CN101768070A - Method for synthesizing crylic acid by catalyzing acetylene carbonyl through palladium - Google Patents
Method for synthesizing crylic acid by catalyzing acetylene carbonyl through palladium Download PDFInfo
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- CN101768070A CN101768070A CN200910058048A CN200910058048A CN101768070A CN 101768070 A CN101768070 A CN 101768070A CN 200910058048 A CN200910058048 A CN 200910058048A CN 200910058048 A CN200910058048 A CN 200910058048A CN 101768070 A CN101768070 A CN 101768070A
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Abstract
The invention provides a method for synthesizing crylic acid by catalyzing acetylene carbonyl through palladium. Acetylene, carbon monoxide and water are used as raw materials and are catalyzed to synthesize the crylic acid under the conditions that the reaction temperature is between 15 and 70 DEG C and the pressure is between 1.5 and 6MPa. The adopted catalyst uses palladium diacetate as a main catalyst; the dosage of the main catalyst is less than that of a traditional nickel-copper catalyst and is only 1/50; sulfoacid, such as methane sulfonate, trifluoromethane sulfonic acid, p-toluenesulfonic acid or the like, serves as an aid; an addition amount of the additive is that the ratio of n(-SO3H) to n(Pd2<+>) is equal to 1:1-10:1; and organic phosphine such as 2-pyridyl diphenylphosphine (2-PyPPh2) as a ligand. Compared with the nickel-copper catalyst, the catalyst has remarkable advantages that: under the mild conditions, such as the temperature of 40 DEG C and the pressure of 5 MPa, the catalyst can catalyze the acetylene carbonyl to synthesize the crylic acid at high efficiency, can effectively avoid the acetylene and the crylic acid undergoing polymerization and other side reactions, saves energy, and has safe operation and low operating expense.
Description
Technical field
The present invention relates to the novel method of the synthetic unsaturated acid of a kind of palladium catalysis alkynes carbonylation reaction, be particularly useful for acetylene oxo process vinylformic acid.
Background technology
Vinylformic acid is one of important source material of water-soluble polymers, and polyacrylic acid and its esters are widely used as the extender of dispersion agent, thickening material, flocculation agent, tackiness agent, coating-forming agent, super water-retaining agent and washing composition etc. by many industrial sectors.The acrylic acid throughput in the world is about 3,500,000 tons/year, mainly concentrate on the U.S., Europe and Japanese, the world 5 big vinylformic acid manufacturers are respectively BASF, ROHM AND HAAS, Celanese chemistry, Japanese catalyst chemistry and Atofina's chemistry, and it adds up to production capacity to account for more than 70% of world's aggregated capacity.According to statistics, estimate 2005～2015, the global vinylformic acid and the ester growth rate of demand will reach more than 4%, and the particularly Chinese major impetus that will become following vinylformic acid and ester demand growth in Asia, average growth rate per annum will reach 8%～10%.Yet the vinylformic acid of China and the production capacity of ester increases slowly, and do not catch up with the needs in market, so the import cumulative year after year of vinylformic acid and ester.
At present, the main method of vinylformic acid production has propylene partial oxidation process and acetylene carbonyl process.The raw material propylene of propylene partial oxidation process too relies on the petroleum resources of growing tension, and petroleum resources belong to Nonrenewable resources, and its resource is most valuable.And the acetylene carbonyl process can be avoided petroleum resources, belongs to the method for non-petroleum path acrylic acid synthesizing.The former exceeds 38% than the latter same production-scale fixed investment, and according to China's prices of raw and semifnished materials meter, cost of raw and processed materials acetylene carbonyl process is lower than propylene partial oxidation process.In addition, the acetylene carbonyl process has and does not rely on large-scale petroleum chemical joint venture and the low advantage of plant investment.And the national science and technology development priority is placed on the chemical utilization of Sweet natural gas and coal, the further investigation of carrying out the acetylene carbonyl process meets the requirement of national long-range development in science and technology just, especially can satisfy the needs of oil starvation, rich gas or rich coal, rich electricity area development fine chemistry industry, promote the development of light and textile industries, drive its derived product processing and exploitation.Therefore, acetylene carbonyl process acrylic acid synthesizing is more promising synthetic method, is the main direction of following acrylic acid synthesizing development.
This method is found by Reppe at first that in nineteen thirty-nine the catalyzer of Cai Yonging was Ni (CO) at that time
4[Chem.Rev.2001,101,3435-3456].But because Ni (CO)
4Boiling point is low, and is volatile, and catalyst loss is serious, and it is big to add toxicity, and labour protection is difficult to solve.Therefore, this catalyzer is not used in suitability for industrialized production.Afterwards, this method obtained industrial application through improving once in countries such as Germany, Japan and the U.S., played crucial effect in the acetylene chemistry epoch.The sixties in 20th century, scope and raising conversion of alkyne and acrylic acid yield for widening catalyzer such as Bhattacharyya, the acrylic acid catalyst system of acetylene oxo process is studied, find when high spot reviews iron-based, cobalt-based and nickel-base catalyst, the highest [the IndEng Chem Proc Des Dev of the activity of nickel naphthenate, 1964,3 (2): 169～176; JAppl Chem, 1963,13:498～505; JAppl Chem, 1966,16:202～205].Under optimal experimental conditions, be catalyzer with the nickel naphthenate, acetylene conversion is that acrylic acid transformation efficiency is 14.2%.The nineties in 20th century, An Yizhe etc. are the carbonyl source with the pure carbon monoxide, have investigated the acrylic acid catalyzer of high-pressure process acetylene oxo process, reaction conditions and technology.Adopting nickel-copper halogen composite catalyst, is solvent with the tetrahydrofuran (THF), carries out the moving reaction of single tube high pressure continuous flow under 200 ℃, 8MPa condition, the transformation efficiency of acetylene reaches about 90%, acrylic acid selectivity is 80%～85%[gas chemical industry, 1991,16 (6): 17-21].Although this type of catalyzer has good activity to acetylene oxo process vinylformic acid, and is serious to equipment corrosion, especially be easy to carbon deposit, blocking pipeline.
Princes and dukes should wait the people that nickelous bromide-cupric bromide system is improved subsequently, have developed a kind of effective catalyst, i.e. nickel acetate-cupric bromide [CN200810045609.5].This type of catalyzer is a part at triphenylphosphine, and methanesulfonic is an auxiliary agent, and at 200 ℃, catalytic conversion and selectivity all are higher than 90% under the 8MPa, and carbon accumulation resisting ability is strong, and is little to equipment corrosion.
Above-mentioned research all is based on nickel-base catalyst catalyzing acetylene oxo process vinylformic acid, and the subject matter of existence is that temperature of reaction and pressure are higher, promptly must just have the acrylic acid activity of catalyzing acetylene oxo process under the 8MPa in the condition of High Temperature High Pressure as 200 ℃.So harsh reaction conditions has proposed high requirement to reactor, pipeline, and promptly material must be high temperature resistant, high pressure resistant, corrosion-resistant; Simultaneously higher with the operational path energy consumption of this catalyst system.And High Temperature High Pressure is easy to side reactions such as association acetylene and acroleic acid polymerization, and is totally unfavorable to industrial application.Yet the existing at present research that is used for the synthetic ester of alkynes carbonylation of palladium catalyst is characterized in that temperature of reaction is low, and pressure is low, good selective [J Organomet Chem, 475 (1994) 57-63].The synthetic acid of alkynes esterification and alkynes carbonylation is similar, but there are differences aspect active, and esterification is easier than acidifying.
Summary of the invention
The purpose of this invention is to provide the acrylic acid novel method of a kind of acetylene oxo process, the catalyzer that is adopted is the palladium system, has good catalytic activity and excellent selectivity under lesser temps, lower pressure.Advantages such as it is low that this catalyzer has energy consumption, and the plant investment cost is few have the wide development application prospect.
The present invention realizes in the following way:
(1) no hydrogen system
Elder generation in solvent and water, adds a certain amount of catalyst dissolution in the autoclave, closes autoclave.Use air twice in the 1MPa nitrogen replacement autoclave subsequently, under agitation condition, in still, feed acetylene to certain pressure such as 0.5MPa then and reach dissolution equilibrium, then feed carbon monoxide to certain pressure as 5～6MPa.Begin to be warming up to temperature of reaction, stir (rotating speed is 1005 rev/mins), finish reaction behind the reaction certain hour and adopt gas-chromatography, gas chromatograph-mass spectrometer that gas phase and liquid phase are analyzed.
(2) contain hydrogen system
Elder generation in solvent and water, adds a certain amount of catalyst dissolution in the autoclave, closes autoclave.Use air twice in the 1MPa nitrogen replacement autoclave subsequently, feed acetylene to certain pressure such as 0.5MPa then and reach dissolution equilibrium under agitation condition in still, the mixed gas that then feeds the hydrogen carbon monoxide is (as v (H
2): v (CO)=1: 1) to certain pressure as 5～6MPa.Begin to be warming up to temperature of reaction, stir (rotating speed is 1005 rev/mins), finish reaction behind the reaction certain hour and adopt gas-chromatography, gas chromatograph-mass spectrometer that gas phase and liquid phase are analyzed.
The solvent that adopts has tetrahydrofuran (THF), acetone, N-Methyl pyrrolidone, N, dinethylformamide etc., this kind solvent is big to the solubleness of acetylene, can guarantee under lower pressure, the higher carbonylation reaction that is easy to of concentration of acetylene in the liquid phase can be avoided the danger of high pressure acetylene operation simultaneously again.The addition of water is 10%～25% of a solvent, has only solvent and water to keep suitable proportioning just to help the dissolving of catalyst dissolution and raw material acetylene, brings into play better catalyzed reaction effect.
Primary Catalysts is a palladium in the catalyzer that adopts, and auxiliary agent is methanesulfonic, trifluoromethayl sulfonic acid, p-methyl benzenesulfonic acid, and part is diphenyl alkyl phosphine, 2-pyridyl diphenylphosphine.The screening of Primary Catalysts has successively been carried out catalytic performance test to Palladous chloride, nitric acid handle, palladium, finds that the palladium effect obviously is better than Palladous chloride, Palladous nitrate; The investigation of part, part triphenylphosphine and the 2-pyridyl diphenylphosphine commonly used to carbonylation have carried out performance evaluation, find triphenylphosphine as part no matter the temperature, pressure condition how modulation does not all obtain product vinylformic acid, and 2-pyridyl diphenylphosphine all can obtain product vinylformic acid in wide in range temperature, pressure condition; The investigation of acid assistant has been carried out catalytic performance test to hydrochloric acid, acetic acid, p-methyl benzenesulfonic acid, methanesulfonic, trifluoromethayl sulfonic acid, trifluoroacetic acid etc., finds sulfonic acid series catalytic performance excellence.
The processing condition that adopt: n (C
2H
2): n (CO) is 1: 1～1: 10; Temperature of reaction is 15～70 ℃, and reaction pressure is 1.5MPa～6.0MPa; The consumption of palladium catalyst be solvent and water quality 0.01～0.5%.
Specific embodiment
Be embodiments of the invention below:
Embodiment one
Take by weighing Pd (CH
3COO)
20.0110g, CH
3SO
2OH 0.11g, 2-PyPPh
20.36g, be dissolved in 50ml acetone+6mlH
2Among the O, add in the 250ml autoclave, use 1MPa N
2Air is 2 times in the displacement still, fills C
2H
2Be saturated to 0.5MPa, fill H subsequently
2To 3MPa, fill CO to 5MPa then, be warming up to 40 ℃, reacted 2.5 hours.Still liquid is orange red, limpid, and the vinylformic acid mass concentration is 12.5%, C
2H
2Transformation efficiency is 41%, is 86% to acrylic acid selectivity.
Embodiment two
Take by weighing Pd (CH
3COO)
20.0120g, p-methyl benzenesulfonic acid 0.38g, 2-PyPPh
20.35g, be dissolved in 47mlN-methyl-2-pyrrolidone+6ml H
2Among the O, add in the 250ml autoclave, use 1MPa N
2Air is 2 times in the displacement still, fills C
2H
2Be saturated to 0.5MPa, fill CO to 5MPa then, be warming up to 40 ℃, reacted 2.5 hours.Still liquid brown, limpid, vinylformic acid mass concentration are 9.57%, C
2H
2Transformation efficiency is 43%, is 83% to acrylic acid selectivity.
Embodiment three
Take by weighing Pd (CH
3COO)
20.0130g, CuBr
20.12g, CH
3SO
2OH 0.11g, 2-PyPPh
20.36g, be dissolved in 47ml N-Methyl pyrrolidone+6ml H
2Among the O, add in the 250ml autoclave, use 1MPaN
2Air is 2 times in the displacement still, fills C
2H
2Be saturated to 0.5MPa, fill CO to 5MPa then, be warming up to 40 ℃, reacted 2.5 hours.Still liquid light red, limpid, vinylformic acid mass concentration are 2.5%, C
2H
2Transformation efficiency is 10%, is 76% to acrylic acid selectivity.
Embodiment four
Take by weighing Pd (CH
3COO)
20.0121g, CF
3SO
2OH 100 μ l, 2-PyPPh
20.36g, be dissolved in 50ml acetone+6mlH
2Among the O, add in the 250ml autoclave, use 1MPaN
2Air is 2 times in the displacement still, fills C
2H
2Be saturated to 0.5MPa, fill H subsequently
2To 2.5MPa, fill CO to 5MPa then, be warming up to 40 ℃, reacted 2.5 hours.Still liquid brown, limpid, vinylformic acid mass concentration are 13.5%, C
2H
2Transformation efficiency is 42%, is 90% to acrylic acid selectivity.
Embodiment five
Take by weighing PdCl
20.0101g, CF
3SO
2OH 100 μ l, 2-PyPPh
20.36g, be dissolved in 50ml acetone+6ml H
2Among the O, add in the 250ml autoclave, use 1MPa N
2Air is 2 times in the displacement still, fills C
2H
2Be saturated to 0.47MPa, fill CO to 5MPa then, be warming up to 40 ℃, reacted 2 hours.Still liquid sorrel, limpid, vinylformic acid mass concentration are 4.5%, C
2H
2Transformation efficiency is 14%, is 80% to acrylic acid selectivity.
Claims (9)
1. a method for synthesizing crylic acid by catalyzing acetylene carbonyl through palladium is characterized in that raw material acetylene is reacted acrylic acid synthesizing by mono-carbonylation.
2. method according to claim 1 is characterized in that the catalyzer that is adopted is made up of divalence palladium, sulfonic acid, organic phosphine.
3. method according to claim 2 is characterized in that the divalence palladium is a palladium, and sulfonic acid is methanesulfonic, trifluoromethayl sulfonic acid or p-methyl benzenesulfonic acid, and organic phosphine is a 2-pyridyl diphenylphosphine.
4. method according to claim 2 is characterized in that the divalence palladium is a Primary Catalysts, and sulfonic acid is auxiliary agent, and organic phosphine is a part.
5. method according to claim 4 is characterized in that n (Pd in this catalyzer
2+): n (phosphine part) is 1: 1～8, n (Pd
2+): n (SO
3H) be 1: 1～10.
6. method according to claim 1 and 2 is characterized in that the catalytic acetylene oxo process vinylformic acid processing condition gentleness of this catalyzer, and temperature of reaction is 15～70 ℃, and pressure is 1.5～6MPa.
7. method according to claim 1 is characterized in that with the synthetic gas being that the carbonyl source does not influence oxo process vinylformic acid.
8. method according to claim 7 is characterized in that the existence of hydrogen in the system does not influence the synthetic vinylformic acid of carbonylation, does not promptly exist hydrogenation to generate propionic acid, propenal, ethene, the side reaction of ethane hydrogenation.
9. according to claim 1,7 or 8 described methods, it is characterized in that carbon monoxide does not need pre-treatment, can be directly used in the carbonylation reaction acrylic acid synthesizing.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106278864A (en) * | 2016-08-11 | 2017-01-04 | 北京神雾环境能源科技集团股份有限公司 | A kind of acrylic acid process of acetylene carbonylation system and system |
| CN107602369A (en) * | 2017-02-28 | 2018-01-19 | 新疆中泰化学股份有限公司 | A kind of preparation method of acrylic acid or acrylate |
| CN109776303A (en) * | 2019-03-11 | 2019-05-21 | 重庆化工职业学院 | It is used to prepare the catalyst of acrylic acid or derivatives thereof |
| CN110152694A (en) * | 2019-06-21 | 2019-08-23 | 石河子大学 | A kind of heterogeneous acetylene carbonylating catalyst and preparation method thereof, application |
| CN113816839A (en) * | 2021-09-23 | 2021-12-21 | 中国成达工程有限公司 | Method for synthesizing butanedialdehyde by acetylene double-hydrogen formyl |
-
2009
- 2009-01-06 CN CN200910058048A patent/CN101768070A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106278864A (en) * | 2016-08-11 | 2017-01-04 | 北京神雾环境能源科技集团股份有限公司 | A kind of acrylic acid process of acetylene carbonylation system and system |
| CN107602369A (en) * | 2017-02-28 | 2018-01-19 | 新疆中泰化学股份有限公司 | A kind of preparation method of acrylic acid or acrylate |
| CN109776303A (en) * | 2019-03-11 | 2019-05-21 | 重庆化工职业学院 | It is used to prepare the catalyst of acrylic acid or derivatives thereof |
| CN109776303B (en) * | 2019-03-11 | 2021-07-20 | 重庆化工职业学院 | Catalyst for preparing acrylic acid or derivatives thereof |
| CN110152694A (en) * | 2019-06-21 | 2019-08-23 | 石河子大学 | A kind of heterogeneous acetylene carbonylating catalyst and preparation method thereof, application |
| CN110152694B (en) * | 2019-06-21 | 2022-03-22 | 石河子大学 | Heterogeneous acetylene carbonylation catalyst and preparation method and application thereof |
| CN113816839A (en) * | 2021-09-23 | 2021-12-21 | 中国成达工程有限公司 | Method for synthesizing butanedialdehyde by acetylene double-hydrogen formyl |
| CN113816839B (en) * | 2021-09-23 | 2024-02-02 | 中国成达工程有限公司 | Method for synthesizing glyoxal through acetylene double hydroformylation |
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Application publication date: 20100707 |