CN101869838B - Nano catalyst for synthesizing glycol by hydrogenation of diester oxalate - Google Patents
Nano catalyst for synthesizing glycol by hydrogenation of diester oxalate Download PDFInfo
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- CN101869838B CN101869838B CN200910111560.3A CN200910111560A CN101869838B CN 101869838 B CN101869838 B CN 101869838B CN 200910111560 A CN200910111560 A CN 200910111560A CN 101869838 B CN101869838 B CN 101869838B
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- hydrogenation
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- oxalate
- diester
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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Abstract
The invention relates to a nano catalyst for synthesizing glycol by the hydrogenation of diester oxalate. Chromic anhydride and copper nitrate are used as raw materials, a reaction is quickly and dispersedly carried out at the presence of ammonium salt in a solution by the modes of high-speed rotary stirring and trace low-speed dripping to form a precipitate of nano particles, and then the nano catalyst is prepared by filtering, drying and baking. The catalyst is used for synthesizing the glycol by the gas-phase catalytic hydrogenation of the diester oxalate, adopts a fixed bed reaction device and has high reaction performance.
Description
Technical field
The present invention relates to a kind of hydrogenation nanocatalyst in oxalate diester hydrogenation synthesizing of ethylene glycol reaction and preparation method thereof that is applied to.
Background technology
Ethylene glycol is very important chemical products and raw material.Synthetic by oxalate diester hydrogenation is a kind of important channel that produces ethylene glycol.Oxalate diester hydrogenation synthesizing of ethylene glycol catalyst used had many patents and bibliographical information both at home and abroad.As: at JP55-42971; US4112245; Organic Reactions, in VII volume, the 1st chapter, adopts CU-Cr or in CU-Cr, adds the cocatalyst such as Zn, Pa as hydrogenation catalyst, obtains good ethylene glycol yield, but exists catalyst activity sharply to descend degradation defect; JP57-123127 report is used Cu-Cr-Mn catalyst, and the conversion ratio of dimethyl oxalate is greater than 97%, selective 94% of ethylene glycol.JP57-122938 has reported that under slightly high liquid air speed, the optionally effect of the conversion ratio of oxalate diester and ethylene glycol is just undesirable with the catalyst that does not contain Cr.
Summary of the invention
The object of the invention is to improve the preparation method of catalyst, prepare nanoscale hydrogenation catalyst, by the nano effect of catalyst, under high liquid air speed condition, selective, conversion ratio and life-span are all improved.
It is that main material dissolves mixing that hydrogenation catalyst has been selected chromic anhydride and copper nitrate, under a certain amount of ammonium salt exists, ammonium salt can be that the solution such as nitrate, carbonate, sulfate or ammonium hydroxide stir by High Rotation Speed and trace dropping mode at a slow speed makes the sediment that reaction is quick, disperse to carry out forming nanoparticle, sediment passes through filtration, oven dry, calcination and compressing tablet again, is prepared into nanocatalyst.Catalyst nano figure is shown in accompanying drawing 1.It is synthetic that catalyst of the present invention is suitable for the hydrogenation of oxalate diester, and the hydrogenation that is particularly suitable for the oxalate diester of 1-4 carbon etc. synthesizes.
Reaction tube is stainless steel fixed bed reaction pipe, catalyst loading amount 5-15ml, and a gas circuit Yi Ye road two-way charging, gas circuit is directly introduced reactor feed gas by high-pressure cylinder interface; Liquid road oxalate raw material, owing to being solid or liquid under normal temperature, is reaction raw materials so adopt its methanol solution or liquid, and gasification pressurization is through the accurate charging of high-pressure metering pump.Two gas circuits are accurately controlled flow by mass flowmenter respectively.The six-way valve that reaction tube outlet is insulation clack box, the online product composition of gas chromatographic analysis reaction tube outlet.Catalyst activation condition: catalyst adopts H
2(50-100%)-N
2(50-0%) gaseous mixture is at 200-240 DEG C, gas space velocity 3000-4500h
-1, careful reduction activation in 15-18 hour under pressure 2.5-3.0MPa condition.Hydrogenation of oxalate for preparing ethylene glycol evaluating catalyst Reaction conditions range: LHSV is in liquid air speed: 0.2-0.5gml
-1(cat) h
-1; In unstripped gas, hydrogen content is 50%-100%, and nitrogen content is 50%-0.Gas space velocity SV is: 3000-6000hr
-1, reaction pressure is 1.0-3.0MPa, reaction temperature is: 200-240 DEG C.Product is analyzed by on-line chromatograph, adopts various components in PEG-20 type capillary column separated product gas, and product liquid is collected in drainer.Flow chart is shown in accompanying drawing 2.In the reaction of oxalate diester hydrogenation synthesizing of ethylene glycol, owing to producing nano effect, under slightly high liquid air speed, the optionally effect of the conversion ratio of oxalate diester and ethylene glycol is comparatively desirable.Catalyst life exceedes 1000 hours.
Catalyst regeneration: if reaction inactivation, the catalyst after inactivation can lead to oxygen burning after 2-4 hour at the scene, adopts H by reaction condition
2(50-100%)-N
2(50-0%) gaseous mixture is at 200-240 DEG C, gas space velocity 3000-4500h
-1, 15-18 hour activating and regenerating of careful reduction under pressure 2.5-3.0MPa condition.
Brief description of the drawings
Fig. 1 is hydrogenation catalyst sample TEM photo; Fig. 2 is that hydrogenation catalyst is evaluated schematic flow sheet.
Detailed description of the invention
Embodiment 1
Catalyst preparation, in reactor, adding water with 0.58 part of ammonium salt by 1 part of copper nitrate and 0.42 part of 8.3 parts of abundant dissolving that add water of chromic anhydride, 2.1 parts of high-speed stirred that turn at 1500-2500 per minute are carefully micro-fully mixes, be precipitated thing, filter, dewater by centrifugal dehydrator again, again by dryer in 130 DEG C of oven dry, then calcination 4 hours at 400 DEG C of temperature in high temperature furnace.Product is the following particle of 20 nanometer (seeing Fig. 1) through transmissioning electric mirror test analysis.Finally become particle for subsequent use product compressing tablet.
Embodiment 2
10 milliliters of catalyst prepared by example 1 are loaded in assessing reactor, 210 DEG C of temperature, and pure hydrogen air speed 3000h
-1, under liquid air speed 0.2g/mlhr and pressure 2.0Mpa condition, oxalate conversion ratio is 100%, glycol selectivity is 96.9%.
Embodiment 3
10 milliliters of catalyst prepared by example 1 are loaded in assessing reactor, at 220 DEG C of temperature, hydrogen gas space velocity 4500h
-1, under liquid air speed 0.5g/mlhr and pressure 2.0Mpa condition, oxalate conversion ratio is 100%, glycol selectivity is 96.5%.
Claims (4)
1. a nano catalyst for synthesizing glycol by hydrogenation of diester oxalate, it is characterized in that, with chromic anhydride and copper nitrate be raw material, under ammonium salt or ammonium hydroxide existence, in solution, stir with trace dropping mode at a slow speed and make the sediment that reaction is quick, disperse to carry out forming nanoparticle by High Rotation Speed, pass through again filtration, oven dry and calcination, be prepared into nanocatalyst; Wherein, ammonium salt is selected from the one in nitrate, carbonate, sulfate.
2. the catalyst as described in right 1 requirement, is characterized in that, this catalyst is suitable for reaction condition: in liquid air speed, LHSV is: 0.2-0.5hr
-1; In unstripped gas, hydrogen content is 50%-100%, and nitrogen content is 50%-0; Gas space velocity SV is: 3000-6000hr
-1, reaction pressure is: P=1.0-3.0MPa, and reaction temperature is: 200-240 DEG C; Catalyst life exceedes 1000 hours.
3. the catalyst as described in right 1 requirement, is characterized in that, after described catalysqt deactivation, can lead at the scene oxygen burning after 2-4 hour, activating and regenerating.
4. the catalyst applications as described in right 1 requirement: the hydrogenation that this catalyst is applicable to oxalate diester synthesizes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910111560.3A CN101869838B (en) | 2009-04-24 | 2009-04-24 | Nano catalyst for synthesizing glycol by hydrogenation of diester oxalate |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910111560.3A CN101869838B (en) | 2009-04-24 | 2009-04-24 | Nano catalyst for synthesizing glycol by hydrogenation of diester oxalate |
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| Publication Number | Publication Date |
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| CN101869838A CN101869838A (en) | 2010-10-27 |
| CN101869838B true CN101869838B (en) | 2014-10-29 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN200910111560.3A Active CN101869838B (en) | 2009-04-24 | 2009-04-24 | Nano catalyst for synthesizing glycol by hydrogenation of diester oxalate |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102659584A (en) * | 2012-05-21 | 2012-09-12 | 天津市碳一有机合成工程设计有限公司 | Chemical reaction system for producing oxalic acid diester as main products by using sodium formate as raw materials |
| CN102659556A (en) * | 2012-05-21 | 2012-09-12 | 天津市碳一有机合成工程设计有限公司 | Chemical reaction system for producing oxalic acid diester and oxalic acid as main products by using sodium formate as raw materials |
| CN107245026A (en) * | 2017-06-22 | 2017-10-13 | 江苏飞翔化工股份有限公司 | The solvent-free method that glycol is prepared by lactone |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5815930A (en) * | 1981-07-21 | 1983-01-29 | Mitsubishi Gas Chem Co Inc | Hydrogenating method of oxalic ester |
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2009
- 2009-04-24 CN CN200910111560.3A patent/CN101869838B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
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Effective date of registration: 20171229 Address after: 562300 Guizhou Province, Xingren Buyi and Miao Autonomous Prefecture Xingren County Economic Development Zone (Industrial Park) Patentee after: Guizhou Xin alcohol science and Technology Development Co., Ltd. Address before: Fuzhou City, Fujian province 350002 Yangqiao Road No. 155 Patentee before: Fujian Institute of Research on the Structure of Matter, Chinese Academy of Scie |
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Denomination of invention: Nano catalyst for synthesizing glycol by hydrogenation of diester oxalate Effective date of registration: 20200525 Granted publication date: 20141029 Pledgee: Guizhou Xinchun Energy Co., Ltd Pledgor: Guizhou Xin alcohol science and Technology Development Co., Ltd. Registration number: Y2020110000003 |