CN1485133A - New pattern catalyst for preparing methyl methacrylate by one-step oxidation-esterification from methylacrolein - Google Patents
New pattern catalyst for preparing methyl methacrylate by one-step oxidation-esterification from methylacrolein Download PDFInfo
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- CN1485133A CN1485133A CNA031007384A CN03100738A CN1485133A CN 1485133 A CN1485133 A CN 1485133A CN A031007384 A CNA031007384 A CN A031007384A CN 03100738 A CN03100738 A CN 03100738A CN 1485133 A CN1485133 A CN 1485133A
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- catalyst
- rare earth
- methyl methacrylate
- esterification
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Abstract
The invention relates to a new composite catalyst mainly comprising palladium,lead,bismuth and rare earth elements. The catalyst is mainly applied in esterification of methyl acraldehyde and methanol to produce methyl methyl-acrylate (MMA). Besides active components of palladium,lead,bismuth and so on, one or several rare earth elements are added, which overcomes drawbacks of the current oxidation- esterification catalysts. The catalyst has a good selectivity and a high conversion rate. The catalyst is simple to be produced, has mild reaction conditions.
Description
Technical field the present invention relates to the novel composite catalyst that a kind of principal component is elements such as palladium, lead, bismuth and rare earth, and this catalyst is mainly used in MAL (MAL) oxidation and produces in the reaction of methyl methacrylate (MMA) with one step of methyl alcohol (MeOH) esterification.
The background technology methyl methacrylate is the topmost polymerization single polymerization monomer of acrylic acid synthesizing resin and plastic.Its synthetic method is in the past mainly based on acetone cyanohydrin method (ACH method), but because raw materials used severe toxicity of this technology path and corrosivity height, accessory substance is many and Atom economy poor (only being 26.99%), now replaced by environmentally friendly technology gradually, wherein with C
4It is main that derivative is produced MMA technology.Initial C
4Derivative is produced methyl methacrylate technology and need be finished through isobutene or the tert-butyl alcohol → MAL → three steps of methacrylic acid → methyl methacrylate, because this route is longer, reasons such as intermediate products methacrylic acid meeting etching apparatus, the direction of research is transferred to isobutene or the tert-butyl alcohol → MAL → methyl methacrylate two-step method gradually now.The present invention relates to the reaction of second step, is raw material with methyl alcohol and MAL promptly, under the effect of catalyst, by the molecular oxygen selective oxidation esterification is taken place simultaneously and obtains MMA.
Pd is the key component that molecular oxygen, methyl alcohol and MAL generation oxidative esterification reaction are produced MMA, but that the result of single metal catalytic is a conversion ratio is low, accessory substance is many, poor selectivity (US3772381).Thereafter patent has been done improvement to this, add a lot of other components and changed this defective, as JP-B-57-35856, JP-A-57-50545 and JP-A-61-243044 Pd, Pb System Catalyst are proposed, JP-B-61-60820, JP-B-62-7902 and JP-A-5-148184 propose the Pd-Bi system, JP-A-61-243044 proposes the Pd-Te system, JP-B-57-35860 proposes the Pd-Tl-Hg system, JP-B-57-19090 proposes Pd-alkaline earth-Zn-Cd system etc., even but these catalyst compositions are identical with carrier, the yield of MMA is also inequality, and reappearance is relatively poor.
Patent is subsequently improved at above shortcoming, as the best reaction result conversion ratio 93.6% of USP5892102, selectivity 97.7%; EP0972759A1 requires acid strength pKa＞4.8, best reaction result conversion ratio 88%, selectivity 96.8.But these improve the progress still be only limited in a certain respect, all have the catalyst of fine performance still to be among the continuous exploration simultaneously to conversion ratio, selectivity, reaction rate.
Summary of the invention the objective of the invention is to find a kind of by MAL simultaneously and the catalyst of methyl alcohol generation esterification production methyl methacrylate by the molecular oxygen selective oxidation, it compared with prior art, except have conversion ratio height, selectivity good advantage, it is simple also to have preparation technology simultaneously, the reaction condition gentleness, the high characteristics of space time yield (being per volume of catalyst, unit interval).
What the present invention obtained is raw material with the MAL, by the molecular oxygen selective oxidation simultaneously and the methyl alcohol generation esterification contained component of catalyst that obtains methyl methacrylate represent with following formula:
PdPb
aBi
bX
cY
dZ
e/ carrier
Wherein Pd is that palladium, Pb are bismuth for plumbous, Bi, X is at least a in iron (Fe), cobalt (Co), zinc (Zn), chromium (Cr), barium (Ba), silver (Ag), germanium (Ge), manganese (Mn), nickel (Ni), copper (Cu), the tellurium (Te), Y is at least a of alkali metal or alkaline-earth metal, and Z is at least a in the rare earth element except that promethium (Pm) and actinium series.A, b, c, d, e represent the atomic ratio a=0.001-0.4 of every kind of element with respect to Pd respectively, b=0.001-0.6, and c=0-0.4, d=0-0.5, e=0.0001-0.5, carrier are CaCO
3, ZnO, MgO, SiO
2, TiO
2, Al
2O
3, activated carbon, molecular sieve, cimita one or more combination.
Specify the present invention with embodiment below, the conversion ratio of term MAL and the definition of the selectivity of methyl methacrylate are as follows:
Embodiment 1
Take by weighing 0.42gPdCl
2Be dissolved in the suitable quantity of water, add 10gCaCO
3, stirring and refluxing one hour.Then the gained mixture is dried, add 20mlHCHO solution again, get solid 1 after stirring, suction filtration, the washing.
Take by weighing 0.46gBi (NO
3)
2, 0.18gPb (AC)
2, 0.72gFe (NO
3)
3Be dissolved in the rare nitric acid of 40ml3%, solid 1 is added, the control temperature stirred one hour about 60 ℃.Then the gained mixture is dried, adds 15mlHCHO solution, stirring, suction filtration, wash solid 2.
With 0.08gCe (NO
3)
3Be dissolved in the 5ml water and make solution, solid 2 is added, stir; Dropwise add ammoniacal liquor, continue to stir 4h, suction filtration, washing, drying obtain solid, and being composition is Pd
5Bi
2PbFeCe
0.2/ CaCO
3Catalyst.
Embodiment 2
Method is with embodiment 1, with 0.08gCe (NO
3)
3Change 0.20gCe (NO into
3)
3, make and consist of Pd
5Bi
2PbFeCe
0.5/ CaCO
3Catalyst.
Embodiment 3
Method is with embodiment 1, with 0.08gCe (NO
3)
3Change 0.41gCe (NO into
3)
3, make and consist of Pd
5Bi
2PbFeCe/CaCO
3Catalyst.
Embodiment 4
Method is with embodiment 1, with 0.08gCe (NO
3)
3Change 0.08gLa (NO into
3)
3, make and consist of Pd
5Bi
2PbFeLa
0.2/ CaCO
3Catalyst.
Embodiment 5
Method is with embodiment 4, with 0.08gCe (NO
3)
3Change 0.20gLa (NO into
3)
3, make and consist of Pd
5Bi
2PbFeLa
0.5/ CaCO
3Catalyst.
Embodiment 6
Method is with embodiment 4, with 0.08gCe (NO
3)
3Change 0.41gLa (NO into
3)
3, make and consist of Pd
5Bi
2PbFeLa/CaCO
3Catalyst.
Embodiment 7
Take by weighing 0.42gPdCl
2Be dissolved in the suitable quantity of water, add 10gCaCO
3, stirring and refluxing one hour.Then the gained mixture is dried, add 20mlHCHO solution again, get solid 1 after stirring, suction filtration, the washing.
Take by weighing 0.46gBi (NO
3)
2, 0.18gPb (AC)
2, 0.72gFe (NO
3)
3Be dissolved in the rare nitric acid of 40ml3%, solid 1 is added, the control temperature stirred one hour about 60 ℃.Then the gained mixture is dried, adds 15mlHCHO solution, stirring, suction filtration, wash solid 2.
With 0.08gCe (NO
3)
3And 0.08gLa (NO
3)
3Be dissolved in the 5ml water and make solution, solid 2 is added, stir; Dropwise add ammoniacal liquor, continue to stir 4h, suction filtration, washing, drying obtain solid, and being composition is Pd
5Bi
2PbFeCe
0.2La
0.2/ CaCO
3Catalyst.
Embodiment 8
In the 200ml three-neck flask, add made catalyst among the 2.0g embodiment 1-embodiment 7, add 3.5g MAL (being equivalent to 4.2ml) and 80g methyl alcohol (being equivalent to 101ml) then successively, NaOH-MeOH solution with 0.3mol/L is regulated pH value to 10.5, stirs.Begin reaction behind the setting air flow 100ml/min, bath temperature to 70 ℃.
Result among the embodiment is as follows:
| Catalyst is formed | MAL conversion ratio (wt%) | MMA selectivity (wt%) | The MAL complete reaction time (h) |
| ????Pd 5Bi 2PbFeCe 0.2/CaCO 3 | ????98.4 | ????97.1 | ????＜3.0 |
| ????Pd 5Bi 2PbFeCe 0.5/CaCO 3 | ????99.9 | ????97.4 | ????＜3.0 |
| ????Pd 5Bi 2PbFeCe/CaCO 3 | ????98.0 | ????97.0 | ????＜3.0 |
| ????Pd 5Bi 2PbFeLa 0.2/CaCO 3 | ????97.8 | ????96.8 | ????＜3.0 |
| ????Pd 5Bi 2PbFeLa 0.5/CaCO 3 | ????98.5 | ????97.1 | ????＜3.0 |
| ????Pd 5Bi 2PbFeLa/CaCO 3 | ????97.1 | ????97.0 | ????＜3.0 |
| ????Pd 5Bi 2PbFeCe 0.2La 0.2/CaCO 3 | ????99.1 | ????97.2 | ????＜3.0 |
Embodiment 9
In the 200ml three-neck flask, add made catalyst among the 2.0g embodiment 1-embodiment 7, add 3.5g MAL (being equivalent to 4.2ml) and 80g methyl alcohol (being equivalent to 101ml) then successively, NaOH-MeOH solution with 0.3mol/L is regulated pH value to 10.5, stirs.Begin reaction behind the setting air flow 150ml/min, bath temperature to 70 ℃.
Result among the embodiment is as follows:
| Catalyst is formed | MAL conversion ratio (wt%) | MMA selectivity (wt%) | The MAL complete reaction time (h) |
| ????Pd 5Bi 2PbFeCe 0.2/CaCO 3 | ????98.2 | ????97.0 | ????＜2.5 |
| ????Pd 5Bi 2PbFeCe 0.5/CaCO 3 | ????99.7 | ????97.1 | ????＜2.5 |
| ????Pd 5Bi 2PbFeCe/CaCO 3 | ????98.1 | ????97.4 | ????＜2.5 |
| ????Pd 5Bi 2PbFeLa 0.2/CaCO 3 | ????97.9 | ????96.9 | ????＜2.5 |
| ????Pd 5Bi 2PbFeLa 0.5/CaCO 3 | ????98.7 | ????97.5 | ????＜2.5 |
| ????Pd 5Bi 2PbFeLa/CaCO 3 | ????97.3 | ????97.1 | ????＜2.5 |
| ????Pd 5Bi 2PbFeCe 0.2La 0.2/CaCO 3 | ????99.2 | ????97.4 | ????＜2.5 |
Claims (5)
1. one kind is used for the new catalyst that methyl methacrylate is produced in the esterification of metering system aldehyde oxidation, it is characterized in that in the presence of molecular oxygen, make MAL and methyl alcohol single step reaction produce methyl methacrylate, this catalyst contains carrier, active constituent is palladium, lead, bismuth, and contain at least a in iron, cobalt, zinc, chromium, barium, silver, germanium, manganese, nickel, copper, the tellurium, alkali metal or alkaline-earth metal at least a, and at least a in the rare earth element.
2. according to the catalyst in the claim 1, wherein rare earth element is other rare earth element scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium except that promethium and actinium series.
3. according to the rare earth element in the claim 2, its existence form can be simple substance, oxide, hydroxide, other compounds or compound.
4. according to the catalyst in the claim 1, wherein carrier is CaCO
3, ZnO, MgO, SiO
2, TiO
2, Al
2O
3, one or more the combination in the activated carbon, molecular sieve, cimita, the carrier of other types also can use.
5. according to the catalyst in the claim 1, its shape can be powder, particle, sphere, column or other shape.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03100738 CN1214865C (en) | 2003-01-22 | 2003-01-22 | New pattern catalyst for preparing methyl methacrylate by one-step oxidation-esterification from methylacrolein |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03100738 CN1214865C (en) | 2003-01-22 | 2003-01-22 | New pattern catalyst for preparing methyl methacrylate by one-step oxidation-esterification from methylacrolein |
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|---|---|
| CN1485133A true CN1485133A (en) | 2004-03-31 |
| CN1214865C CN1214865C (en) | 2005-08-17 |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100453177C (en) * | 2006-05-15 | 2009-01-21 | 北京化工大学 | Catalyst for producing methyl-acrylate from methyl-acrolein and its production |
| CN101376629B (en) * | 2007-08-27 | 2012-05-30 | 中国石油天然气股份有限公司 | Method for producing unsaturated fatty acid ester by oxidative esterification |
| CN103420835A (en) * | 2013-07-01 | 2013-12-04 | 太仓市恒益医药化工原料厂 | Method for preparing methyl methacrylate by using methacrolein |
| CN105233822A (en) * | 2014-07-11 | 2016-01-13 | 中国石油化工股份有限公司 | Super-gravity catalyst for oxidizing and esterifying aldehyde into carboxylate ester and application of super-gravity catalyst |
| CN105705238A (en) * | 2013-07-29 | 2016-06-22 | 罗门哈斯公司 | Oxidative esterification catalyst |
| US9676699B2 (en) | 2013-07-29 | 2017-06-13 | Rohm And Haas Company | Preparation of methyl methacrylate via an oxidative esterification process |
| CN107074727A (en) * | 2014-10-31 | 2017-08-18 | 罗门哈斯公司 | Oxidative esterification method for manufacturing methyl methacrylate |
| CN107519892A (en) * | 2016-06-20 | 2017-12-29 | 中国科学院大连化学物理研究所 | A kind of support type oxidative esterification catalyst and its preparation method and application |
| CN108137474A (en) * | 2015-09-16 | 2018-06-08 | 赢创罗姆有限公司 | From the alkyl methacrylate synthesizing methyl acrylic acid based on methacrolein |
| CN108126761A (en) * | 2016-12-01 | 2018-06-08 | 中国科学院大连化学物理研究所 | A kind of cobalt-based composite particle-loaded article and preparation and the synthesis of carboxylate |
| CN109772345A (en) * | 2019-01-05 | 2019-05-21 | 山东理工大学 | The preparation of the Raney nickel of oxidation of aldehydes lactate synthesis ester and its application that catalyst system is total to ionic liquid |
| CN110075835A (en) * | 2019-05-24 | 2019-08-02 | 厦门大学 | A kind of catalyst and its preparation method and application of step oxidative esterification legal system methyl methacrylate |
| 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 |
-
2003
- 2003-01-22 CN CN 03100738 patent/CN1214865C/en not_active Expired - Lifetime
Cited By (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100453177C (en) * | 2006-05-15 | 2009-01-21 | 北京化工大学 | Catalyst for producing methyl-acrylate from methyl-acrolein and its production |
| CN101376629B (en) * | 2007-08-27 | 2012-05-30 | 中国石油天然气股份有限公司 | Method for producing unsaturated fatty acid ester by oxidative esterification |
| CN103420835A (en) * | 2013-07-01 | 2013-12-04 | 太仓市恒益医药化工原料厂 | Method for preparing methyl methacrylate by using methacrolein |
| 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 |
| CN105705238A (en) * | 2013-07-29 | 2016-06-22 | 罗门哈斯公司 | Oxidative esterification catalyst |
| JP2016527082A (en) * | 2013-07-29 | 2016-09-08 | ローム アンド ハース カンパニーＲｏｈｍ Ａｎｄ Ｈａａｓ Ｃｏｍｐａｎｙ | Oxidative esterification catalyst |
| US9676699B2 (en) | 2013-07-29 | 2017-06-13 | Rohm And Haas Company | Preparation of methyl methacrylate via an oxidative esterification process |
| CN105233822A (en) * | 2014-07-11 | 2016-01-13 | 中国石油化工股份有限公司 | Super-gravity catalyst for oxidizing and esterifying aldehyde into carboxylate ester and application of super-gravity catalyst |
| 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 |
| CN107074727A (en) * | 2014-10-31 | 2017-08-18 | 罗门哈斯公司 | Oxidative esterification method for manufacturing methyl methacrylate |
| CN108137474A (en) * | 2015-09-16 | 2018-06-08 | 赢创罗姆有限公司 | From the alkyl methacrylate synthesizing methyl acrylic acid based on methacrolein |
| CN108137474B (en) * | 2015-09-16 | 2021-09-17 | 罗姆化学有限责任公司 | Synthesis of methacrylic acid from alkyl methacrylate based on methacrolein |
| CN107519892A (en) * | 2016-06-20 | 2017-12-29 | 中国科学院大连化学物理研究所 | A kind of support type oxidative esterification catalyst and its preparation method and application |
| CN107519892B (en) * | 2016-06-20 | 2019-11-22 | 中国科学院大连化学物理研究所 | A kind of support type oxidative esterification catalyst and its preparation method and application |
| CN108126761A (en) * | 2016-12-01 | 2018-06-08 | 中国科学院大连化学物理研究所 | A kind of cobalt-based composite particle-loaded article and preparation and the synthesis of carboxylate |
| 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 |
| CN109772345A (en) * | 2019-01-05 | 2019-05-21 | 山东理工大学 | The preparation of the Raney nickel of oxidation of aldehydes lactate synthesis ester and its application that catalyst system is total to ionic liquid |
| CN109772345B (en) * | 2019-01-05 | 2022-03-04 | 山东理工大学 | Preparation of nickel catalyst for synthesizing ester by aldehyde oxidation esterification and application of nickel catalyst and ionic liquid co-catalysis system |
| CN110075835A (en) * | 2019-05-24 | 2019-08-02 | 厦门大学 | A kind of catalyst and its preparation method and application of step oxidative esterification legal system methyl methacrylate |
| CN110075835B (en) * | 2019-05-24 | 2022-03-29 | 厦门大学 | Catalyst for preparing methyl methacrylate by one-step oxidation esterification method and preparation method and application thereof |
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