CN102000586A - Catalyst for preparing 1,2-propylene glycol from hydroxyacetone hydrogenation as well as preparation method and application thereof - Google Patents

Catalyst for preparing 1,2-propylene glycol from hydroxyacetone hydrogenation as well as preparation method and application thereof Download PDF

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CN102000586A
CN102000586A CN 201010551038 CN201010551038A CN102000586A CN 102000586 A CN102000586 A CN 102000586A CN 201010551038 CN201010551038 CN 201010551038 CN 201010551038 A CN201010551038 A CN 201010551038A CN 102000586 A CN102000586 A CN 102000586A
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China
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catalyst
preparation
cobalt
hydroxypropanone
reaction
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李浔
袁燕平
张跃飞
戴益民
朱志平
周艺
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Changsha University of Science and Technology
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Changsha University of Science and Technology
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Abstract

The invention relates to a catalyst for preparing 1,2-propylene glycol from hydroxyacetone hydrogenation under milder conditions as well as a preparation method and application thereof. The catalyst is composite oxide of copper and chrome or a composite oxide of cobalt and chrome, wherein the atomic ratios of Cu to Cr and Co to Cr are respectively 1:5-5:1. The catalyst can be used for catalyzing the hydroxyacetone hydrogenation to generate the 1,2-propylene glycol under the milder conditions, has high conversion rate and selectivity, and greatly reduces the reaction pressure and temperature as well as production cost.

Description

Be used for hydroxypropanone-hydrogenation preparing 1, the Catalysts and its preparation method of 2-propane diols and application
Technical field
The present invention relates to a kind of hydroxypropanone-hydrogenation preparing 1 that is used for, the catalyst of 2-propane diols, its preparation method and this catalyst be in hydroxypropanone-hydrogenation preparing 1, the application in the reaction of 2-propane diols.
Background technology
Along with the exhaustion of petroleum resources on the earth, the regenerative resource biodiesel obtains developing energetically, and the also dramatic growth thereupon of its byproduct glycerine comes very big impact for traditional glycerine market again, and the price of glycerine descends greatly.Because the finite capacity in traditional glycerine market, some manufacturer is compelled against one's will, and glycerine directly can only be burned.Therefore, consider, seek for glycerine and new utilize approach significant from the angle of utilization of resources, environmental protection and economic benefit.
1, the 2-propane diols is a kind of important chemical material.Its main application is preparation unsaturated polyester (UP), surfactant, plasticizer, emulsifying agent and demulsifier, also be widely used in addition in food, medicine and the cosmetics industry, use as hygroscopic agent, mould inhibitor, anticorrisive agent, pharmaceutical carrier, antifreeze, lubricant and solvent.At present, industrial 1, the 2-propane diols mainly makes by the hydrolysis of petrochemicals expoxy propane, complex process, cost are higher, and are that raw material produces 1 to produce the diesel oil by-product glycerin, and then not only cost is low for the 2-propane diols, and aboundresources, saved fossil feedstock effectively.
Glycerine can generate 1, the 2-propane diols by hydrogenation catalyst.At present, domestic and international research concentrates on glycerine hydrogenation one-step method preparation 1,2-propane diols mostly.This method reaction condition is relatively harsher, and 1, the selectivity of 2-propane diols is lower, is difficult to realize large-scale industrial production.Suppes etc. have studied glycerine recently through dehydration and hydrogenation two-step method preparation 1, the variation route of 2-propane diols, that is: and glycerine changes hydroxypropanone-into by dehydration, and hydroxypropanone-generates 1 through hydrogenation reaction again, the 2-propane diols.This method reaction condition gentleness, accessory substance is few, and 1,2-propane diols selectivity is higher.Two-step method is most possible at present realize glycerine hydrogenolysis system 1, the production route of 2-propane diols reaction industryization.The research of two-step method at present mainly concentrates on the first step, and for the second step hydroxypropanone-hydrogenation preparing 1, the research report of 2-propane diols is rarely found.
Summary of the invention
The object of the present invention is to provide a kind of hydroxypropanone-hydrogenation preparing 1 that is used for, the catalyst of 2-propane diols, its preparation method and application.
The objective of the invention is to realize in the following way:
Described catalyst is the composite oxides of copper and chromium or the composite oxides of cobalt and chromium, and wherein the atomic ratio of Cu/Cr and Co/Cr is respectively 1: 5-5: 1, wherein be preferably 1: 2-2: 1.
More specifically, the composite oxides of described copper and chromium are preferably CuCr 20 4, the composite oxides of described cobalt and chromium are preferably CoCr 20 4
The present invention also provides a kind of aforementioned Preparation of catalysts method, by Prepared by Sol Gel Method, detailed process is as follows: the mantoquita of solubility or the cobalt salt chromic salts with solubility is dissolved in the deionized water, places 60 ℃ of-70 ℃ of water-baths, magnetic agitation obtains solution A; 1-2 doubly is dissolved in the deionized water to the peptizing agent of metal ion integral molar quantity, obtains solution B; Then solution B is poured in the solution A, keep 60 ℃ of-90 ℃ of water-baths and magnetic agitation, until thick gel occurring, this gel is placed 100 ℃ of-120 ℃ of dry 2h-3h of thermostatic drying chamber, be transferred to then under 400 ℃ of-600 ℃ of conditions of Muffle furnace and calcine 2h-3h, obtain described catalyst, the atomic ratio that the rate of charge of described mantoquita and chromic salts or cobalt salt and chromic salts satisfies Cu/Cr and Co/Cr is respectively 1: 5-5: 1.
The mantoquita of wherein said solubility is selected from one or more in copper nitrate, Schweinfurt green, copper sulphate and the copper chloride.。
Wherein said solubility cobalt salt is selected from one or more in cobalt nitrate, cobalt acetate and the cobalt chloride.
Wherein said solubility chromic salts is selected from one or more in chromic nitrate, chromic acetate and the ammonium dichromate.
Described peptizing agent is citric acid, triethanolamine, Cetrimide etc.
The atomic ratio that the rate of charge of described mantoquita and chromic salts or cobalt salt and chromic salts satisfies Cu/Cr and Co/Cr is respectively 1: 2-2: 1.
Described catalyst need carry out the original position prereduction under the atmosphere of hydrogen before use, and reducing condition is: 200 ℃-300 ℃ of temperature, Hydrogen Vapor Pressure 1MPa-3MPa, and recovery time 3h-5h.
The described catalyst of the application can be used for catalysis hydroxypropanone-hydrogenation preparing 1, the reaction of 2-propane diols, wherein reaction condition is: with pure hydroxypropanone-is raw material, 160 ℃-240 ℃ of temperature, Hydrogen Vapor Pressure 1MPa-3MPa, reaction time 5-10h, catalyst amount are 0.2g/10mL raw material-1g/10mL raw material.Preferred reaction conditions is: 180 ℃-200 ℃ of temperature, Hydrogen Vapor Pressure 2.5MPa-3MPa, reaction time 8h, catalyst amount are 0.5g/10mL raw material-0.8g/10mL raw material.
Use catalyst of the present invention under relatively mild condition, to generate 1 by catalysis hydroxypropanone-hydrogenation, the 2-propane diols has improved the conversion ratio and 1 of hydroxypropanone-, the selection rate of 2-propane diols greatly, and reduced reaction pressure and temperature, reduced production cost.
The specific embodiment
Following examples are intended to illustrate the present invention rather than limitation of the invention further.The present invention can implement by the described mode of summary of the invention.
Embodiment 1
The 0.005mol copper nitrate is dissolved in the 50mL deionized water with 0.010mol chromic nitrate (the Cu/Cr atomic ratio is 1: 2), place 60 ℃ of water-baths, magnetic agitation, the 0.03mol citric acid is dissolved in the 50mL deionized water, the citric acid solution that obtains is poured in the front metal solion, keep 80 ℃ of water-baths and magnetic agitation, until thick gel occurring, this gel is placed 120 ℃ of dry 2h of thermostatic drying chamber, be transferred to then under 600 ℃ of conditions of Muffle furnace and calcine 2h, get CuCr 2O 4Catalyst.
Accurately take by weighing the above-mentioned catalyst of 0.8g, place autoclave, airtight back goes out air in the still with hydrogen exchange, charges into the hydrogen of 3Mpa, is heated to 300 ℃, keeps 5h, carries out the original position prereduction of catalyst.Afterwards, discharge hydrogen, add the 10mL hydroxypropanone-in autoclave, airtight back goes out air in the still with hydrogen exchange, charges into the hydrogen of 2Mpa, is heated to 200 ℃, starts stirring simultaneously, reaction 8h.After reaction finished, the question response still was cooled to room temperature, and centrifugation product and catalyst with the product gas chromatographic analysis, calculate the conversion ratio and 1 of hydroxypropanone-, and the selection rate of 2-propane diols is respectively 98% and 96.5%.
Embodiment 2
Preparation of Catalyst is with embodiment 1, and difference is that the Cu/Cr atomic ratio is 1: 5.
Prereduction and hydrogenation conditions and operating process are with embodiment 1.
Reaction result: the conversion ratio of hydroxypropanone-and 1, the selection rate of 2-propane diols is respectively 75% and 78.2%.
Embodiment 3
Preparation of Catalyst is with embodiment 1, and difference is that the Cu/Cr atomic ratio is 1: 1.
Prereduction and hydrogenation conditions and operating process are with embodiment 1.
Reaction result: the conversion ratio of hydroxypropanone-and 1, the selection rate of 2-propane diols is respectively 94% and 92.4%.
Embodiment 4
Preparation of Catalyst is with embodiment 1, and difference is that the Cu/Cr atomic ratio is 5: 1.
Prereduction and hydrogenation conditions and operating process are with embodiment 1.
Reaction result: the conversion ratio of hydroxypropanone-and 1, the selection rate of 2-propane diols is respectively 93% and 90.3%.
Embodiment 5
Preparation of Catalyst is with embodiment 1, and difference is that the metal active constituent raw material is a cobalt nitrate.
Prereduction and hydrogenation conditions and operating process are with embodiment 1.
Reaction result: the conversion ratio of hydroxypropanone-and 1, the selection rate of 2-propane diols is respectively 97% and 95.8%.
Embodiment 6
Preparation of Catalyst is with embodiment 5, and difference is that the Co/Cr atomic ratio is 1: 5.
Prereduction and hydrogenation conditions and operating process are with embodiment 1.
Reaction result: the conversion ratio of hydroxypropanone-and 1, the selection rate of 2-propane diols is respectively 73% and 75.8%.
Embodiment 7
Preparation of Catalyst is with embodiment 5, and difference is that the Co/Cr atomic ratio is 1: 1.
Prereduction and hydrogenation conditions and operating process are with embodiment 1.
Reaction result: the conversion ratio of hydroxypropanone-and 1, the selection rate of 2-propane diols is respectively 92% and 93.2%.
Embodiment 8
Preparation of Catalyst is with embodiment 5, and difference is that the Co/Cr atomic ratio is 5: 1.
Prereduction and hydrogenation conditions and operating process are with embodiment 1.
Reaction result: the conversion ratio of hydroxypropanone-and 1, the selection rate of 2-propane diols is respectively 91% and 88.6%.
Embodiment 9
Catalyst is with embodiment 1.
Prereduction and hydrogenation conditions and operating process are with embodiment 1, and difference is that reaction temperature is 160 ℃.
Reaction result: the conversion ratio of hydroxypropanone-and 1, the selection rate of 2-propane diols is respectively 90% and 94.1%.
Embodiment 10
Catalyst is with embodiment 1.
Prereduction and hydrogenation conditions and operating process are with embodiment 1, and difference is that reaction temperature is 240 ℃.
Reaction result: the conversion ratio of hydroxypropanone-and 1, the selection rate of 2-propane diols is respectively 100% and 75.6%.
Embodiment 11
Catalyst is with embodiment 1.
Prereduction and hydrogenation conditions and operating process are with embodiment 1, and difference is that Hydrogen Vapor Pressure is 1MP.
Reaction result: the conversion ratio of hydroxypropanone-and 1, the selection rate of 2-propane diols is respectively 92% and 89.5%.
Embodiment 12
Catalyst is with embodiment 1.
Prereduction and hydrogenation conditions and operating process are with embodiment 1, and difference is that Hydrogen Vapor Pressure is 2.5Mp.
Reaction result: the conversion ratio of hydroxypropanone-and 1, the selection rate of 2-propane diols is respectively 98% and 96.2%.

Claims (14)

1. one kind is used for hydroxypropanone-hydrogenation preparing 1, and the catalyst of 2-propane diols, described catalyst are the composite oxides of copper and chromium or the composite oxides of cobalt and chromium, and wherein the atomic ratio of Cu/Cr and Co/Cr is respectively 1: 5-5: 1.
2. catalyst according to claim 1 is characterized in that: the atomic ratio of described Cu/Cr and Co/Cr is respectively 1: 2-2: 1.
3. catalyst according to claim 2 is characterized in that: the composite oxides of described copper and chromium are CuCr 2O 4, the composite oxides of described cobalt and chromium are CoCr 2O 4
4. according to each described catalyst of claim 1-3, it is characterized in that: described catalyst need carry out the original position prereduction under the atmosphere of hydrogen before use, reducing condition is: 200 ℃-300 ℃ of temperature, Hydrogen Vapor Pressure 1MPa-3MPa, and recovery time 3h-5h.
5. each described Preparation of catalysts method of claim 1-3, by Prepared by Sol Gel Method, detailed process is as follows: the mantoquita of solubility or the cobalt salt chromic salts with solubility is dissolved in the deionized water, places 60 ℃ of-70 ℃ of water-baths, magnetic agitation obtains solution A; 1-2 doubly is dissolved in the deionized water to the peptizing agent of metal ion integral molar quantity, obtains solution B; Then solution B is poured in the solution A, keep 60 ℃ of-90 ℃ of water-baths and magnetic agitation, until thick gel occurring, this gel is placed 100 ℃ of-120 ℃ of dry 2h-3h of thermostatic drying chamber, be transferred to then under 400 ℃ of-600 ℃ of conditions of Muffle furnace and calcine 2h-3h, obtain described catalyst, the atomic ratio that the rate of charge of described mantoquita and chromic salts or cobalt salt and chromic salts satisfies Cu/Cr and Co/Cr is respectively 1: 5-5: 1.
6. preparation method according to claim 5 is characterized in that: described soluble copper salt is selected from one or more in copper nitrate, Schweinfurt green, copper sulphate and the copper chloride.
7. preparation method according to claim 5 is characterized in that: described solubility cobalt salt is selected from one or more in cobalt nitrate, cobalt acetate and the cobalt chloride.
8. preparation method according to claim 5 is characterized in that: described solubility chromic salts is selected from one or more in chromic nitrate, chromic acetate and the ammonium dichromate.
9. preparation method according to claim 5 is characterized in that: described peptizing agent is citric acid, triethanolamine or Cetrimide.
10. preparation method according to claim 5 is characterized in that: the atomic ratio that the rate of charge of described mantoquita and chromic salts or cobalt salt and chromic salts satisfies Cu/Cr and Co/Cr is respectively 1: 2-2: 1.
11. according to each described preparation method of claim 5-10, it is characterized in that: prepared catalyst need carry out the original position prereduction under the atmosphere of hydrogen before use, reducing condition is: 200 ℃-300 ℃ of temperature, Hydrogen Vapor Pressure 1MPa-3MPa, and recovery time 3h-5h.
12., be used for catalysis hydroxypropanone-hydrogenation preparing 1, the reaction of 2-propane diols according to each described Application of Catalyst of claim 1-3.
13. application according to claim 12, it is characterized in that: the described catalysis hydroxypropanone-hydrogenation preparing 1 that is used for, the reaction condition of the reaction of 2-propane diols is: with pure hydroxypropanone-is raw material, 160 ℃-240 ℃ of temperature, Hydrogen Vapor Pressure 1MPa-3MPa, reaction time 5-10h, catalyst amount are 0.2g/10mL raw material-1g/10mL raw material.
14. application according to claim 13 is characterized in that: reaction condition is: 180 ℃-200 ℃ of temperature, Hydrogen Vapor Pressure 2.5MPa-3MPa, reaction time 8h, catalyst amount are 0.5g/10mL raw material-0.8g/10mL raw material.
CN 201010551038 2010-11-19 2010-11-19 Catalyst for preparing 1,2-propylene glycol from hydroxyacetone hydrogenation as well as preparation method and application thereof Pending CN102000586A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105709760A (en) * 2014-12-04 2016-06-29 中国石油化工股份有限公司 Copper-chromium catalyst and its preparation method and use

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101311152A (en) * 2007-05-24 2008-11-26 中国科学院大连化学物理研究所 Process and device for directly synthesizing high carbon primary alcohol form CO hydrogenation
CN101371986A (en) * 2008-05-15 2009-02-25 大连理工大学 Method for preparing Cu-Cr metallic oxide with high specific surface area and application

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101311152A (en) * 2007-05-24 2008-11-26 中国科学院大连化学物理研究所 Process and device for directly synthesizing high carbon primary alcohol form CO hydrogenation
CN101371986A (en) * 2008-05-15 2009-02-25 大连理工大学 Method for preparing Cu-Cr metallic oxide with high specific surface area and application

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
《Environ.Sci.Technol.》 20001128 DAE-CHUL KIM et al. Application of Spinel-Type Cobalt Chromite as a Novel Catalyst for Combustion of Chlorinated Organic Pollutants 第222-226页 1-3 第35卷, 第1期 2 *
《Journal of Solid State Chemistry》 20001231 G. L. Castiglioni et al. Synthesis and Properties of Spinel-Type Co+Cu+Mg+Zn+Cr Mixed Oxides 第526－532页 1-14 第152卷, 2 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105709760A (en) * 2014-12-04 2016-06-29 中国石油化工股份有限公司 Copper-chromium catalyst and its preparation method and use
CN105709760B (en) * 2014-12-04 2018-10-12 中国石油化工股份有限公司 A kind of Cu-Cr catalyst and its preparation method and application

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Application publication date: 20110406