CN1214865C - 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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- CN1214865C CN1214865C CN 03100738 CN03100738A CN1214865C CN 1214865 C CN1214865 C CN 1214865C CN 03100738 CN03100738 CN 03100738 CN 03100738 A CN03100738 A CN 03100738A CN 1214865 C CN1214865 C CN 1214865C
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- catalyst
- methyl methacrylate
- mal
- esterification
- caco
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Abstract
The present invention relates to a novel composite catalyst which has the main components of palladium, plumbum, bismuth, rare earths and other elements. The catalyst is mainly applied to the oxidization of methylacrolein (MAL) and the esterification of oxidized MAL with methanol (MeOH) to produce methyl methacrylate (MMA) in one step. Besides the palladium, the plumbum, the bismuth and other active components, one or some of the rare earth elements are added into the catalyst, and thus, the defects of the existing oxidizing and esterifying catalysts are overcome. Besides the advantages of high conversion rate and good selectivity, the novel composite catalyst has the characteristics of simple preparation process, mild reaction condition and high space time yield (namely unit volume of the catalyst and unit time).
Description
Technical field the present invention relates to the preparation that a kind of principal component is the composite catalyst of 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 (O), the tellurium (Te), Y is at least a of alkali metal or alkaline-earth metal, and Z is at least a in rare earth element scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and the lutetium except that promethium (Pm).A, b, c, d, e represent the atomic ratio a=0.001-0.4 of every kind of element with respect to Pd, b=0.001-0.6, c=0-0.4, d=0-0.5, e=0.0001-0.5 respectively.
Catalyst middle rare earth element can be one or more combination of simple substance, oxide, hydroxide.Carrier can be CaCO
3, ZnO, MgO, SiO
2, TiO
2, Al
2O
3, activated carbon, molecular sieve, cimita one or more combination.Catalyst shape can be powder, particle, sphere, column.
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 0.42g PdCl
2Be dissolved in the suitable quantity of water, add 10gCaCO
3, stirring and refluxing one hour.Then the gained mixture is dried, add 20ml HCHO solution again, get solid 1 after stirring, suction filtration, the washing.
Take by weighing 0.46gBi (NO
3)
2, 0.18g Pb (AC)
2, 0.72g Fe (NO
3)
3Be dissolved in 40ml 3% rare nitric acid, 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 0.20g Ce (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 0.41g Ce (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 0.08g La (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 0.20g La (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 0.41g La (NO into
3)
3, make and consist of Pd
5Bi
2PbFeLa/CaCO
3Catalyst.
Embodiment 7
Take by weighing 0.42g PdCl
2Be dissolved in the suitable quantity of water, add 10gCaCO
3, stirring and refluxing one hour.Then the gained mixture is dried, add 20ml HCHO solution again, get solid 1 after stirring, suction filtration, the washing.
Take by weighing 0.46gBi (NO
3)
2, 0.18g Pb (AC)
2, 0.72g Fe (NO
3)
3Be dissolved in 40ml 3% rare nitric acid, 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 (4)
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, makes MAL and methyl alcohol single step reaction produce methyl methacrylate, and this catalyst is represented 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, Z is at least a in the rare earth element except that promethium (Pm), 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, c=0-0.4, d=0-0.5, e=0.0001-0.5.
2. according to the rare earth element in the claim 1, its existence form is one or more combination of simple substance, oxide, hydroxide.
3. 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.
4. according to the catalyst in the claim 1, its shape is powder, particle, sphere, column.
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 |
Applications Claiming Priority (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 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1485133A CN1485133A (en) | 2004-03-31 |
| CN1214865C true CN1214865C (en) | 2005-08-17 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 03100738 Expired - Lifetime 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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Families Citing this family (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 |
| TW201509901A (en) | 2013-07-29 | 2015-03-16 | Rohm & Haas | Oxidative esterification process |
| TW201509522A (en) | 2013-07-29 | 2015-03-16 | Rohm & Haas | Oxidative esterification 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 |
| JP6661629B2 (en) * | 2014-10-31 | 2020-03-11 | ローム アンド ハース カンパニーＲｏｈｍ Ａｎｄ Ｈａａｓ Ｃｏｍｐａｎｙ | Oxidative esterification method for making methyl methacrylate |
| EP3144291A1 (en) * | 2015-09-16 | 2017-03-22 | Evonik Röhm GmbH | Synthesis of methacrylic acid from methacrolein based alkyl methacrylate |
| 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 |
| CN108126761B (en) * | 2016-12-01 | 2021-06-08 | 中国科学院大连化学物理研究所 | Cobalt-based composite particle load, preparation and synthesis of carboxylic 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 |
| 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 |
| 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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- 2003-01-22 CN CN 03100738 patent/CN1214865C/en not_active Expired - Lifetime
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