CN103769095B - Hydrogenation of Dimethyl Oxalate reaction generates ethylene glycol catalyst and preparation method thereof - Google Patents
Hydrogenation of Dimethyl Oxalate reaction generates ethylene glycol catalyst and preparation method thereof Download PDFInfo
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Abstract
Hydrogenation of Dimethyl Oxalate reaction generates ethylene glycol catalyst and preparation method thereof, relate to a kind of catalyst and preparation method thereof, this catalyst is with copper nitrate, Schweinfurt green or copper chloride for copper source, with alkoxy silane, high-purity silicon powder, high-purity gas-phase silica, Ludox for silicon source.With ammonia, carbamide, ammonium hydrogen carbonate as precipitant.Introduce period of element Table VIII, IB, Group IIB transition metal chloride and nitrate and prepare Cu M Si catalyst as promoter, employing co-precipitation, sol-gal process.Catalyst preparation step is: silicon source processes through solvent volatilization self-assembly method and obtains mesoporous SiO2, active component and precipitant complexation are obtained copper M ammonia complexing solution, above-mentioned complex solution loads to mesoporous SiO2Carrier obtains Cu M Si catalyst.Cu 10 30%, promoter M 0.005 5%, surplus is mesoporous SiO2, catalyst has good prospects for commercial application.
Description
Technical field
The present invention relates to a kind of catalyst and preparation method thereof, particularly relate to a kind of Hydrogenation of Dimethyl Oxalate reaction and generate ethylene glycol catalyst and preparation method thereof.
Background technology
Ethylene glycol (EG) is a kind of important basic chemical industry raw material, the alcohols material widely applied is the second largest class alcohol after methanol, mainly for the production of polyster fibre and coating and packaging material polyester resin, accounting for more than the 80% of consumption figure, remaining is used for producing antifreezing agent, lubricant, explosive etc..
The traditional method producing ethylene glycol is that petrochemical industry route, i.e. epoxyethane water are legal.Obtained oxirane by ethylene through gaseous oxidation, then be hydrated preparing ethylene glycol through liquid-phase catalysis.But, there is rich coal, few gas, oil-poor energy general layout in China's oil inadequate resource, therefore opens up and be of great practical significance and long-range strategic importance by the new technique of coal generating gas production ethylene glycol.Usually said " coal-ethylene glycol " technique is with coal as raw material, by gasifying, convert, purify and respectively obtaining CO and H after separating-purifying2, wherein CO is synthesized by catalytic coupling and the refined dimethyl oxalate. that produces, then through and H2Carry out hydrogenation reaction and by obtaining the process of polyester grade ethylene glycol after refining.This technological process is short, energy consumption is little, low cost, is the most domestic coal-ethylene glycol technology receiving publicity the highest.The most both at home and abroad to CO gaseous oxidation preparing oxalate coupling reaction relative maturity, and it is to realize industrialized committed step that oxalate catalytic hydrogenation is prepared this step of ethylene glycol, and the stability of catalyst and life problems are the Important Problems of scientific research.
The current domestic aggregation announcing grasp coal-ethylene glycol technology specifically includes that the emerging product in space portion of Japan high chemistry agency, eastern Chinese workers' journey aggregation, Fujian thing structure institute, Dan Hua group, Henan coal industry aggregation；University Of Tianjin, the raw engineering of favour, China's this energy aggregation；East China University of Science, Pu, Shanghai scape, Huai Hua group aggregation；Hua Yi group etc..Each research institution all claims the technology of oneself to reach industrialized standard, but due to various problems such as the restriction of catalyst, mostly existence and stability are bad, and product quality is the most up to standard, and catalyst life is short.Simultaneously as differences such as catalyst system, reaction condition, evaluating apparatus, analysis means, the levels of catalysts difference of report is relatively big, and comparability is not the strongest.
Chinese Academy of Sciences's Fujian thing structure used Cu-Cr series catalysts, the technological accumulation by more than 20 years is cooperated with enterprise, it is thus achieved that a series of lab scale technology with entirely autonomous intellectual property and mould examination technology.Jiangsu technical team of Dan Hua group has a long-term accumulation of chemical industry new technological industry, the most multinomial chemical industry new technology such as pioneering " carbonization legal system ammonium hydrogen carbonate ", " carbonylation synthesis acetic anhydride " and " pressure-variable adsorption separates CO ".
External coal-ethylene glycol project development is earlier mainly based on Japan and the U.S..Relatively early, technology relative maturity, nineteen eighty-two priority has applied for the catalyst patent of 7 preparing ethylene glycol by using dimethyl oxalate plus hydrogen in the coal-ethylene glycol project research of company of Ube Industries Ltd..Catalyst system is respectively Cu-Si, Cu-Ti, Cu-Cr-Mn etc., and introduces auxiliary agent raising catalyst performance.Method for preparing catalyst mainly uses coprecipitation, infusion process, sol-gal process.UCC company of the U.S. started in 1985 to have applied for two about Hydrogenation of Dimethyl Oxalate patent, the Cu-Si catalyst that US 4677234 technology is mainly prepared with curpic carbonate and ammonium carbonate for raw material；US 4628128 describes Cu-Si catalyst prepared by a kind of infusion process.Italy ARCO company also applied in 1976 one about Hydrogenation of Dimethyl Oxalate catalyst, US 4112245 mainly uses coprecipitation to prepare Cu-Zn-Cr and Cu-Cr System Catalyst, and introduces the auxiliary agents such as Ca and Cr.
Hydrogenation of Dimethyl Oxalate catalyst is mainly based on Cu-Si and Cu-Cr two individual system, although Cu-Cr catalyst activity is preferably, but Cr is hypertoxic, it is big to pollute, the most superseded.So Cu-Si System Catalyst has good DEVELOPMENT PROSPECT.But report Cu-Si system mostly all introduces various auxiliary agent, and the mechanism of action of auxiliary agent and action effect the most indefinite.Catalyst syntheti c route is still based on traditional coprecipitation, infusion process, sol-gal process etc..
The import volume of China's ethylene glycol reaches about 7,200,000 tons at present, and importation dependence remains at more than 70%, and main employing epoxyethane water is legal.
Summary of the invention
It is an object of the invention to provide a kind of Hydrogenation of Dimethyl Oxalate reaction and generate ethylene glycol catalyst and preparation method thereof, the method catalyst carries out dimethyl oxalate. gas phase and takes off the reaction being hydrogenated to ethylene glycol, there is high one way feed stock conversion and target product selectivity, method for preparing catalyst is simple, with low cost, has high stability simultaneously.
It is an object of the invention to be achieved through the following technical solutions:
Hydrogenation of Dimethyl Oxalate reaction generates ethylene glycol catalyst, and described catalyst active component is metal Cu and its oxides 10-30%, and promoter is period of element Table VIII, IB, Group IIB transition metal chloride and nitrate 0.005-5%, and surplus is mesoporous SiO2；The reaction that catalyst is suitable for is that dimethyl oxalate. two ends methoxyl group occurs hydrogenation reaction simultaneously, generates ethylene glycol and by-product carbinol；Precipitant used includes ammonia, carbamide, ammonium hydrogen carbonate, sodium carbonate；Silicon source used includes mesoporous SiO2, alkoxy silane, high-purity silicon powder, high-purity gas-phase silica, Ludox；Copper source includes copper nitrate, Schweinfurt green and copper chloride, and load capacity is at 10%-30%.
Hydrogenation of Dimethyl Oxalate reaction generates ethylene glycol catalyst preparation method, and described method includes mesoporous SiO2Carrier uses solvent volatilization self-assembly preparation method thereof, and its specific surface area is 200～1000m2/ g, preparation process is:
Under continuous agitation by surfactant (Pluronic P123,
PEO20-PPO70-PEO20, Aldrich) it is dissolved in ethanol；Silicon source raw material is added sequentially in above-mentioned solution, is stirred at room temperature further 4-10 hour after all dissolving；Temperature is mentioned 60 DEG C, within continuously stirred 48 hours, removes solvent, form xerogel；Mesoporous SiO is obtained after being calcined 4 hours at 700 DEG C by above-mentioned xerogel2；
The preparation method of catalyst includes that co-precipitation-infusion process, sol-gal process prepare Cu-M-Si catalyst；The preparation process of two kinds of methods is respectively as follows:
1) co-precipitation-infusion process: be first dissolved in deionized water in copper source and promoter M, adds precipitant (ammonia, carbamide, ammonium hydrogen carbonate) and obtains copper-M-ammonia complexing solution, by the mesoporous SiO of preparation2Carrier modulation becomes aqueous solution, join under stirring condition in above-mentioned complex solution, 60 DEG C of continuously stirred dippings 12 hours, being sufficiently impregnated with load, filtration washing to filtrate is colourless and pH=7, gained filtration cakes torrefaction 12 hours, 450 DEG C of calcinings form crystal conversion in 3-8 hour, last shaping of catalyst, pelletize, reduction；
2) sol-gal process: first copper source and promoter is dissolved in deionized water, is stirred at room temperature 4 hours after adding ethanol and silicon source；Above-mentioned solution is sealed, keeps 72 hours under room temperature, obtain the gel of green homogeneous transparent；Gel adding alkali compounds, ammonia, carbamide, ammonium hydrogen carbonate, soaking through sodium carbonate 2-12 hour, is washed with deionized, filters until filtrate is colourless, filter cake 120 DEG C is dried 12 hours, the lower 450 DEG C of roastings of air conditions 5 hours, and molding, granulating reduces.
Described Hydrogenation of Dimethyl Oxalate reaction generation ethylene glycol catalyst preparation method, described surfactant (Pluronic P123, PEO20-PPO70-PEO20,
Aldrich) usage ratio is 0.02%-2%.
Described Hydrogenation of Dimethyl Oxalate reaction generates ethylene glycol catalyst preparation method, and its reaction temperature of described gas phase hydrogenation reaction is 150～300 DEG C, and reaction pressure is 1.5-3MPa.
Detailed description of the invention
Below in conjunction with embodiment, the invention will be further described.
Embodiment 1:
Step one: weigh 2g Pluronic P123 dispersant and be dissolved in 300ml ethanol.
Step 2: weighing 31g tetraethoxysilane and add in above-mentioned solution, after room temperature with constant stirring is until all dissolving, continuing stirring 8 hours.
Step 3: remove solvent in continuously stirred 48 hours at 60 DEG C and form xerogel, gel is calcined at 700 DEG C 4 hours and prepare mesoporous SiO2。
Step 4: by the above-mentioned mesoporous SiO of gained 8g under room temperature2Add in 300ml deionized water, strong stirring divide sprinkle even.
Step 5: weigh 7.5g Cu (NO3)2·3H2O is dissolved in 200ml deionized water.Add 25ml strong aqua ammonia, make copper ammonia complexation solution.
Step 6: under room temperature, the copper ammonia complexation solution of step 5 gained is joined the mesoporous SiO that step 4 is modulated2In aqueous solution, stir 1 hour.Then heat to 60 DEG C of continuously stirred dippings 24 hours, be sufficiently impregnated with load.
Step 7: filtration washing to filtrate is colourless and pH=7, gained filtration cakes torrefaction 12 hours, 450 DEG C of calcinings form crystal conversion in 8 hours.Last shaping of catalyst, pelletize, reduction.20-40 mesh catalyst loads in reactor, reaction condition: reaction temperature 170 DEG C, reaction pressure 2.5MPa, hydrogen ester ratio 80.
The results are shown in Table one.
Embodiment 2:
Step one, two, three, four with embodiment 1.
Step 5: weigh 7.5g Cu (NO3)2·3H2O and 0.1 Fe (NO3)3·9H2O is dissolved in 200ml deionized water.Add 25ml strong aqua ammonia, make copper-ferrum-ammonia complexing solution.
Step 6: under room temperature, the copper-ferrum-ammonia complexing solution of step 5 gained is joined the mesoporous SiO of step 4 modulation2In aqueous solution, stir 1 hour.Then heat to 60 DEG C of continuously stirred dippings 24 hours, be sufficiently impregnated with load.
Step 7: with embodiment 1
The results are shown in Table one.
Embodiment 3:
Step one, two, three, four with embodiment 1.
Step 5: weigh 7.5g Cu (NO3)2·3H2O and 0.1 Ni (NO3)3·6H2O is dissolved in 200ml deionized water.Add 25ml strong aqua ammonia, make copper-nickel-ammonia complexing solution.
Step 6: under room temperature, the copper-nickel-ammonia complexing solution of step 5 gained is joined the mesoporous SiO of step 4 modulation2In aqueous solution, stir 1 hour.Then heat to 60 DEG C of continuously stirred dippings 24 hours, be sufficiently impregnated with load.
Step 7: with embodiment 1
The results are shown in Table one.
Embodiment 4:
Step one, two, three, four with embodiment 1.
Step 5: weigh 7.5g Cu (NO3)2·3H2O and 0.1 Co (NO3)3·6H2O is dissolved in 200ml deionized water.Add 25ml strong aqua ammonia, make copper-cobalt-ammonia complexing solution.
Step 6: under room temperature, the copper-cobalt-ammonia complexing solution of step 5 gained is joined the mesoporous SiO of step 4 modulation2In aqueous solution, stir 1 hour.Then heat to 60 DEG C of continuously stirred dippings 24 hours, be sufficiently impregnated with load.
Step 7: with embodiment 1
The results are shown in Table one.
Embodiment 5:
Step one, two, three, four with embodiment 1.
Step 5: weigh 7.5g Cu (NO3)2·3H2O and 0.09g PdCl2It is dissolved in 200ml deionized water.Add 25ml strong aqua ammonia, make copper-palladium-ammonia complexing solution.
Step 6: under room temperature, the copper-palladium-ammonia complexing solution of step 5 gained is joined the mesoporous SiO of step 4 modulation2In aqueous solution, stir 1 hour.Then heat to 60 DEG C of continuously stirred dippings 24 hours, be sufficiently impregnated with load.
Step 7: with embodiment 1
The results are shown in Table one.
Embodiment 6:
Step one: with embodiment 1.
Step 2: weigh 40g concentration 20%(percentage by weight) Ludox add in above-mentioned solution, continue stirring 8 hours.
Step 3, four with embodiment 1.
Step 5, six, seven with embodiment 3
The results are shown in Table one.
Embodiment 7:
Step one: with embodiment 1.
Step 2: with embodiment 6
Step 3, four with embodiment 1.
Step 5: weigh 10g CuCl2·2H2O and 0.09g PdCl2It is dissolved in 200ml deionized water.Add 25ml strong aqua ammonia, make copper-palladium-ammonia complexing solution.
Step 6, seven with embodiment 6
The results are shown in Table one.
Embodiment 8:
Step one: 7.5gCu (NO3)2·3H2O adds 50ml deionized water dissolving.Adding ethanol and tetraethyl orthosilicate (TEOS), proportioning is n(TEOS): n(ethanol): n(water)=1:4:11, it is stirred at room temperature 4 hours.
Step 2: sealed by above-mentioned solution, keeps 72 hours under room temperature, obtains the gel of green homogeneous transparent.
Step 3: gel is added ammonia soak, then 75 DEG C be evaporated liquid after, 120 DEG C be dried 24 hours.
Step 4: gained solid is washed with deionized, filters until filtrate is colourless, filter cake 120 DEG C is dried 12 hours.
Step 5: the lower 450 DEG C of roastings of air conditions 5 hours, molding, sieves.
Step 6: 20-40 mesh catalyst loads in reactor, reaction temperature 170 DEG C, reaction pressure 2.5MPa, hydrogen ester ratio 80.
The results are shown in Table one.
Embodiment 9:
Step one: 10g CuCl2·2H2O adds 50ml deionized water dissolving.Add ethanol and 40g concentration 20%(percentage by weight) Ludox, be stirred at room temperature 4 hours.
Step 2, three, four, five, six with embodiment 8
The results are shown in Table one.
Embodiment 10:
Step one: 7.5gCu (NO3)2·3H2O and 0.09g PdCl2Add 50ml deionized water dissolving.Add the mesoporous SiO of gained in ethanol and embodiment 128g, is stirred at room temperature 4 hours.
Step 2, three, four, five, six with embodiment 9.
The results are shown in Table one.
Table one
| Embodiment | DMO conversion ratio % | EG selectivity % |
| 1 | 100 | 97.3 |
| 2 | 99 | 95.2 |
| 3 | 100 | 96.6 |
| 4 | 100 | 97.2 |
| 5 | 100 | 98.1 |
| 6 | 100 | 97.6 |
| 7 | 100 | 97.8 |
| 8 | 100 | 97.6 |
| 9 | 100 | 95.8 |
| 10 | 100 | 98.3 |
Note: DMO is dimethyl oxalate., and EG is ethylene glycol.
Claims (1)
1. Hydrogenation of Dimethyl Oxalate reaction generates ethylene glycol catalyst, it is characterised in that described catalyst prepares according to following steps:
Step one: weigh 2g Pluronic P123 dispersant and be dissolved in 300ml ethanol；
Step 2: weighing 31g tetraethoxysilane and add in step one gained solution, after room temperature with constant stirring is until all dissolving, continuing stirring 8 hours；
Step 3: remove solvent in continuously stirred 48 hours at 60 DEG C and form xerogel, xerogel is calcined at 700 DEG C 4 hours and prepare mesoporous SiO2；
Step 4: 7.5g Cu (NO3)2·3H2O and 0.09g PdCl2Add 50ml deionized water dissolving, add ethanol and the mesoporous SiO of step 3 gained28g, is stirred at room temperature 4 hours；
Step 5: sealed by step 4 gained solution, keeps 72 hours under room temperature, obtains the gel of green homogeneous transparent；
Step 6: step 5 gained gel is added ammonia and soaks, after 75 DEG C are evaporated liquid, 120 DEG C are dried 24 hours；
Step 7: be washed with deionized by step 6 gained solid, filter until filtrate is colourless, filter cake 120 DEG C is dried 12 hours；
Step 8: the lower 450 DEG C of roastings of air conditions 5 hours, molding, sieves, and obtains 20-40 mesh catalyst.
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| CN109569601A (en) * | 2018-12-05 | 2019-04-05 | 中触媒新材料股份有限公司 | A kind of efficient stable carried copper-base catalyst and preparation method thereof |
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| JP2017171599A (en) * | 2016-03-23 | 2017-09-28 | 高化学技術株式会社 | Solid catalyst and method for producing ethylene glycol using the solid catalyst |
| CN109569621B (en) * | 2017-09-29 | 2021-10-01 | 中国石油化工股份有限公司 | Catalyst composition, method of manufacture and use thereof |
| CN109569616B (en) * | 2017-09-29 | 2021-11-30 | 中国石油化工股份有限公司 | Catalyst composition, preparation method and application thereof |
| CN109718765A (en) * | 2018-12-06 | 2019-05-07 | 河南能源化工集团研究总院有限公司 | A kind of silicon powder directly prepares the preparation method of hydrogenation of dimethyl oxalate to synthesizing ethylene glycol catalyst |
| CN111905734B (en) * | 2020-07-06 | 2023-01-24 | 太原理工大学 | High-efficiency copper-based catalyst for preparing ethylene glycol by dimethyl oxalate hydrogenation and preparation method thereof |
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| CN102319581B (en) * | 2011-07-14 | 2013-07-24 | 河南煤业化工集团研究院有限责任公司 | Efficient oxalic ester hydrogenation catalyst and preparation method thereof |
| CN102716744B (en) * | 2012-06-18 | 2014-07-02 | 河南煤业化工集团研究院有限责任公司 | Preparation method for synthesizing copper-based catalyst by sol-gel ammonia still process |
| CN102764656B (en) * | 2012-08-06 | 2015-05-20 | 久泰能源科技有限公司 | High-efficiency hydrogenation catalyst and method for preparing same |
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| CN109569601A (en) * | 2018-12-05 | 2019-04-05 | 中触媒新材料股份有限公司 | A kind of efficient stable carried copper-base catalyst and preparation method thereof |
| CN109569601B (en) * | 2018-12-05 | 2021-07-13 | 中触媒新材料股份有限公司 | High-efficiency stable supported copper-based catalyst and preparation method thereof |
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Effective date of registration: 20170324 Address after: 226000 Nantong economic and Technological Development Zone, Jiangsu, Shun Road, No. 1, building -11, 6 Patentee after: High chemical (Jiangsu) chemical new material Co., Ltd. Address before: 110142 Shenyang economic and Technological Development Zone, Liaoning, No. 11 Patentee before: Shenyang University of Chemical Technology |