CN102225883B - Cu/TiO2 catalyst, preparation method thereof, and method for catalyzing glycerin hydrogenolysis with Cu/TiO2 catalyst - Google Patents
Cu/TiO2 catalyst, preparation method thereof, and method for catalyzing glycerin hydrogenolysis with Cu/TiO2 catalyst Download PDFInfo
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- CN102225883B CN102225883B CN 201110056529 CN201110056529A CN102225883B CN 102225883 B CN102225883 B CN 102225883B CN 201110056529 CN201110056529 CN 201110056529 CN 201110056529 A CN201110056529 A CN 201110056529A CN 102225883 B CN102225883 B CN 102225883B
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Abstract
The invention which belongs to the field of organic catalysis relates to a Cu/TiO2 catalyst, a preparation method thereof, and a method for catalyzing glycerin hydrogenolysis with the Cu/TiO2 catalyst. The invention discloses the method for preparing propylene glycol through glycerin hydrogenolysis with the Cu/TiO2 catalyst which can be used to selectively prepare products of propylene glycol, hydroxy acetone, glycol and the like by catalyzing a glycerin vapor phase hydrogenolysis under conditions of a normal pressure and a temperature of 180 to 300 DEG C. A mass ratio of Cu to TiO2 in the catalyst is 5-20:100, the Cu/TiO2 catalyst is prepared through an isopyknic immersion method, and raw materials comprise Cu(NO3)2.3H2O and TiO2. The copper loaded catalyst prepared in the invention has no heavy metal chromium which pollutes environment, and has good catalytic activity and stability in reaction processes. The reaction is carried out under normal pressure, so the reaction provided in the invention is better than glycerin catalytic hydrogenolysis reactions which perform a high conversion rate only under the condition of high reaction pressure.
Description
Technical field
The invention belongs to the organic catalysis field, relate to Cu/TiO
2(used TiO
2Be rutile titanium dioxide) method of catalyzer, preparation method and hydrogenolysis catalysis of glycerin thereof, refer in particular to different mass than the Cu/TiO that forms
2The continuous hydrogenolysis of the gas phase of catalyst glycerine, 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 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 the important intermediate of synthetic 1,2-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 and prepared 1,2-propylene glycol technology, and this technology has 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 1,2-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
In order to overcome above-mentioned deficiency of the prior art, prepared Cu/TiO
2Catalyzer, i.e. Cu/TiO
2(be that mass ratio is 5:100,10:100 20:100), is used for the reaction of catalyzing glycerol phase hydrogenolysis, and 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/TiO
2Catalyst glycerine hydrogenolysis generates the method for propylene glycol, it is characterized in that using Cu/TiO
2Catalyzer catalyzing glycerol phase hydrogenolysis between 180 ℃ ~ 300 ℃ under normal pressure, 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/TiO
2Catalyzer is characterized in that its mass ratio is 5-20:100.
Wherein said TiO
2Be rutile titanium dioxide.
Wherein said Cu/TiO
2Catalyzer, its preparation method is:
Cu/TiO
2Catalyzer prepares by equi-volume impregnating, and raw material is Cu (NO
3)
23 H
2O and TiO
2, at first measure carrier TiO
2The dipping volume, than composition requirement, the raw material that takes by weighing respective amount mixes according to the quality of catalyzer, incipient impregnation needs in the process to stir and makes copper nitrate solution and carrier TiO
2Full and uniform dipping; Sample is dry 12 h under 120 ℃, and 450 ℃ of roasting 2 h make Cu/TiO
2Catalyst Precursors; Cu/TiO
2Catalyst Precursors sieves into 20-40 order particle at 14 MPa lower sheetings.
Wherein said Cu/TiO
2Catalyzer 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.Used TiO in the specific embodiment of the invention
2Be rutile titanium dioxide.
Embodiment 1
Preparation of Catalyst:
Cu/TiO
2(5:100) catalyzer prepares by equi-volume impregnating: at first measure carrier TiO
2The dipping volume.According to the composition requirement of catalyzer, the raw material that takes by weighing respective amount is respectively Cu (NO
3)
23H
2O and TiO
2, incipient impregnation need to stir in the process and makes copper nitrate solution and TiO
2Full and uniform dipping.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 with the speed of 5 mL/h under the normal pressure, after 350 ℃ of vaporizations, enter reactor.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, Cu/TiO during the differential responses temperature
2
Glycerine gas phase catalysis hydrogenolysis (5g:100g)
The transformation efficiency of reaction product selectivity and raw material glycerine
Embodiment 2
With embodiment 1, but change Cu/TiO in the catalyzer
2Ratio be respectively 10:100,20:100, the gained result sees Table 2 respectively, table 3.
Under table 2 normal pressure, Cu/TiO during the differential responses temperature
2
Glycerine gas phase catalysis hydrogenolysis (10g:100g)
The transformation efficiency of reaction product selectivity and raw material glycerine
Under table 3 normal pressure, Cu/TiO during the differential responses temperature
2
Glycerine gas phase catalysis hydrogenolysis (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/TiO that form
2Catalyst series is effective catalyzing glycerol phase hydrogenolysis all, at normal pressure, under the gas-phase reaction condition, along with temperature is elevated to approximately 100% from about 83% from 180 ℃ of transformation efficiencys that are elevated to 300 ℃ of glycerine, illustrates at Cu/TiO
2Under the catalyst series catalysis, the transformation efficiency of glycerine raises with temperature.Under different temperature of reaction, the products distribution difference of glycerin catalytic hydrogenolysis gained.With respect to Cu/Al
2O
3Catalyst series, Cu/TiO
2Catalyst 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.
With Cu/Al
2O
3Catalyst series is the same, contrast table 1 and table 2, and table 3 is at each temperature of reaction, Cu/TiO
2Catalyst series is along with TiO
2The increase of content has improved the selectivity of pyruvic alcohol.
Contrast table 3 and table 2, table 1 is at each temperature of reaction, Cu/TiO
2Catalyst series has improved the selectivity of 1,2-propylene glycol along with the increase of Cu content.
Claims (1)
1.Cu/TiO
2Catalyst glycerine hydrogenolysis generates the method for propylene glycol, it is characterized in that using Cu/TiO
2Catalyzer catalyzing glycerol phase hydrogenolysis between 180 ℃ ~ 300 ℃ under normal pressure, selectivity prepares propylene glycol, pyruvic alcohol and ethylene glycol;
Wherein said glycerine phase hydrogenolysis reaction adopts atmospheric fixed bed reactor to carry out;
Wherein said Cu/TiO
2The mass ratio of catalyzer is 5-20:100;
Wherein said TiO
2Be rutile titanium dioxide;
Wherein said Cu/TiO
2The Preparation of catalysts method is: Cu/TiO
2Catalyzer prepares by equi-volume impregnating, and raw material is Cu (NO
3)
23 H
2O and TiO
2, at first measure carrier TiO
2The dipping volume, than composition requirement, the raw material that takes by weighing respective amount mixes according to the quality of catalyzer, incipient impregnation needs in the process to stir and makes copper nitrate solution and carrier TiO
2Full and uniform dipping; Sample is dry 12 h under 120 ℃, and 450 ℃ of roasting 2 h make Cu/TiO
2Catalyst Precursors; Cu/TiO
2Catalyst Precursors sieves into 20-40 order particle at 14 MPa lower sheetings;
Wherein said Cu/TiO
2Catalyzer before use must activated pre-treatment, and its method is: with 1.5 ℃/min temperature programming to 240 ℃, be 1:9H with volume ratio simultaneously from room temperature
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 purging 3 h at 285 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110056529 CN102225883B (en) | 2011-03-10 | 2011-03-10 | Cu/TiO2 catalyst, preparation method thereof, and method for catalyzing glycerin hydrogenolysis with Cu/TiO2 catalyst |
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|---|---|---|---|
| CN 201110056529 CN102225883B (en) | 2011-03-10 | 2011-03-10 | Cu/TiO2 catalyst, preparation method thereof, and method for catalyzing glycerin hydrogenolysis with Cu/TiO2 catalyst |
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| CN102225883A CN102225883A (en) | 2011-10-26 |
| CN102225883B true CN102225883B (en) | 2013-08-21 |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102924233B (en) * | 2012-10-20 | 2015-04-15 | 青岛科技大学 | Method for preparing propylene glycol by glycerin hydrogenolysis |
| WO2014081951A1 (en) | 2012-11-21 | 2014-05-30 | University Of Tennesee Research Foundation | Methods, systems and devices for simultaneous production of lactic acid and propylene glycol from glycerol |
| CN111701591A (en) * | 2020-06-16 | 2020-09-25 | 北京石油化工学院 | Hydrogenation catalyst, preparation method thereof and method for preparing fatty alcohol by hydrogenation of fatty acid ester |
| CN114054021B (en) * | 2020-07-31 | 2023-05-12 | 中国科学院大连化学物理研究所 | Application of Cu catalyst in alkane dehydrogenation reaction |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0523015A2 (en) * | 1991-07-10 | 1993-01-13 | NOVAMONT S.p.A. | A method of hydrogenating glycerol |
| CN101054339A (en) * | 2007-05-31 | 2007-10-17 | 上海华谊丙烯酸有限公司 | Process for preparing n-propanol by hydrogenating glycerol |
| CN101704718A (en) * | 2009-11-05 | 2010-05-12 | 南开大学 | Catalyst for liquid-phase hydrogenation of natural glycerin for preparing 1,2-propanediol and preparation method thereof |
| CN101898946A (en) * | 2010-06-29 | 2010-12-01 | 江苏大学 | Method for hydrogenolysis catalysis of glycerin |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7663004B2 (en) * | 2002-04-22 | 2010-02-16 | The Curators Of The University Of Missouri | Method of producing lower alcohols from glycerol |
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2011
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0523015A2 (en) * | 1991-07-10 | 1993-01-13 | NOVAMONT S.p.A. | A method of hydrogenating glycerol |
| CN101054339A (en) * | 2007-05-31 | 2007-10-17 | 上海华谊丙烯酸有限公司 | Process for preparing n-propanol by hydrogenating glycerol |
| CN101704718A (en) * | 2009-11-05 | 2010-05-12 | 南开大学 | Catalyst for liquid-phase hydrogenation of natural glycerin for preparing 1,2-propanediol and preparation method thereof |
| CN101898946A (en) * | 2010-06-29 | 2010-12-01 | 江苏大学 | Method for hydrogenolysis catalysis of glycerin |
Non-Patent Citations (3)
| Title |
|---|
| Junhua Wang.Biodiesel derived glycerol hydrogenolysis to 1,2-propanediol on Cu/MgO catalysts.《Bioresource Technology》.2010,第101卷(第18期),7088-7092. * |
| JunhuaWang.Biodieselderivedglycerolhydrogenolysisto1 2-propanediol on Cu/MgO catalysts.《Bioresource Technology》.2010 |
| zhenle Yuan * |
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