CN102153446A - Cu/MgO catalyst, preparation method thereof and method for catalyzing glycerin hydrogenolysis - Google Patents
Cu/MgO catalyst, preparation method thereof and method for catalyzing glycerin hydrogenolysis Download PDFInfo
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- CN102153446A CN102153446A CN2011100565304A CN201110056530A CN102153446A CN 102153446 A CN102153446 A CN 102153446A CN 2011100565304 A CN2011100565304 A CN 2011100565304A CN 201110056530 A CN201110056530 A CN 201110056530A CN 102153446 A CN102153446 A CN 102153446A
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Abstract
The invention belongs to the field of organic catalysis, relates to a Cu/MgO catalyst, a preparation method thereof and a method for catalyzing glycerin hydrogenolysis, and discloses a method for catalyzing glycerin hydrogenolysis by using the Cu/Mg catalyst. The method is characterized by comprising the following steps of: catalyzing glycerin gas-phase hydrogenolysis under normal pressure and at the temperature of between 180 DEG C and 300 DEG C by using the Cu/Mg catalyst; and selectively preparing products including propylene glycol, hydroxy-acetone, ethylene glycol and the like, wherein the mass ratio of the Cu/MgO catalyst is (5-20):100; and the Cu/MgO catalyst is prepared from Cu(NO3)2.3H2O and MgO by using an isopyknic immersion method. A copper-loadd catalyst prepared by using the preparation method does not contain heavy metal chromium which pollutes the environment, and has high catalytic activity and stability in the reacting process. A reaction is undergone under normal pressure, and is superior to other glycerin catalysis hydrogenolysis reactions which can only show high transformation ratios under high reaction pressures.
Description
Technical field
The invention belongs to the organic catalysis field, the method that relates to Cu/MgO catalyzer, preparation method and hydrogenolysis catalysis of glycerin thereof, refer in particular to the gas phase continuous hydrogenolysis of different mass than the Cu/MgO catalyst glycerine of forming, the selectivity preparation comprises the method for products such as propylene glycol, pyruvic alcohol, ethylene glycol.
Background technology
Because biofuel has huge environmental benefit and economic benefit, the biofuel industry is rapidly developed in recent years.But also brought the generation of a large amount of by products such as glycerine in the time of the development of biofuel industry.Rationally utilize these superfluous glycerine to help to increase whole biofuel Industrial economic benefit.At present, glycerine can be converted into the high chemical of added value by many-sided approach, as catalytic hydrogenolysis, and catalyzed oxidation, green approach such as catalytic dehydration.Wherein, utilizing the glycerin catalytic hydrogenolysis to generate propylene glycol receives much concern.The catalytic hydrogenolysis primary product of glycerine is a propylene glycol, pyruvic alcohol, and ethylene glycol, these all are important Elementary Chemical Industry raw materials.For example, propylene glycol be unsaturated polyester, Resins, epoxy, urethane resin important source material, the consumption of this respect accounts for about 45% of propylene glycol aggregate consumption, this unsaturated polyester is used for topcoating and reinforced plastics in a large number.The viscosity of propylene glycol and good hygroscopicity, and nontoxic, thereby in food, medicine and cosmetic industry, be widely used as moisture adsorbent, antifreezing agent, lubricant and solvent.Pyruvic alcohol is the raw material of preparation acrylic resin, also is to synthesize 1, the important intermediate of 2-propylene glycol.The raw material of traditional mode of production propylene glycol is the propylene oxide that derives from oil, and its price is bigger with the oil price fluctuation, and production cost is higher.So adopting with glycerine is raw material, under certain conditions, is the Chemicals that have more added value with transformation of glycerol, has become the focus of research.
From the more existing patent reports of glycerine synthesizing propanediol, as the nineties in 20th century, Germany Degussa company (application number 93114516.3) is raw material with glycerine, at 250 ℃ ~ 300 ℃ aqueous glycerin solutions that use 10% ~ 40% wt, the first step generates propenal and pyruvic alcohol by the strongly-acid solid catalysis with dehydrating glycerin, and second step is with propenal water and generation 3-hydroxy propanal in an acidic catalyst; The 3rd step generated 1, ammediol and 1,2-propylene glycol by 3-hydroxy propanal and pyruvic alcohol hydrogenation reaction.Reaction process is long, and productive rate is low.U.S. Missouri university has developed by biodiesel byproduct product glycerine preparation 1, and 2-propylene glycol technology, this technology have two steps: the first step, glycerine generate the intermediate pyruvic alcohol under normal pressure; In second step, pyruvic alcohol hydrogenation under the Cu-Cr catalyst effect generates 1, the 2-propylene glycol.But the existence of chromium element easily causes environmental pollution, is harmful to HUMAN HEALTH, does not meet the developing direction of green chemical industry.Chinese patent CN 1053176C provides a kind of dehydrating glycerin to prepare propenal, the method for the rehydrated hydrogenation preparing propylene glycol of propenal, and this procedure complexity, product yield is low.
Summary of the invention
The present invention has prepared the Cu/MgO catalyzer in order to overcome above-mentioned the deficiencies in the prior art, and promptly Cu/MgO(is mass ratio 5:100,10:100,20:100), be respectively applied for the reaction of catalyzing glycerol phase hydrogenolysis, the selectivity preparation comprises products such as pyruvic alcohol, ethylene glycol, propylene glycol.This method has the catalyst activity height, the glycerol conversion yield height, and good product selectivity, the reaction conditions gentleness, advantage such as environmental pollution is little for the glycerin catalytic hydrogenolysis provides a kind of new effective way, thereby effectively solves the problem that prior art exists.
Technical scheme of the present invention is as follows:
Cu/Mg catalyst glycerine hydrogenolysis generates the method for propylene glycol, it is characterized in that using Cu/Mg catalyzer catalyzing glycerol phase hydrogenolysis between 180 ℃ ~ 300 ℃ under normal pressure, and the selectivity preparation comprises products such as propylene glycol, pyruvic alcohol, ethylene glycol.
Glycerine phase hydrogenolysis reaction described in the technique scheme adopts atmospheric fixed bed reactor to carry out.
Wherein said Cu/MgO catalyzer is characterized in that its mass ratio is 5-20:100.
Wherein said Cu/MgO catalyzer, its preparation method is:
The Cu/MgO catalyzer prepares by equi-volume impregnating, and raw material is Cu (NO
3)
23 H
2O and MgO at first measure the dipping volume of carrier MgO, and than composition requirement, the raw material that takes by weighing respective amount mixes according to the quality of catalyzer, and incipient impregnation needs in the process to stir and makes copper nitrate solution and the full and uniform dipping of carrier MgO; Sample is dry 12 h under 120 ℃, and 450 ℃ of roasting 2 h make the Cu/MgO catalyst Precursors; The Cu/MgO catalyst Precursors at 14 MPa lower sheetings, is sieved into 20-40 order particle.
Wherein said Cu/MgO catalyst Precursors before use must activated pre-treatment, and its method is: with 1.5 ℃/min temperature programming to 240 ℃, use H from room temperature simultaneously
2-N
2Gas mixture (1:9/V:V) purges reduction.Subsequently, approximately with 1 ℃/.min temperature programming to 285 ℃, slowly improve gas mixture H simultaneously
2Content, final H
2-Volume fraction is stable to 30%, and stops about 3 h of purging at 285 ℃.This method can be reduced to zerovalent copper with the cupric in the catalyzer more completely.
The prepared copper loaded catalyst of the present invention does not contain the heavy metal chromium of contaminate environment, has good catalytic activity and stability in reaction process.Reaction is to carry out under normal pressure, is better than other just can show higher conversion under the reaction pressure conditions of higher glycerin catalytic hydrogenolysis.Reaction is that continuous one-step carries out, and processing requirement is simple, and product is easy to separate, and is applicable to industrial requirement.
Embodiment
The present invention will be further described below in conjunction with concrete embodiment.
Embodiment 1
Preparation of Catalyst:
Cu/MgO(5:100) catalyzer prepares by equi-volume impregnating: the dipping volume of at first measuring carrier MgO.According to the composition requirement of catalyzer, the raw material that takes by weighing respective amount is respectively Cu (NO
3)
23H
2O and MgO, incipient impregnation need to stir in the process and makes copper nitrate solution and the full and uniform dipping of MgO.Sample is dry 12 h under 120 ℃, and 450 ℃ of roasting 2 h make catalyst Precursors.Catalyst Precursors sieves into 20-40 order particle at 14 MPa lower sheetings.
The pre-activated of catalyzer is handled:
Catalyzer described in the technique scheme before use must activated pre-treatment, and its method is: with 1.5 ℃/min temperature programming to 240 ℃, use H from room temperature simultaneously
2-N
2Gas mixture (1:9/V:V) purges reduction.Subsequently, approximately with 1 ℃/.min temperature programming to 285 ℃, slowly improve gas mixture H simultaneously
2Content, final H
2-Volume fraction is stable to 30%, and stops about 3 h of purging at 285 ℃.This method can be reduced to zerovalent copper with the cupric in the catalyzer more completely.
The reaction of glycerine phase hydrogenolysis:
With 20 % aqueous glycerin solutions, be transported to the vaporizing chamber of said fixing bed bioreactor under the normal pressure, after 350 ℃ of vaporizations, enter reactor with the speed of 5 mL/h.Close N
2Air-flow keeps H
2Flow rate is 250 mL/min, keeps temperature of reactor and carry out glycerine gas phase catalysis hydrogenolysis under 180 ℃, and question response is collected product with product through the ice-water bath condensation after stablizing 30 min, serial sampling 1 h.Sample is analyzed with gas chromatograph (marker method).
Repeat above-mentioned steps, the temperature that only changes glycerine phase hydrogenolysis reactor is respectively 210 ℃, 240 ℃, 270 ℃, 300 ℃, carries out glycerine gas phase catalysis hydrogenolysis, and the transformation efficiency of products therefrom selectivity and glycerine sees Table 1.
Under table 1 normal pressure, the glycerine gas phase catalysis hydrogenolysis of Cu/MgO during the differential responses temperature (5g:100g)
The transformation efficiency of reaction product selectivity and raw material glycerine
Embodiment 2
With embodiment 1, but the ratio of Cu/MgO is respectively 10:100 in the change catalyzer, 20:100, and the gained result sees Table 2 respectively, table 3.
Under table 2 normal pressure, the glycerine gas phase catalysis hydrogenolysis of Cu/MgO during the differential responses temperature (10g:100g)
The transformation efficiency of reaction product selectivity and raw material glycerine
Under table 3 normal pressure, the glycerine gas phase catalysis hydrogenolysis of Cu/MgO during the differential responses temperature (20g:100g)
The transformation efficiency of reaction product selectivity and raw material glycerine
From table 1 to table 3 as can be seen, the different Cu/MgO catalyst series of forming are effective catalyzing glycerol phase hydrogenolysis all, at normal pressure, under the gas-phase reaction condition, along with temperature is elevated to about 84% from 180 ℃ of transformation efficiencys that are elevated to 300 ℃ of glycerine from about 36%, explanation is under the catalysis of Cu/MgO catalyst series, and the transformation efficiency of glycerine raises with temperature.Under different temperature of reaction, the products distribution difference of glycerin catalytic hydrogenolysis gained.The Cu/MgO catalyst series is to the transformation efficiency of glycerine and lower to the selectivity of monohydroxy-alcohol, and is higher to the selectivity of pyruvic alcohol, and all shows under each temperature of reaction its good selectivity.
Contrast table 1 and table 2, table 3, in each temperature of reaction, the Cu/MgO catalyst series has improved the selectivity of pyruvic alcohol along with the increase of MgO content.
Contrast table 3 and table 2, table 1, in each temperature of reaction, the Cu/MgO catalyst series has been along with the increase of Cu content has improved 1, the selectivity of 2-propylene glycol, and also low temperature helps its production.
MgO is a basic supports, and this explanation glycerin catalytic hydrogenolysis also can carry out under alkalescence.
Claims (5)
1.Cu/Mg the method for catalyst glycerine hydrogenolysis is characterized in that using Cu/Mg catalyzer catalyzing glycerol phase hydrogenolysis between 180 ℃ ~ 300 ℃ under normal pressure, selectivity prepares propylene glycol, pyruvic alcohol and ethylene glycol.
2. the method for Cu/Mg catalyst glycerine hydrogenolysis according to claim 1 is characterized in that the atmospheric fixed bed reactor of wherein said glycerine phase hydrogenolysis reaction employing carries out.
3. the method for Cu/Mg catalyst glycerine hydrogenolysis according to claim 1, the mass ratio that it is characterized in that wherein said Cu/MgO catalyzer is 5-20:100.
4. the method for Cu/Mg catalyst glycerine hydrogenolysis according to claim 1 is characterized in that wherein said Cu/MgO Preparation of catalysts method is: the Cu/MgO catalyzer prepares by equi-volume impregnating, and raw material is Cu (NO
3)
23 H
2O and MgO at first measure the dipping volume of carrier MgO, and than composition requirement, the raw material that takes by weighing respective amount mixes according to the quality of catalyzer, and incipient impregnation needs in the process to stir and makes copper nitrate solution and the full and uniform dipping of carrier MgO; Sample is dry 12 h under 120 ℃, and 450 ℃ of roasting 2 h make the Cu/MgO catalyst Precursors; The Cu/MgO catalyst Precursors at 14 MPa lower sheetings, is sieved into 20-40 order particle.
5. the method for Cu/Mg catalyst glycerine hydrogenolysis according to claim 4, it is characterized in that wherein said Cu/MgO catalyst Precursors before use must activated pre-treatment, its method is: with 1.5 ℃/min temperature programming to 240 ℃, is the H of 1:9 from room temperature simultaneously with volume ratio
2-N
2Gas mixture purges reduction, subsequently with 1 ℃/.min temperature programming to 285 ℃, slowly improves gas mixture H simultaneously
2Content, final H
2-Volume fraction is stable to 30%, and stops about 3 h of purging at 285 ℃.
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| CN2011100565304A CN102153446B (en) | 2011-03-10 | 2011-03-10 | Cu/MgO catalyst, preparation method thereof and method for catalyzing glycerin hydrogenolysis |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104722301A (en) * | 2015-03-04 | 2015-06-24 | 浙江工业大学之江学院 | Preparation method of catalyst for preparing dihydroxy acetone by selective oxidation of glycerinum and application method thereof |
| CN104888778A (en) * | 2015-04-27 | 2015-09-09 | 大连理工大学 | Glucose hydrogenolysis catalysis Cu/MgO catalyst and preparation method thereof |
| US9447011B2 (en) | 2012-11-21 | 2016-09-20 | University Of Tennessee Research Foundation | Methods, systems and devices for simultaneous production of lactic acid and propylene glycol from glycerol |
| CN109896940A (en) * | 2017-12-07 | 2019-06-18 | 中国科学院大连化学物理研究所 | A kind of Zinc oxide-base catalyst is used for hydroxypropanone- synthetic method |
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| CN101214440A (en) * | 2008-01-14 | 2008-07-09 | 南京工业大学 | Catalyst for preparing 1, 2-propylene glycol by hydrogenolysis of glycerol and preparation method thereof |
| CN101522600A (en) * | 2006-10-27 | 2009-09-02 | 科莱恩金融(Bvi)有限公司 | Process for preparing 1,2-propanediol by hydrogenolysis of glycerol |
| WO2009149830A1 (en) * | 2008-06-10 | 2009-12-17 | Clariant International Ltd | Method for producing 1,2-propanediol by hydrogenolysis of glycerin |
| CN101925564A (en) * | 2008-01-30 | 2010-12-22 | 花王株式会社 | Method for producing hydrogenolysis product of polyhydric alcohol |
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2011
- 2011-03-10 CN CN2011100565304A patent/CN102153446B/en not_active Expired - Fee Related
Patent Citations (4)
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| CN101522600A (en) * | 2006-10-27 | 2009-09-02 | 科莱恩金融(Bvi)有限公司 | Process for preparing 1,2-propanediol by hydrogenolysis of glycerol |
| CN101214440A (en) * | 2008-01-14 | 2008-07-09 | 南京工业大学 | Catalyst for preparing 1, 2-propylene glycol by hydrogenolysis of glycerol and preparation method thereof |
| CN101925564A (en) * | 2008-01-30 | 2010-12-22 | 花王株式会社 | Method for producing hydrogenolysis product of polyhydric alcohol |
| WO2009149830A1 (en) * | 2008-06-10 | 2009-12-17 | Clariant International Ltd | Method for producing 1,2-propanediol by hydrogenolysis of glycerin |
Non-Patent Citations (1)
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| ZHENLE YUAN ET AL.: "Biodiesel derived glycerol hydrogenolysis to 1,2-propanediol on Cu/MgO catalysts", 《BIORESOURCE TECHNOLOGY》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9447011B2 (en) | 2012-11-21 | 2016-09-20 | University Of Tennessee Research Foundation | Methods, systems and devices for simultaneous production of lactic acid and propylene glycol from glycerol |
| CN104722301A (en) * | 2015-03-04 | 2015-06-24 | 浙江工业大学之江学院 | Preparation method of catalyst for preparing dihydroxy acetone by selective oxidation of glycerinum and application method thereof |
| CN104888778A (en) * | 2015-04-27 | 2015-09-09 | 大连理工大学 | Glucose hydrogenolysis catalysis Cu/MgO catalyst and preparation method thereof |
| CN104888778B (en) * | 2015-04-27 | 2017-03-29 | 大连理工大学 | A kind of Cu/MgO catalyst of catalysis glucose hydrogenolysis and preparation method thereof |
| CN109896940A (en) * | 2017-12-07 | 2019-06-18 | 中国科学院大连化学物理研究所 | A kind of Zinc oxide-base catalyst is used for hydroxypropanone- synthetic method |
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