CN1745896A - Synthesis of ferro-niobium ellestadite aluminium molecular sieve from pyruvic acid - Google Patents
Synthesis of ferro-niobium ellestadite aluminium molecular sieve from pyruvic acid Download PDFInfo
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- CN1745896A CN1745896A CN 200510028625 CN200510028625A CN1745896A CN 1745896 A CN1745896 A CN 1745896A CN 200510028625 CN200510028625 CN 200510028625 CN 200510028625 A CN200510028625 A CN 200510028625A CN 1745896 A CN1745896 A CN 1745896A
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- niobium
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- molecular sieve
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Abstract
A NdFeSiPAl molecular sieve catalyst for synthesizing pyruvate is prepared through proportionally mixing distilled water, phosphoric acid, Fe source, Al source, Si source, Nd source and triethylamine, stirring until becoming gel, constant-temp crystallizing, baking and calcining. Its advantages are high catalytic oxidizing and catalytic esterifying activity, high conversion rate and high selectivity.
Description
Technical field
The invention belongs to technical field of organic synthesis, relate to have oxidation, esterification performance bifunctional molecule sieve catalyst, relate in particular to the ferro-niobium aluminium silicophosphate molecular sieve Preparation of catalysts method that is used for the pyruvate synthesis technique.
Background technology
The pyruvic acid series compound is important organic synthesis and medicinal intermediates, and its synthetic method has winestone acid system, lactate method, electrochemical process etc.The pyroracemic aldehyde method of Ti Chuing is a kind of rising pyruvic acid and the preparation technology of its esters in recent years.The production method comparative maturity of pyroracemic aldehyde generally is to utilize 1, and the oxidative dehydrogenation in the presence of the Ag catalyst of 2-propane diols makes, and has realized industrialization.The further oxidation of pyroracemic aldehyde just can be obtained pyruvic acid, at last pyruvic acid and methyl alcohol reaction are generated methyl pyruvate.But pyroracemic aldehyde oxidation, esterification generate the process route of pyruvate activity of such catalysts, selectivity and stability are all had higher requirements, and still do not have the industrialization report at present.
Organic carboxylic ester is that a class is widely used in the important industrial chemicals in the industry such as spices, coating, plastics, binding agent and organic synthesis, and for a long time, dense H is continued to use in synthesizing of this class ester always
2SO
4Make catalyst.But there are many problems in this production method: (1) in esterification process because dense H
2SO
4Dehydration and oxidation can cause some side reactions, be present in the reaction system thereby produce compounds such as a spot of unsaturated compound, ether or sulfuric ester, this will and reclaim unreacted raw material and cause a lot of difficulties to the separation and purification of product; (2) in the last handling process of product, inevitably can produce the waste liquid that has genotoxic potential, if untimely processing, will contaminated environment; (3) H
2SO
4Also etching apparatus seriously causes the raising of production cost; (4) in a single day careless in the work as if operating personnel, may cause and burn; (5) catalyst can't reclaim and reuse.Obviously, the novel environment-friendly catalyst of research and development replaces the dense H of traditional catalyst
2SO
4Synthesize organic carboxylic ester, become a problem demanding prompt solution.
Summary of the invention
The purpose of this utility model is, for overcoming the various shortcoming that traditional catalyst for esterification reaction concentrated sulfuric acid brings, produce the synthesis technique of pyruvate at pyroracemic aldehyde oxidation, esterification, a kind of bifunctional molecule sieve catalyst with good catalytic oxidation and catalytic esterification performance is provided.
For achieving the above object, the technical scheme that adopts is: the selective oxidation performance of finding the FeAlPO-5 molecular sieve catalyst in the previous research work that oxidation reaction is carried out is fine, attempt in skeleton, to add these hetero atoms of Si, Nb, improve the acidity of catalyst, synthetic a kind of bifunctional molecule sieve catalyst that has oxidation, the suitable pyruvate synthesis technique of esterification performance simultaneously.
(1) ferro-niobium aluminium silicophosphate molecular sieve Preparation of catalysts method, concrete steps are:
A) the mole proportioning by each raw material in the mixture adds following raw materials according and stirring successively in beaker, until forming even gel;
Distilled water H
2O 60～100H
2O
Phosphoric acid 85%H
3PO
40.5～1.5P
2O
5
Source of iron: ferric nitrate Fe (NO
3)
39H
2O 0.1～0.5Fe
2O
3
Aluminium source: boehmite Al
2O
32H
2O 0.5～1.5Al
2O
3
Silicon source: ethyl orthosilicate (C
2H
5)
4SiO
40.1～0.5SiO
2
Niobium source: niobium hydroxide Nb (OH)
50.01～0.1Nb
2O
5
Template agent: triethylamine (Et
3) N 1.0～2.0 (Et
3) N
B) will in the above-mentioned gel immigration sealing, 100～200 ℃ of constant temperature, continuous crystallization 24～72 hours be arranged in the stainless steel cauldron of teflon gasket;
C) above-mentioned crystallization product 100～200 ℃ of oven dry 10～24 hours, uses Muffle furnace 500～600 ℃ of roastings 2～4 hours through after filtering and washing then.
(2) ferro-niobium aluminium silicophosphate molecular sieve catalyst is used for the synthesis technique of pyruvate.
Good effect of the present utility model is: ferro-niobium aluminium silicophosphate molecular sieve catalyst, be the well behaved bifunctional molecule sieve catalyst of a kind of catalytic oxidation, catalytic esterification, the preparation method is simple, recyclable repeated use, free from environmental pollution, safety and environmental protection is a kind of environmentally friendly catalyst.Be oxidized to pyruvic acid at pyroracemic aldehyde, in the synthetic methyl pyruvate technology of pyruvic acid and methyl alcohol, adopt ferro-niobium aluminium silicophosphate molecular sieve catalyst conversion ratio can reach 53.5%, selectivity is greater than 98%.
The specific embodiment
Embodiment 1
Ferro-niobium aluminium silicophosphate molecular sieve Preparation of catalysts method, step is:
A) the mole proportioning by each raw material in the mixture adds following raw materials according and stirring successively in beaker, until forming even gel, is pick up speed, can stir down at warm 30～40 ℃;
Distilled water H
2O 60～100H
2O
Phosphoric acid 85%H
3PO
4AR level (Shanghai connection and chemical plant) 0.5～1.5P
2O
5
Ferric nitrate Fe (NO
3)
39H
2O AR level (Peng Zhen barracks chemical plant, Shanghai) 0.1～0.5Fe
2O
3
Boehmite Al
2O
32H
2O (factory of shanghai refinery) 0.5～1.5Al
2O
3
Ethyl orthosilicate (C
2H
5)
4SiO
4AR level (Chinese Medicine group) 0.1～0.5SiO
2
Niobium hydroxide Nb (OH)
5AR level (east, Ningxia tantalum industry) 0.01～0.1Nb
2O
5
Triethylamine (Et
3) N AR level (the Shanghai phenanthrene reaches industry and trade Co., Ltd) 1.0～2.0 (Et
3) N
B) will have in the stainless steel cauldron of teflon gasket in the above-mentioned gel immigration, sealing is put into insulating box, 100～200 ℃ of constant temperature, continuous crystallization 24～72 hours;
C) above-mentioned crystallization product uses Muffle furnace 500～600 ℃ of roastings 2～4 hours through filtering and wash the back 100 ℃～200 ℃ oven dry 10～24 hours then.
The ferro-niobium aluminium silicophosphate molecular sieve catalyst of preparation gained is designated as sample 1; Press method and step shown in the embodiment 1 in addition, and mole proportioning in the mixture, not adding niobium source (niobium hydroxide), preparation iron silicon phosphorus aluminium FeAPSO-5 molecular sieve catalyst is designated as sample 2; Do not add niobium source (niobium hydroxide) and silicon source (ethyl orthosilicate) preparation iron phosphorus aluminium FeAlPO-5 catalyst, be designated as sample 3, make performance comparison with the present invention.
Catalytic oxidation:
Cyclohexane, solvent acetonitrile, oxidant TBHP, 70 ℃ of reaction temperatures add above-mentioned three kinds of catalyst (being sample 1, sample 2, sample 3) respectively, and product is cyclohexanol and cyclohexanone, and total conversion is respectively:
| Sample | 1 | 2 | 3 |
| Total conversion | 7.73％ | 6.67％ | 3.37％ |
Catalytic esterification:
Isobutyric acid and methyl alcohol reaction, solvent acetonitrile adds above-mentioned three kinds of catalyst respectively, and reaction temperature is 120 ℃, and product is a methyl isobutyrate, and total conversion is respectively:
| Sample | 1 | 2 | 3 |
| Total conversion | 68.42％ | 25.00％ | 5.85％ |
Performance comparison shows: ferro-niobium silicon phosphorus Al catalysts of the present invention is a kind of bifunctional molecule sieve catalyst with good catalytic oxidation and catalytic esterification performance.
Embodiment 2
Ferro-niobium aluminium silicophosphate molecular sieve catalyst is used for the synthesis technique of pyruvate, and pyroracemic aldehyde and methyl alcohol under the effect of ferro-niobium silicon phosphorus aluminum bifunctional molecular sieve catalyst, oxidative esterification reaction take place as the raw material of preparation pyruvate, generate methyl pyruvate.
Because pyroracemic aldehyde instability, polycondensation easily, commodity pyroracemic aldehyde by outsourcing can't carry out gas-phase reaction, so present embodiment has been set up the continuous reaction unit of a cover, make reaction from 1, the oxidation of 2-propane diols prepares pyroracemic aldehyde and begins, and in the back reaction propane diols is oxidized to pyroracemic aldehyde, catalyst is selected silver-colored supported catalyst, and research institute provides by the Shanghai petrochemical industry.The pyroracemic aldehyde for preparing directly enters second reaction unit, and the raw material as the preparation pyruvate under the effect of ferro-niobium silicon phosphorus aluminum bifunctional molecular sieve catalyst oxidative esterification reaction takes place with methyl alcohol, generates methyl pyruvate.Heat the problem of bringing again with regard to cooling in the middle of having reduced pyroracemic aldehyde like this.
(1) 1, the 2-propane diols is oxidized to pyroracemic aldehyde, continuous reaction apparatus flow process with methyl alcohol generation oxidative esterification reaction is again: at first nitrogen and air mixing preheating in blender, regulate oxygen content wherein, add 1 of the amount of determining, enter first reactor generation oxidation reaction after the preheating of 2-mixed with propylene glycol, reaction condition is: temperature is 250～470 ℃, and air speed is 0.5～2.0h
-1, oxygen/propane diols (mol ratio)=(0.5～2.0): (0.3～1.5), O
2Concentration=3.5～5.8%.
(2) above-mentioned product enters blender and mixes with another strand air and methyl alcohol after the preheating, enters second reactor generation oxidative esterification reaction, and temperature is 50～350 ℃, and air speed is 0.5～4.0h
-1, obtain target product.
Observe the influence of temperature and air speed to reaction, the result shows, use the ferro-niobium aluminium silicophosphate molecular sieve as catalyst, under 100～200 ℃, air mass flow is at 20～80ml/min, material molar ratio 1,2-propane diols: methyl alcohol: air=(0.2～2.0): (0.5～3.0): in (1～20) scope, reaction effect the best.Adopt ferro-niobium silicon phosphorus aluminum bifunctional molecular sieve catalyst can reach 53.5% to the conversion ratio of methyl pyruvate synthetic reaction, selectivity is greater than 98%.
Claims (2)
1, ferro-niobium aluminium silicophosphate molecular sieve Preparation of catalysts method, step is:
1) in beaker, adds following raw materials according and stirring successively, until forming even gel by mole proportioning in the mixture;
Distilled water H
2O 60～100H
2O
Phosphoric acid 85%H
3PO
40.5～1.5P
2O
5
Source of iron: ferric nitrate Fe (NO
3)
39H
2O 0.1～0.5Fe
2O
3
Aluminium source: boehmite Al
2O
32H
2O 0.5～1.5Al
2O
3
Silicon source: ethyl orthosilicate (C
2H
5)
4SiO
40.1～0.5SiO
2
Niobium source: niobium hydroxide Nb (OH)
50.01～0.1Nb
2O
5
Template agent: triethylamine (Et
3) N 1.0～2.0 (Et
3) N
2) will in the above-mentioned gel immigration sealing, 100～200 ℃ of constant temperature, continuous crystallization 24～72 hours be arranged in the stainless steel cauldron of teflon gasket;
3) after above-mentioned crystallization product filters and washs,, use Muffle furnace then 500～600 ℃ of roastings 2～4 hours 100～200 ℃ of oven dry 10～24 hours.
2, the described ferro-niobium aluminium silicophosphate molecular sieve of claim 1 catalyst is used for the synthesis technique of pyruvate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200510028625XA CN100345634C (en) | 2005-08-09 | 2005-08-09 | Synthesis of ferro-niobium ellestadite aluminium molecular sieve from pyruvic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200510028625XA CN100345634C (en) | 2005-08-09 | 2005-08-09 | Synthesis of ferro-niobium ellestadite aluminium molecular sieve from pyruvic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1745896A true CN1745896A (en) | 2006-03-15 |
| CN100345634C CN100345634C (en) | 2007-10-31 |
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ID=36165713
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|---|---|---|---|
| CNB200510028625XA Expired - Fee Related CN100345634C (en) | 2005-08-09 | 2005-08-09 | Synthesis of ferro-niobium ellestadite aluminium molecular sieve from pyruvic acid |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101643413B (en) * | 2009-09-07 | 2013-01-16 | 上海交通大学 | One pot method for preparing aryl-alpha-keto ester based on arylethyl ketone |
| CN105646223A (en) * | 2014-12-04 | 2016-06-08 | 中国科学院大连化学物理研究所 | Method used for preparing succinic acid diester via catalytic oxidation esterification of levulinic acid |
| CN106622272A (en) * | 2016-11-25 | 2017-05-10 | 南宁市黑晶信息技术有限公司 | Preparation method of composite molecular sieve based catalyst used for synthesis of pyruvate |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5888921A (en) * | 1995-10-25 | 1999-03-30 | Abb Lummus Global Inc. | Binary molecular sieves having a core and shell of different structures and compositions |
| US6319872B1 (en) * | 1998-08-20 | 2001-11-20 | Conoco Inc | Fischer-Tropsch processes using catalysts on mesoporous supports |
| JP4168214B2 (en) * | 1998-10-15 | 2008-10-22 | 三菱瓦斯化学株式会社 | Methylamine production catalyst and method for producing the catalyst |
| US6500972B2 (en) * | 2001-01-03 | 2002-12-31 | Chinese Petroleim Corp. | Synthesis of TMBQ with transition metal-containing molecular sieve as catalysts |
-
2005
- 2005-08-09 CN CNB200510028625XA patent/CN100345634C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101643413B (en) * | 2009-09-07 | 2013-01-16 | 上海交通大学 | One pot method for preparing aryl-alpha-keto ester based on arylethyl ketone |
| CN105646223A (en) * | 2014-12-04 | 2016-06-08 | 中国科学院大连化学物理研究所 | Method used for preparing succinic acid diester via catalytic oxidation esterification of levulinic acid |
| CN105646223B (en) * | 2014-12-04 | 2017-12-26 | 中国科学院大连化学物理研究所 | A kind of method that levulic acid catalysis oxidation esterification prepares succinate |
| CN106622272A (en) * | 2016-11-25 | 2017-05-10 | 南宁市黑晶信息技术有限公司 | Preparation method of composite molecular sieve based catalyst used for synthesis of pyruvate |
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| Publication number | Publication date |
|---|---|
| CN100345634C (en) | 2007-10-31 |
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Granted publication date: 20071031 |