CN101073784A - Resin catalyst for producing methyl-methacrylate and its production - Google Patents
Resin catalyst for producing methyl-methacrylate and its production Download PDFInfo
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- CN101073784A CN101073784A CN 200710057680 CN200710057680A CN101073784A CN 101073784 A CN101073784 A CN 101073784A CN 200710057680 CN200710057680 CN 200710057680 CN 200710057680 A CN200710057680 A CN 200710057680A CN 101073784 A CN101073784 A CN 101073784A
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Abstract
The invention is concerned with a kind of resin activator to product methylmethacrylate. The carrier is stirene-acrylate-divinylbenzene. copolymer resin, and the loaded active component quality ration is 2 to 5 percent of palladium, 0 to 3 percent of bismuth, 0.3 to 1 percent of lead, 0.3 to 1 percent of iron, and 0 to 1 percent of lanthanum or cerium. Dip resin carrier into ethanol for 3 to 4 h and at the temperature is 20 to 30 degree, filtrate and dry for standby. Prepare the mixed solution by dissolving palladium chloride,bismuth chloride,lead nitrate,ferric nitrate, lanthanum nitrate or cerium nitrate into N. N'-dimethylformamide organic solution. Dip the disposed carrier into the mixed solution and dry, then dip into NaOH methanol solution and carry eoxidized and activated reaction to prepare activator. The activator has high selectivity, good catalyzing nature and long work time.
Description
Technical field
The invention belongs to the catalyst technology of preparation methyl methacrylate, further relate to a kind of resin catalyst of preparing methyl methacrylate and preparation method thereof that is used to.
Background technology
The existing multinomial patent of catalyst for preparing methyl methacrylate by MAL and methyl alcohol single step reaction in the presence of molecular oxygen relates to, wherein the catalyst research of palladium-containing metal is comparatively extensive, as JP-A-57-50545, US4638085, the disclosed palladium of CN1207959-plumbous type catalyst, the disclosed palladium of CN1251086, JP-B-62-7902-bismuth type catalyst, the disclosed palladium of JP-A-61-243044-tellurium type catalyst, the disclosed palladium-thallium of JP-B-57-35860-mercury type catalyst etc.Yet above patent all adopts inorganic material such as aluminium oxide, zinc oxide, calcium carbonate as carrier.Though aluminium oxide, zinc oxide, calcium carbonate carrier have high mechanical properties, there is following shortcoming in they: the water that reaction generates is adsorbed on the surface, activated centre, and reaction is had inhibitory action; Aluminium oxide, zinc oxide, calcium carbonate carrier can be corroded by the accessory substance unsaturated carboxylic acid, cause catalyst life to reduce.
Summary of the invention
The purpose of this invention is to provide a kind of resin catalyst of preparing methyl methacrylate and preparation method thereof that is used to, be used to prepare methyl methacrylate, have the selectivity height, the characteristics that catalytic performance is good with the resin catalyst of this method preparation.
A kind of resin catalyst that is used to prepare methyl methacrylate is characterized in that, the carrier of this catalyst is the styrene diethylene benzene copoly mer resin, and the specific area of carrier is 300～800m
2/ g, average pore size 2～30nm; The active component of load with respect to the mass percentage content of carrier is on the carrier: palladium is 2%～5%, and bismuth is 0～3%, and lead is 0.3%～1%, and iron is 0.3%～1%, and lanthanum is 0～1%.
The preparation method of above-mentioned catalysis skill is as follows:
(1) the styrene diethylene benzene copoly mer resin carrier was soaked in ethanol 3～4 hours under 20～30 ℃ of conditions, filter and be placed on dry for standby in 60 ℃ of baking ovens;
(2) palladium bichloride, bismuth chloride, plumbi nitras, ferric nitrate and lanthanum nitrate are dissolved in the N.N-dimethyl formamide organic solvent, are mixed with the mixed solution of lanthanum nitrate of ferric nitrate, the 0～0.01g/mL of plumbi nitras, the 0.007～0.023g/mL of bismuth chloride, the 0.0016～0.005g/mL of the palladium bichloride that contains 0.011～0.028g/mL, 0～0.015g/mL;
(3) will press incipient impregnation in the mixed solution of step (2) preparation through the pretreated carrier of step (1), and flood 5～6 hours at 20～30 ℃, soaked carrier places 70 ℃～90 ℃ oven dryings; The NaOH methanol solution that carrier drying is placed on 0.005g/ml～0.02g/ml soaked 4～6 hours; Carrier is at hydrogen flow rate 20～60ml/min, 120～220 ℃ of reduction temperatures, and 8～12 hours recovery times were carried out reduction activation, and obtaining carrier is the styrene diethylene benzene copoly mer resin, is loaded with the catalyst of palladium, bismuth, lead, iron and lanthanum.
A kind of resin catalyst that is used to prepare methyl methacrylate is characterized in that, the carrier of this catalyst is the styrene diethylene benzene copoly mer resin, and the specific area of carrier is 300～800m
2/ g, average pore size 2～30nm; The active component of load with respect to the mass percentage content of carrier is on the carrier: palladium is 2%～5%, and bismuth is 0～3%, and lead is 0.3%～1%, and iron is 0.3%～1%, and cerium is 0～1%.
Above-mentioned Preparation of catalysts method is as follows:
(1) the styrene diethylene benzene copoly mer resin carrier was soaked in ethanol 3～4 hours under 20～30 ℃ of conditions, filter and be placed on dry for standby in 60 ℃ of baking ovens;
(2) palladium bichloride, bismuth chloride, plumbi nitras, ferric nitrate and cerous nitrate are dissolved in the N.N-dimethyl formamide organic solvent, are mixed with the mixed solution of cerous nitrate of ferric nitrate, the 0～0.01g/mL of plumbi nitras, the 0.007～0.023g/mL of bismuth chloride, the 0.0016～0.005g/mL of the palladium bichloride that contains 0.011～0.028g/mL, 0～0.015g/mL;
(3) will press incipient impregnation in the mixed solution of step (2) preparation through the pretreated carrier of step (1), and flood 5～6 hours at 20～30 ℃, soaked carrier places 70 ℃～90 ℃ oven dryings; The NaOH methanol solution that carrier drying is placed on 0.005g/ml～0.02g/ml soaked 4～6 hours; Carrier is at hydrogen flow rate 20～60ml/min, 120～220 ℃ of reduction temperatures, and 8～12 hours recovery times were carried out reduction activation, and obtaining carrier is the styrene diethylene benzene copoly mer resin, is loaded with the catalyst of palladium, bismuth, lead, iron and cerium.
The present invention selects for use organic resin material as carrier, and stable in properties is not corroded by acid, water, and can eliminate the influence that generates water.Simultaneously, specific area is big, and active constituent loading is evenly distributed.Characteristics such as the resin catalyst of preparation is used to prepare methyl methacrylate, has the selectivity height, and catalytic performance is good, the life-span is long.
The specific embodiment
Embodiment 1
Take by weighing specific area 500m
2The styrene diethylene benzene copoly mer resin of/g, average pore size 18nm (this resin is purchased in Chemical Plant of Nankai Univ.) 20g is dipped under 25 ℃ of conditions in the ethanol and soaked 4 hours, filters that to be placed in 60 ℃ of baking ovens oven dry stand-by.In the 60mlN.N-dimethyl formamide, dissolve 0.667g palladium bichloride, 0.096g plumbi nitras, 0.433g ferric nitrate under 70 ℃ of conditions.Then solution is poured in the styrene diethylene benzene copoly mer carrier, stirred and to make carrier impregnation even, flood and be placed in 90 ℃ of baking ovens drying in 6 hours 6 hours.The NaOH methanol solution of dry back immersion 60ml0.01g/ml 4 hours, fully dry under 90 ℃ of conditions equally.Place the hydrogen reducing device at last, hydrogen flow rate 40ml/min, reduction is 10 hours under 200 ℃ of conditions, and the catalyst that obtains contains Pd2%, Pb0.3%, Fe0.3% (carrier quality relatively).
In being furnished with the 200ml flask of reflux condenser, add this catalyst of 2.0g, 3.28g MAL and 60g methyl alcohol, speed aerating oxygen with 10ml/min, reaction is 6 hours under 50 ℃ of conditions, and the MAL conversion ratio is 92.3%, and the selectivity of methyl methacrylate is 96.8%.
Embodiment 2
Adopt the method identical with embodiment 1 to prepare catalyst, just add 1.67g palladium bichloride, 0.321g plumbi nitras, 1.44g ferric nitrate in the maceration extract, the catalyst that obtains contains Pd5%, and Pb 1%, Fe 1% (relative carrier quality).The catalyst that use makes reacts under the condition identical with embodiment 1, and the MAL conversion ratio is 94.2%, and the selectivity of methyl methacrylate is 96.6%.
Embodiment 3
Adopt the method identical to prepare catalyst with embodiment 1, just adding 0.667g palladium bichloride, 0.308g bismuth chloride, 0.096g plumbi nitras, 0.433g ferric nitrate in the maceration extract, the catalyst that obtains contains Pd2%, Bi1%, Pb0.3%, Fe0.3%, (carrier quality relatively).The catalyst that use makes reacts under the condition identical with embodiment 1, and the MAL conversion ratio is 94.1%, and the selectivity of methyl methacrylate is 97.0%.
Embodiment 4
Adopt the method identical to prepare catalyst, just add the 1.67g palladium bichloride in the maceration extract with embodiment 1,0.924g bismuth chloride, 0.321g plumbi nitras, 1.44g ferric nitrate, the catalyst that obtains contains Pd5%, Bi3%, Pb1%, Fe1% (relative carrier quality).The catalyst that use makes reacts under the condition identical with embodiment 1, and the MAL conversion ratio is 95.7%, and the selectivity of methyl methacrylate is 96.8%.
Embodiment 5
Adopt the method identical to prepare catalyst, adding 1.00g palladium bichloride in the maceration extract just, 0.308g bismuth chloride, 0.192g plumbi nitras, 0.866g ferric nitrate with embodiment 1, the catalyst that obtains contains Pd3%, Bi1%, Pb0.6%, Fe0.6% (carrier quality relatively).The catalyst that use makes reacts under the condition identical with embodiment 1, and the MAL conversion ratio is 95.2%, and the selectivity of methyl methacrylate is 97.5%.
Embodiment 6
Adopt the method identical to prepare catalyst, adding 1.00g palladium bichloride in the maceration extract just, 0.462g bismuth chloride, 0.192g plumbi nitras, 0.866g ferric nitrate with embodiment 1, the catalyst that obtains contains Pd3%, Bi1.5%, Pb0.6%, Fe0.6% (carrier quality relatively).The catalyst that use makes reacts under the condition identical with embodiment 1, and the MAL conversion ratio is 95.6%, and the selectivity of methyl methacrylate is 97.9%.
Embodiment 7
Adopt the method identical to prepare catalyst with embodiment 1, just add the 1.00g palladium bichloride in the maceration extract, 0.462g bismuth chloride, 0.192g plumbi nitras, 0.866g ferric nitrate, 0.187g lanthanum nitrate, the catalyst that obtains contains Pd3%, Bi1.5%, Pb0.6%, Fe0.6%, La0.3% (carrier quality relatively).The catalyst that use makes reacts under the condition identical with embodiment 1, and the MAL conversion ratio is 95.2%, and the selectivity of methyl methacrylate is 98.2%.
Embodiment 8
Adopt the method identical to prepare catalyst with embodiment 1, just add the 1.00g palladium bichloride in the maceration extract, 0.462g the cerous nitrate of bismuth chloride, 0.192g plumbi nitras, 0.866g ferric nitrate, 0.186g, the catalyst that obtains contains Pd3%, Bi1.5%, Fe0.6%, Pb0.6%, Ce0.3% (carrier quality relatively).The catalyst that use makes reacts under the condition identical with embodiment 1, and the MAL conversion ratio is 95.3%, and the selectivity of methyl methacrylate is 98.4%.
Comparative Examples 1
Adopt the method identical to prepare catalyst, just add the 1.00g palladium bichloride in the maceration extract with embodiment 1,0.462g bismuth chloride, 0.321g plumbi nitras, the catalyst that obtains contains Pd3%, Pb1% (relative carrier quality).The catalyst that use makes reacts under the condition identical with embodiment 1, and the MAL conversion ratio is 79.7%, and the selectivity of methyl methacrylate is 83.2%.
Comparative Examples 2
Adopt the method identical to prepare catalyst, just add the 1.00g palladium bichloride in the maceration extract with embodiment 1,0.308g bismuth chloride, 0.866g ferric nitrate, the catalyst that obtains contains Pd3%, Bi1% (relative carrier quality).The catalyst that use makes reacts under the condition identical with embodiment 1, and the MAL conversion ratio is 82.2%, and the selectivity of methyl methacrylate is 84.9%.
Claims (4)
1, a kind of resin catalyst that is used to prepare methyl methacrylate is characterized in that, the carrier of this catalyst is the styrene diethylene benzene copoly mer resin, and the specific area of carrier is 300～800m
2/ g, average pore size 2～30nm; The active component of load with respect to the mass percentage content of carrier is on the carrier: palladium is 2%～5%, and bismuth is 0～3%, and lead is 0.3%～1%, and iron is 0.3%～1%, and lanthanum is 0～1%.
2, a kind of resin catalyst that is used to prepare methyl methacrylate is characterized in that, the carrier of this catalyst is the styrene diethylene benzene copoly mer resin, and the specific area of carrier is 300～800m
2/ g, average pore size 2～30nm; The active component of load with respect to the mass percentage content of carrier is on the carrier: palladium is 2%～5%, and bismuth is 0～3%, and lead is 0.3%～1%, and iron is 0.3%～1%, and cerium is 0～1%.
3, a kind of preparation method who is used to prepare the resin catalyst of methyl methacrylate is characterized in that may further comprise the steps:
(1) the styrene diethylene benzene copoly mer resin carrier was soaked in ethanol 3～4 hours under 20～30 ℃ of conditions, filter and be placed on dry for standby in 60 ℃ of baking ovens;
(2) palladium bichloride, bismuth chloride, plumbi nitras, ferric nitrate and lanthanum nitrate are dissolved in the N.N-dimethyl formamide organic solvent, are mixed with the mixed solution of lanthanum nitrate of ferric nitrate, the 0～0.01g/mL of plumbi nitras, the 0.007～0.023g/mL of bismuth chloride, the 0.0016～0.005g/mL of the palladium bichloride that contains 0.011～0.028g/mL, 0～0.015g/mL;
(3) will press incipient impregnation in the mixed solution of step (2) preparation through the pretreated carrier of step (1), and flood 5～6 hours at 20～30 ℃, soaked carrier places 70 ℃～90 ℃ oven dryings; The NaOH methanol solution that carrier drying is placed on 0.005g/ml～0.02g/ml soaked 4～6 hours; Carrier is at hydrogen flow rate 20～60ml/min, 120～220 ℃ of reduction temperatures, and 8～12 hours recovery times were carried out reduction activation, and obtaining carrier is the styrene diethylene benzene copoly mer resin, is loaded with the catalyst of palladium, bismuth, lead, iron and lanthanum.
4, a kind of preparation method who is used to prepare the resin catalyst of methyl methacrylate is characterized in that may further comprise the steps:
(1) the styrene diethylene benzene copoly mer resin carrier was soaked in ethanol 3～4 hours under 20～30 ℃ of conditions, filter and be placed on dry for standby in 60 ℃ of baking ovens;
(2) palladium bichloride, bismuth chloride, plumbi nitras, ferric nitrate and cerous nitrate are dissolved in the N.N-dimethyl formamide organic solvent, are mixed with the mixed solution of cerous nitrate of ferric nitrate, the 0～0.01g/mL of plumbi nitras, the 0.007～0.023g/mL of bismuth chloride, the 0.0016～0.005g/mL of the palladium bichloride that contains 0.011～0.028g/mL, 0～0.015g/mL;
(3) will press incipient impregnation in the mixed solution of step (2) preparation through the pretreated carrier of step (1), and flood 5～6 hours at 20～30 ℃, soaked carrier places 70 ℃～90 ℃ oven dryings; The NaOH methanol solution that carrier drying is placed on 0.005g/ml～0.02g/ml soaked 4～6 hours; Carrier is at hydrogen flow rate 20～60ml/min, 120～220 ℃ of reduction temperatures, and 8～12 hours recovery times were carried out reduction activation, and obtaining carrier is the styrene diethylene benzene copoly mer resin, is loaded with the catalyst of palladium, bismuth, lead, iron and cerium.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2007100576800A CN100469446C (en) | 2007-06-20 | 2007-06-20 | Resin catalyst for producing methyl-methacrylate and its production |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100576800A CN100469446C (en) | 2007-06-20 | 2007-06-20 | Resin catalyst for producing methyl-methacrylate and its production |
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| Publication Number | Publication Date |
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| CN101073784A true CN101073784A (en) | 2007-11-21 |
| CN100469446C CN100469446C (en) | 2009-03-18 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014146481A1 (en) * | 2013-03-18 | 2014-09-25 | The Hong Kong University Of Science And Technology | Development of high-efficiency adsorbent from e-waste and aluminosilicate-based materials for removal of toxic heavy metal ions from wastewater |
| CN105705238A (en) * | 2013-07-29 | 2016-06-22 | 罗门哈斯公司 | Oxidative esterification catalyst |
| WO2020107539A1 (en) * | 2018-11-29 | 2020-06-04 | 中国科学院大连化学物理研究所 | Preparation method for catalyst for producing methyl methacrylate, and application thereof |
-
2007
- 2007-06-20 CN CNB2007100576800A patent/CN100469446C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014146481A1 (en) * | 2013-03-18 | 2014-09-25 | The Hong Kong University Of Science And Technology | Development of high-efficiency adsorbent from e-waste and aluminosilicate-based materials for removal of toxic heavy metal ions from wastewater |
| US10639623B2 (en) | 2013-03-18 | 2020-05-05 | The Hong Kong University Of Science And Technology | Development of a high-efficiency adsorbent from E-waste and aluminosilicate-based materials for the removal of toxic heavy metal ions from wastewater |
| CN105705238A (en) * | 2013-07-29 | 2016-06-22 | 罗门哈斯公司 | Oxidative esterification catalyst |
| US9770708B2 (en) | 2013-07-29 | 2017-09-26 | Rohm And Haas Company | Oxidative esterification catalyst |
| CN105705238B (en) * | 2013-07-29 | 2018-07-03 | 罗门哈斯公司 | Oxidative esterification catalyst |
| WO2020107539A1 (en) * | 2018-11-29 | 2020-06-04 | 中国科学院大连化学物理研究所 | Preparation method for catalyst for producing methyl methacrylate, and application thereof |
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| CN100469446C (en) | 2009-03-18 |
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