CN100417446C - Forming method of methacrylic acid catalyst synthesized by selective oxidation of methylacrolein - Google Patents
Forming method of methacrylic acid catalyst synthesized by selective oxidation of methylacrolein Download PDFInfo
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- CN100417446C CN100417446C CNB2006100252084A CN200610025208A CN100417446C CN 100417446 C CN100417446 C CN 100417446C CN B2006100252084 A CNB2006100252084 A CN B2006100252084A CN 200610025208 A CN200610025208 A CN 200610025208A CN 100417446 C CN100417446 C CN 100417446C
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Abstract
The present invention relates to a forming method of heteropoly salt catalysts for synthesizing methacrylic acid by methacrolein through selective oxidation reactions. In the method, at least one kind of organic additives and heat conducting diluting agents are added to catalyst powder, and then, mixtures are molded to be prepared to be catalyst finished products. The prepared catalysts have the advantages of high mechanical strength, long service life and high activity and selectivity.
Description
Technical field
The present invention relates to forming method and the application thereof of MAL (MAL) by the heteropolyacid salt catalyst of selective oxidation reaction synthesize methyl acrylic acid (MAA), described catalyst has the high characteristics of mechanical strength height, long service life, activity and selectivity.
Background technology
Methacrylic acid is a kind of important organic synthesis raw material, and the chemical products of being derived by methacrylic acid reach more than hundred kinds, are widely used in fields such as weaving, coating, leather, building.Most of in the world at present MAA produces with the acetone cyanohydrin method, but this method has unsurmountable shortcoming, shows that mainly toxicity is big, and the serious and by-product of equipment corrosion is big and difficult etc.What big petrochemical corporation (complex) of several families of Japan's eighties developed is raw material with the isobutene or the tert-butyl alcohol, and via the synthetic MAA of MAL intermediate two-step oxidation, its yield can reach 60%, is present more advanced process route.
The existing a large amount of reports of patent that relate to the synthetic MAA catalyst of MAL oxidation, the main category of invention is heteropolyacid catalyst (JP55-2619, CN1130171A, US5093521 etc.) around P-Mo, but defectives such as heteropolyacid catalyst has poor heat stability, mechanical strength is low, service life is short, generation MAA poor selectivity.For fear of these defectives, existing a large amount of patents have been done improvement to this, use metal sulfate to improve the mechanical strength of catalyst in catalyst is formed as JP55-79340 and CN1126718A, but have reduced the reactivity and the selectivity of catalyst; US4621155 and EP0454375A1 join ammonium salt or nitrogenous heterocyclic compound in the carbon monoxide-olefin polymeric, to improve the selectivity of MAA, have but caused the reduction of mechanical strength.JP59-183832 joins in the carbon monoxide-olefin polymeric ceramic whisker improving activity of such catalysts, but since ceramic whisker cost an arm and a leg and be difficult to industrial production.The CN1273232A suggestion separates catalyst bed so that the multiple reaction district to be provided, and the multi-catalyst that will have different activities place corresponding multiple reaction district to obtain inhomogenous Temperature Distribution so that prevent the gathering of heat, but be disadvantageous to Preparation of catalysts like this.CN1647854A reacts in the steel reactor of internal diameter 15mm and obtains result preferably, but mechanical strength behind the catalyst compression molding is significantly reduced, and can not satisfy need of industrial production.
Summary of the invention
Technical problem to be solved by this invention provides a kind of forming method that is used for methacrylic acid catalyst synthesized by selective oxidation of methylacrolein, to satisfy industrial needs.The preformed catalyst that is obtained has certain shape and size, the mechanical strength height, and long service life has good activity and selectivity in the course of reaction of selectively oxidizing methyl acrylic aldehyde to synthesize methyl propenoic acid.
Gained purpose of the present invention provides a kind of forming method of metering system acid catalyst, sees Chinese invention patent 200410084590.7 for details about the composition of heteropolyacid salt catalyst and the preparation method of catalyst fines.
The forming method that is used for methacrylic acid catalyst synthesized by selective oxidation of methylacrolein that the present invention provides comprise the steps: with catalyst fines, organic additive and heat conduction mixing diluents evenly after, it is cylindric to adopt extruding machine to be molded as, and preferably is molded as the hollow and annular cylinder of diameter 5mm, through hole internal diameter 1mm, long 5mm.Catalyst fines also can be directly and the heat conduction mixing diluents, and then add auxiliary agent.Said organic additive can be selected ethanol, 1, and one or more in 4-butanediol, polyethylene glycol, the tert-butyl alcohol, polyether-ether-ketone, polyether ethersulfone, acetone, the MEK mix use.The heat conduction diluent can be selected SiC, MoO
3, WO
3, TiO
2Or ZrO
2In a kind of.Auxiliary agent plays the effect that improves surface of solids performance, can also play the pore-creating effect in follow-up heat treatment process, increases catalyst specific surface.
With catalyst fines weight is benchmark, and heat conduction diluent addition is 0～50 weight %, is preferably 2～30 weight %; The organic additive addition is 5～60 weight %, is preferably 10～30 weight %.Briquetting pressure 200N with heating in the air atmosphere of hollow and annular cylinder under 250～450 ℃ that obtains 110 hours, obtains finished catalyst.
The process that catalyst by the preparation of above-mentioned forming method is used for the synthetic MAA of vapor phase catalytic oxidation MAL is: the dilute gas mixture of raw material MAL, air or molecule-containing keto and steam feed and carry out the selective oxidation reaction in the stainless steel fixed bed reactors of diameter 25mm, long 3m and synthesize MAA after preheating.In the dilute gas mixture of used molecule-containing keto, molecular oxygen can come from pure oxygen, oxygen enrichment or air, and diluent gas can be N
2, CO, CO
2Or H
2Among the O one or more are pressed the composite mixture of arbitrary proportion.Oxidation reaction condition is: 220～450 ℃ of temperature, preferred 260～400 ℃; Pressure 0.05～0.5MPa, preferred normal pressure; The total air speed 500～5000h of reaction raw materials gaseous mixture
-1, preferred 1000～3500h
-1The molar concentration 1～20% of MAL, preferred 3～8%; O
2With the mol ratio 0.5～8 of MAL, preferred 1～5; The mol ratio of steam and MAL is 1～15, preferred 3～10.Conversion ratio and the selectivity computing formula of the synthetic MAA of MAL oxidation are as follows:
The specific embodiment
Below the reactivity worth of the forming method and the synthetic MAA of catalysis MAL selective oxidation thereof of high strength catalyst will be described with specific embodiment, but scope of the present invention is not limited to these embodiment.
Embodiment 1
A kind of usefulness 85 (Mo
12P
1.5K
1.5Sb
0.5Cu
0.3As
0.2V
0.5In
0.3Cs
0.2Mo
2)/15ZrO
2The preparation and the forming method of the heteropolyacid salt catalyst of expression (constituting the atomic ratio and the heat conduction diluent of the metallic element of active component) are as follows:
Restrain ammonium paramolybdates, 2.9 gram ammonium metavanadates, 4.2 gram potassium hydroxide and 2.0 gram cesium nitrates with 105.9 and be dissolved in the distilled water of 200 grams, get the solution first.7.4 gram phosphoric acid and 1.4 gram arsenic acids are dissolved in the 20 gram water, obtain solution second.With 5.7 the gram trichloride antimonies be dissolved in 30 the gram 10% weight diluted hydrochloric acid aqueous solution in, add again 3.6 the gram copper nitrates and 4.5 the gram indium nitrates get solution third.Under agitation earlier solution second is joined in the solution first, then solution third is added, and regulate the pH=6 of mixed liquor, and be warming up to 70 ℃ of slakings 5 hours with ammoniacal liquor.Behind 100 ℃ of following evaporates to dryness, 110 ℃ of down oven dry, and 250 ℃ of roastings 3 hours in air atmosphere, obtain pressed powder.In this pressed powder, add 14.4 gram MoO
3Get catalyst precarsor.Get 85 gram catalyst precursor powder and 15 gram ZrO
2Mixing, add 15 milliliter 1, the 4-butanediol, under the pressure of 200N molded be diameter 5mm, through hole internal diameter 1mm, long 5mm at the hollow and annular cylinder, roasting 6 hours in 380 ℃ of air stream then, make final finished catalyst, the malleation mechanical strength of measuring catalyst with particle crush strength analyzer is 33.4kg/cm
2, the side pressure mechanical strength is 3.5kg/cm.
1300 gram catalyst granules are directly packed in the tubular fixed-bed reactor of diameter 25mm, long 3m, at 320 ℃ (hot(test)-spot temperatures), normal pressure, MAL: O
2: N
2: H
2O=1: 2: 8: 10, air speed 1500h
-1Under carry out selective oxidation reaction.Reaction is carried out gathering after 80 hours product and is carried out gas chromatographic analysis, and the MAL conversion ratio is 85.4%, MAA selectivity 87.9%.Continue reaction 2000 hours under this condition, analysis result is a MAL conversion ratio 85.7%, MAA selectivity 88.1%.Deterioration does not take place in catalyst.
Embodiment 2～9
Except that the kind and consumption that change organic additive, all the other all prepare catalyst by embodiment 1 identical condition and method, and the results are shown in Table 1 after 80 hours for the mechanical strength of preformed catalyst and reaction.
The intensity of different organic additives of table 1 and consumption compacted under catalyst thereof and 80 hours result of reaction
| Title | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 |
| Auxiliary agent title and consumption | 15 milliliter 1, the 4-butanediol | 15 milliliters of Macrogol 200s | 10 milliliter 1,4-butanediol and 5 gram polyether ethersulfones | 10 milliliter 1,4-butanediol and 5 gram polyether-ether-ketones | 15 milliliters of ethanol |
| Malleation intensity, kg/cm 2 | 33.4 | 30.1 | 38.2 | 40.5 | 26.3 |
| Side pressure strength, kg/cm 2 | 3.5 | 3.0 | 3.6 | 3.7 | 2.5 |
| The MAL conversion ratio, % | 85.4 | 89.4 | 88.2 | 86.6 | 84.2 |
| The MAA selectivity, % | 87.9 | 80.7 | 87.7 | 88.7 | 80.8 |
| Title | Embodiment 6 | Embodiment 7 | Embodiment 8 | Embodiment 9 | Comparative example 1 |
| Auxiliary agent title and consumption | 15 milliliters of tert-butyl alcohols | 15 milliliters of MEKs | 10 milliliter 1, the 4-butanediol is kept to | 20 milliliter 1, the 4-butanediol is kept to | 15 ml waters |
| Malleation intensity, kg/cm 2 | 25.1 | 34.2 | 24.2 | 34.2 | 33.8 |
| Side pressure strength, kg/cm 2 | 2.7 | 3.3 | 3.3 | 3.3 | 3.0 |
| The MAL conversion ratio, % | 83.5 | 84.3 | 85.6 | 85.0 | 78.1 |
| The MAA selectivity, % | 85.7 | 86.1 | 85.2 | 86.1 | 76.9 |
Comparative example 1
Except replacing 15 milliliter 1 with 15 ml waters, outside the 4-butanediol, all the other all prepare catalyst by embodiment 1 identical method.The malleation mechanical strength of catalyst is 33.8kg/cm
2, the side pressure mechanical strength is 3.0kg/cm.Carry out the selective oxidation reaction by embodiment 1 identical method, the result who reacted 80 hours is: the MAL conversion ratio is 78.1%, MAA selectivity 76.9%.
Comparative example 2
Except the hollow and annular cylinder of catalyst being extruded shape diameter 5mm, through hole internal diameter 1mm, long 5mm changed the cylinder of diameter 5mm, long 5mm into, all the other all prepared catalyst by embodiment 1 identical method.The malleation mechanical strength of catalyst is 35.2kg/cm
2, the side pressure mechanical strength is 7.2kkg/cm.Carry out the selective oxidation reaction by embodiment 1 identical method, the result who reacted 80 hours is: the MAL conversion ratio is 88.2%, MAA selectivity 80.1%.
Embodiment 11～13
Except restraining SiC, WO with 15
3, TiO
2Replace 15 gram ZrO
2Outward, all the other all prepare catalyst by embodiment 1 identical method.The composition of catalyst, mechanical strength and reaction the results are shown in Table 2 in 80 hours.
The composition of table 2 catalyst, mechanical strength and reaction result
| Embodiment | Catalyst is formed | Malleation/side pressure strength, kg/cm | Reaction temperature (focus), ℃ | The MAL conversion ratio, % | The MAA selectivity, % |
| 11 | 85(Mo 12P 1.5K 1.5Sb 0.5Cu 0.3As 0.2V 0.5In 0.3Cs 0.2Mo 2)/15SiC 2 | 33.2/3.2 | 320 | 87.0 | 87.9 |
| 12 | 85(Mo 12P 1.5K 1.5Sb 0.5Cu 0.3As 0.2V 0.5In 0.3Cs 0.2Mo 2)/15WO 3 | 32.8/3.2 | 320 | 85.5 | 88 |
| 13 | 85(Mo 12P 1.5K 1.5Sb 0.5Cu 0.3As 0.2V 0.5In 0.3Cs 0.2Mo 2)/15TiO 2 | 33.5/3.3 | 322 | 87.2 | 85.5 |
Embodiment 14～16
Except reaction velocity becomes 800h
-1, 2000h
-1, 2500h
-1Outward, the catalyst that all the other all prepare by embodiment 1 identical method evaluation the results are shown in Table 3.
Table 3 differential responses conditioned response result
| The example example | Reaction velocity, h -1 | Reaction temperature (focus), ℃ | The MAL conversion ratio, % | The MAA selectivity, % |
| 14 | 800 | 305 | 88.0 | 84.3 |
| 15 | 2000 | 330 | 84.1 | 88.0 |
| 16 | 2500 | 340 | 81.2 | 89.2 |
Claims (4)
1. forming method that is used for methacrylic acid catalyst synthesized by selective oxidation of methylacrolein is characterized in that at least a organic additive and heat conduction diluent being joined P-Mo before molded is in the heteropolyacid salt catalyst powder; The catalyst activity component is the [PMo of Keggin structure
12O
40]
3-Heteropolyacid salt; Organic additive is polyvinyl alcohol, ethanol, 1, one or more in 4-butanediol, polyethylene glycol, the tert-butyl alcohol, polyether-ether-ketone, polyether ethersulfone, acetone, the MEK, and accounting for P-Mo is 10～30 weight % of heteropolyacid salt catalyst powder weight; The heat conduction diluent is SiC, MoO
3, WO
3, TiO
2, ZrO
2In a kind of, accounting for P-Mo is 2～30 weight % of heteropolyacid salt catalyst powder weight; With P-Mo is after heteropolyacid salt catalyst powder, heat conduction diluent and organic additive mix, under 200N pressure, be molded as diameter 5mm, through hole internal diameter 1mm, the hollow and annular cylinder of long 5mm, heated in the air atmosphere under 250～450 ℃ 1～10 hour then, make finished catalyst.
2. the Application of Catalyst of a forming method according to claim 1 preparation, it is characterized in that this catalyst is used for the process that the MAL vapor phase catalytic oxidation prepares methacrylic acid and is: the dilute gas mixture of raw material MAL, air or molecule-containing keto and steam feed and carry out the selective oxidation reaction in the fixed bed shell reactor that this catalyst is housed after preheating; Molecular oxygen comes from pure oxygen, oxygen enrichment or air, and diluent gas is N
2, CO, CO
2Or H
2Among the O one or more are pressed the composite mixture of arbitrary proportion.
3. the Application of Catalyst of forming method according to claim 2 preparation is characterized in that the condition that this catalyst is used for the reaction of MAL vapor phase catalytic oxidation is: 220～450 ℃ of temperature; Pressure is 0.05～0.5MPa; The total air speed 500～5000h of reaction raw materials gaseous mixture
-1MAL molar concentration 1～20%; O
2With the mol ratio of MAL be 0.5～8; The mol ratio of steam and MAL is 1～15.
4. the Application of Catalyst of forming method according to claim 3 preparation is characterized in that the condition that this catalyst is used for the reaction of MAL vapor phase catalytic oxidation is: 260～400 ℃ of temperature; Pressure is normal pressure; The total air speed 1000～3500h of reaction raw materials gaseous mixture
-1MAL molar concentration 3～8%; O
2With the mol ratio of MAL be 1～5; The mol ratio of steam and MAL is 3～10.
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|---|---|---|---|
| CNB2006100252084A CN100417446C (en) | 2006-03-29 | 2006-03-29 | Forming method of methacrylic acid catalyst synthesized by selective oxidation of methylacrolein |
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| CNB2006100252084A CN100417446C (en) | 2006-03-29 | 2006-03-29 | Forming method of methacrylic acid catalyst synthesized by selective oxidation of methylacrolein |
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| CN100417446C true CN100417446C (en) | 2008-09-10 |
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| CN102114427B (en) * | 2010-12-13 | 2013-03-20 | 上海华谊丙烯酸有限公司 | Method for preparing catalyst in preparation of acrylic acid by oxidizing acrolein |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5969148A (en) * | 1982-10-12 | 1984-04-19 | Ube Ind Ltd | Activating method of catalyst for producing methacrylic acid |
| US4621155A (en) * | 1980-06-26 | 1986-11-04 | Nippon Shokubai Kagaku Kogyo Co. Ltd. | Process for preparation of methacrylic acid |
| CN1047985A (en) * | 1990-01-10 | 1990-12-26 | 齐鲁石油化工公司研究院 | Produce the catalyzer and the application of methacrylic acid |
| CN1647854A (en) * | 2004-11-26 | 2005-08-03 | 上海华谊丙烯酸有限公司 | Catalyst for selectively oxidizing methyl acrylic aldehyde to synthesize methyl propenoic acid and its use |
-
2006
- 2006-03-29 CN CNB2006100252084A patent/CN100417446C/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4621155A (en) * | 1980-06-26 | 1986-11-04 | Nippon Shokubai Kagaku Kogyo Co. Ltd. | Process for preparation of methacrylic acid |
| JPS5969148A (en) * | 1982-10-12 | 1984-04-19 | Ube Ind Ltd | Activating method of catalyst for producing methacrylic acid |
| CN1047985A (en) * | 1990-01-10 | 1990-12-26 | 齐鲁石油化工公司研究院 | Produce the catalyzer and the application of methacrylic acid |
| CN1647854A (en) * | 2004-11-26 | 2005-08-03 | 上海华谊丙烯酸有限公司 | Catalyst for selectively oxidizing methyl acrylic aldehyde to synthesize methyl propenoic acid and its use |
Non-Patent Citations (2)
| Title |
|---|
| 用于生产甲基丙烯酸的杂多酸催化剂的研究. 郑维义等.工业催化，第3期. 1993 |
| 用于生产甲基丙烯酸的杂多酸催化剂的研究. 郑维义等.工业催化，第3期. 1993 * |
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Effective date of registration: 20170210 Address after: 201424 Fengxian District Cang Road, lane, Lane 357, room 100, room 295 Patentee after: Shanghai Hua Yi new material Co., Ltd Address before: 200137 Pudong North Road, Shanghai, No. 2031, No. Patentee before: Shanghai Huayi Acrylic Acid Co., Ltd. |