixed drying materials, compressing tablet.Under nitrogen atmosphere, roasting is 3～8 hours between 380～450 ℃, and 300～380 ℃ of roastings promptly made catalyst of the present invention after 3～5 hours under air purge at last.
The conversion ratio of catalyst MAL of the present invention (MAL) can keep the selectivity of methyl methacrylate (MMA) to reach more than 90% up to more than 95%, and catalyst stability is good; Space time yield is that the reaction of catalyst improves greatly than with Pd, and this catalyst is applicable to fixed bed reactors, and be 20～28s time of contact, and the Pd catalyst generally is only applicable to batch reactor, and the reaction time needs a few hours; Catalyst of the present invention does not adopt precious metals pd, and the Preparation of catalysts cost reduces greatly, and manufacturing process is simple.
Superficies at the H with Keggin structure, Mo, P, V heteropoly acid exist a large amount of free electrons and H
+Because heteropoly acid has bigger spatial configuration of molecules, cloud density is low, outer-shell electron and H
+Have good flowability, this heteropoly acid itself has oxidisability and acidity.Adopt above heteropoly acid to be the basis, make it to become the catalyst that meets the reaction requirement by interpolation Cs, X, Y, Z etc.; Add organic base (heterocyclic compounds such as quinoline, pyridine, piperidines) in the preparation process and improve the specific surface of this catalyst and then augmenting response activity.
The specific embodiment:
Embodiment 1:
PMo with 50 grams
11V
1O
4031H
2O is dissolved in 20 ml waters, slowly adds CsNO
31.5 gram, KNO
30.50 gram, Bi (NO
3)
35H
2O0.50 gram, Cu (NO
3)
23H
2O1.00 gram, As
2O
50.50 gram, restrain 20 milliliters the dilute nitric acid solution that quinoline are dissolved in 10, and mix with above solution, stir, dried by the fire 5 hours down, make 40-60 order particle behind pulverizing, porphyrize, the compressing tablet at 105 ℃, fed nitrogen 3 hours at 400 ℃ then, be cooled to 350 ℃, and bubbling air got final product in 3 hours, gas flow is 50ml/min.Promptly obtain H
2.4PMo
11VCs
0.33K
0.23Bi
0.05Cu
0.19As
0.1O
40Catalyst.
Applicable cases: reaction raw materials: the mol ratio of methyl alcohol, water, MAL, air is 2: 1: 1: 6; Reaction condition: get above-mentioned catalyst 3 grams and in fixed bed reactors, carry out 290 ℃ of reaction temperatures, normal pressure, cumulative volume air speed 200h
-1Product: methyl alcohol, water, air, MMA, MAA, MAL and other acetate, CO, CO
2Reaction result: MAL conversion ratio 88.4%, MMA selectivity 90.6%.
Embodiment 2:
H with 50 grams
5PMo
10V
233H
2O is dissolved in 20 ml waters, slowly adds CsNO
32.00 gram adds KNO
30.50 gram, Cu (NO
3)
23H
2O0.50 gram, As
2O
50.70 gram is dissolved in dilute nitric acid solution with 5 gram quinoline, and mixes with above solution, stirs, and dries by the fire 5 hours down at 80 ℃, makes 40-60 order particle behind pulverizing, porphyrize, the compressing tablet.Fed nitrogen 5 hours at 380 ℃ then, be cooled to 350 ℃ then, bubbling air got final product in 5 hours, and gas flow is 50ml/min.Promptly obtain H
3.2PMo
10V
2Cs
0.47K
0.23Bi
0.05Cu
0.10As
0.13O
40Catalyst.
Applicable cases: reaction raw materials: the mol ratio of methyl alcohol, water, MAL, air is 2: 1: 1: 6; Reaction condition: get 3 gram catalyst and in fixed bed reactors, carry out 280 ℃ of temperature, normal pressure, cumulative volume air speed 180h
-1, product: methyl alcohol, water, air, MMA, MAA, MAL and other acetate, CO, CO
2Reaction result: MAL conversion ratio 89.7%, MMA selectivity 85.7%.
Embodiment 3
H with 50 grams
4PMo
11V31H
2O is dissolved in 20 ml waters, slowly adds NaNO
30.40 gram, CsNO
32.00 gram, Fe (NO
3)
39H
2O1.58 gram, AgNO
30.66 gram is dissolved in dilute nitric acid solution with 5 gram quinoline, and mixes with above solution, stirs, and dries by the fire 5 hours down at 130 ℃, makes 40-60 order particle behind pulverizing, porphyrize, the compressing tablet.Fed nitrogen 8 hours at 450 ℃ then, be cooled to 350 ℃ then, bubbling air got final product in 3 hours, and gas flow is 50ml/min.Promptly obtain H
2.58PMo
11VCs
0.48Na
0.22Fe
0.18Ag
0.18O
40Catalyst.
Applicable cases: reaction raw materials: the mol ratio of methyl alcohol, water, MAL, air is 3: 1: 1: 6; Reaction condition: get 3 gram catalyst and in fixed bed reactors, carry out 280 ℃ of temperature, normal pressure, cumulative volume air speed 300h
-1Product: methyl alcohol, water, air, MMA, MAA, MAL and other acetate, CO, CO
2Reaction result: MAL conversion ratio 63.6%, the selectivity 92.4% of MMA.
Embodiment 4
H with 50 grams
4PMo
11V31H
2O is dissolved in 20 ml waters, slowly adds CsNO
32.00 gram adds RbNO
30.73 gram, Ce (NO
3)
21.11 gram, As
2O
50.70 gram is dissolved in dilute nitric acid solution with 5 gram pyridines, and mixes with above solution, stirs, and dries by the fire 5 hours down at 105 ℃, makes 40-60 order particle behind pulverizing, porphyrize, the compressing tablet.Fed nitrogen 8 hours at 410 ℃ then, be cooled to 350 ℃ then, bubbling air got final product in 4 hours, and gas flow is 50ml/min.Promptly obtain H
2.19PMo
11VCs
0.48Rb
0.23Ce
0.2As
0.14O
40Catalyst.
Applicable cases: reaction raw materials: the mol ratio of methyl alcohol, water, MAL, air is 2: 1: 1: 5; Reaction condition: get 3 gram catalyst and in fixed bed reactors, carry out 280 ℃ of temperature, normal pressure, cumulative volume air speed 120h
-1Product: methyl alcohol, water, air, MMA, MAA, MAL and other acetate, CO, CO
2Reaction result: MAL conversion ratio 93.2%, the selectivity 85.7% of MMA.
Embodiment 5
H with 50 grams
4PMo
11V31H
2O is dissolved in 20 ml waters, slowly adds CsNO
32.00 gram, RbNO
30.73 gram, La (NO
3)
21.11 gram, As
2O
50.70 gram is dissolved in dilute nitric acid solution with 5 gram quinoline, and mixes with above solution, stirs, and dries by the fire 5 hours down at 100 ℃, makes 40-60 order particle behind pulverizing, porphyrize, the compressing tablet.Fed nitrogen 8 hours at 410 ℃ then, be cooled to 350 ℃ then, bubbling air got final product in 3 hours, and gas flow is 50ml/min.Promptly obtain H
2.19PMo
11VCs
0.48Rb
0.23La
0.2As
0.14O
40Catalyst.
Applicable cases: reaction raw materials: the mol ratio of methyl alcohol, water, MAL, air is 2: 1: 1: 4; Reaction condition: get 3 gram catalyst and in fixed bed reactors, carry out 290 ℃ of temperature, normal pressure, cumulative volume air speed 120h
-1Product: methyl alcohol, water, air, MMA, MAA, MAL and other acetate, CO, CO
2The conversion ratio of reaction result MAL is 96.92%, and the selectivity of MMA is 80.14%.
Embodiment 6
H with 50 grams
4PMo
11V31H
2O is dissolved in 20 ml waters, slowly adds CsNO
32.00 gram, NaNO
30.80 gram, Cr (NO
3)
20.64 gram, As
2O
50.70 gram is dissolved in dilute nitric acid solution with 5 gram quinoline, and mixes with above solution, stirs, and dries by the fire 5 hours down at 100 ℃, makes 40-60 order particle behind pulverizing, porphyrize, the compressing tablet.Fed nitrogen 8 hours at 410 ℃ then, be cooled to 350 ℃ then, bubbling air got final product in 3 hours, and gas flow is 50ml/min.Promptly obtain H
2.19PMo
11VCs
0.48Rb
0.23Cr
0.2As
0.14O
40Catalyst.
Applicable cases: reaction raw materials: the mol ratio of methyl alcohol, water, MAL, air is 3: 1: 1: 4; Reaction condition: get 3 gram catalyst and in fixed bed reactors, carry out 290 ℃ of temperature, normal pressure, cumulative volume air speed 180h
-1Product: methyl alcohol, water, air, MMA, MAA, MAL and other acetate, CO, CO
2The conversion ratio of reaction result MAL is 96.72%, and the selectivity of MMA is 90.34%.
Claims (3)
1. directly produce the catalyst of methyl methacrylate by MAL for one kind, be a kind of heteropolyacid catalyst with Keggin architectural feature, it is composed as follows:
H
aPMo
bV
cCs
dX
eY
fZ
gO
i
H, P, Mo, V, Cs, O represents hydrogen respectively, phosphorus, molybdenum, vanadium, caesium and oxygen, X represents to be selected from sodium, potassium, at least a element in the rubidium, Y represents chosen from Fe, copper, zinc, chromium, magnesium, cobalt, manganese, barium, gallium, cerium, at least a element in the lanthanum, Z represents to be selected from antimony, bismuth, arsenic, germanium, zirconium, tellurium, silver, selenium, silicon, tungsten, at least a element in the boron, a, b, c, d, e, f, g, i represents each atoms of elements ratio respectively, when a=0.05～5, b=8～11, c=1～4, d=0.01～2, e=0.01～2, f=0.01～1, g=0.01～1, b+c=12 wherein, i is the atom ratio that satisfies the needed oxygen of valence of above-mentioned each component.
2. claim 1 Preparation of catalysts method, concrete grammar and step are: earlier with the H of 80～120 mass parts
aPMo
bV
cO
i20～35H
2O is water-soluble, a=0.05～5 wherein, and b=8～11, c=1～4, i is the atom ratio that satisfies the needed oxygen of valence of above-mentioned each component; The CsNO that adds 4～8 mass parts
3Nitrate or oxide with the Z element of the nitrate of the Y element of the nitrate of the X element of 0.5～2 mass parts or oxide, 1～2 mass parts or oxide, 1～2 mass parts; The quinoline of getting 10～50 mass parts is dissolved in rare nitric acid, and above-mentioned two kinds of solution are mixed, stir, and then with mixed drying materials, compressing tablet, roasting, promptly makes catalyst.
3. according to the preparation method of claim 2, it is characterized in that: mixed material is dried down at 80-130 ℃, compressing tablet, and under nitrogen atmosphere, roasting is 3～8 hours between 380～450 ℃ then, 300～380 ℃ of roastings 3～5 hours under air purge at last promptly make catalyst.
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|---|---|---|---|
| CNB2006100804179A CN100453177C (en) | 2006-05-15 | 2006-05-15 | Catalyst for producing methyl-acrylate from methyl-acrolein and its production |
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|---|---|---|---|
| CNB2006100804179A CN100453177C (en) | 2006-05-15 | 2006-05-15 | Catalyst for producing methyl-acrylate from methyl-acrolein and its production |
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|---|---|
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| CN100453177C true CN100453177C (en) | 2009-01-21 |
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Families Citing this family (11)
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|---|---|---|---|---|
| CN102039143B (en) * | 2010-11-18 | 2012-12-19 | 中国海洋石油总公司 | Preparation method of catalyst for acrylic acid by oxidizing acraldehyde |
| CN102909029B (en) * | 2012-11-20 | 2014-01-15 | 中国海洋石油总公司 | Preparing method of catalyst for producing crylic acid |
| CN105233822B (en) * | 2014-07-11 | 2017-12-19 | 中国石油化工股份有限公司 | A kind of hypergravity catalyst for being used for oxidation of aldehydes esterification for carboxylate and its application |
| CN105749944A (en) * | 2016-03-23 | 2016-07-13 | 重庆紫光海力催化剂有限公司 | Catalyst for preparing alpha-methacrylic acid from 2-methylacrolein with gas-phase catalytic oxidation method |
| KR102463952B1 (en) * | 2018-04-26 | 2022-11-04 | 미쯔비시 케미컬 주식회사 | Method for producing catalyst for methacrylic acid production, and method for producing methacrylic acid and methacrylic acid ester |
| CN111233667A (en) * | 2018-11-29 | 2020-06-05 | 中国科学院大连化学物理研究所 | Improved method for preparing methyl methacrylate |
| CN114425355B (en) * | 2020-09-27 | 2023-08-15 | 中国石油化工股份有限公司 | Catalyst for preparing methacrolein by fixed bed, preparation method and application |
| CN112630094B (en) * | 2020-10-28 | 2022-11-18 | 中石化宁波工程有限公司 | Test method and reaction device for measuring reaction conversion rate of acetone cyanohydrin based on density |
| CN113976179B (en) * | 2021-11-04 | 2024-02-09 | 淄博市翔力致高新材料有限责任公司 | Hollow structure catalyst and preparation method and application thereof |
| CN113893879B (en) * | 2021-11-04 | 2024-02-06 | 淄博市翔力致高新材料有限责任公司 | Heteropoly acid catalyst and preparation method and application thereof |
| CN118125920A (en) * | 2024-04-30 | 2024-06-04 | 山东悦天化学有限责任公司 | Methyl methacrylate synthesis method |
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| US5892102A (en) * | 1996-02-09 | 1999-04-06 | Mitsubishi Rayon Co., Ltd. | Catalyst used in production of carboxylic acid esters and process for producing these esters |
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| CN1524614A (en) * | 2003-09-12 | 2004-09-01 | 中国科学院过程工程研究所 | Catalyst for one step oxidation esterification of unsaturated aldehyde to produce unsaturated carboxylate |
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2006
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5892102A (en) * | 1996-02-09 | 1999-04-06 | Mitsubishi Rayon Co., Ltd. | Catalyst used in production of carboxylic acid esters and process for producing these esters |
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| CN1485133A (en) * | 2003-01-22 | 2004-03-31 | 中国科学院过程工程研究所 | New pattern catalyst for preparing methyl methacrylate by one-step oxidation-esterification from methylacrolein |
| JP2004268027A (en) * | 2003-02-17 | 2004-09-30 | Mitsubishi Rayon Co Ltd | Method of producing methacrylic acid production catalyst |
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