CN104557461A - Method for preparing 1,2-propylene glycol through adopting metal for hydrothermal reduction of carbohydrate - Google Patents

Method for preparing 1,2-propylene glycol through adopting metal for hydrothermal reduction of carbohydrate Download PDF

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Publication number
CN104557461A
CN104557461A CN201410854044.0A CN201410854044A CN104557461A CN 104557461 A CN104557461 A CN 104557461A CN 201410854044 A CN201410854044 A CN 201410854044A CN 104557461 A CN104557461 A CN 104557461A
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reaction
carbohydrate
metal
prepares
propylene glycol
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CN104557461B (en
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金放鸣
王杰
姚国栋
张华�
霍志保
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Shanghai Jiaotong University
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Shanghai Jiaotong University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring

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  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract

The invention relates to a method for preparing 1,2-propylene glycol through adopting metal for hydrothermal reduction of carbohydrate. The method includes the following steps: adding a catalyst, a reducing agent and carbohydrate in a reactor according to the molar ratio of (0.01-0.03): (1-9): 1; controlling the filling rate to be 25-60%, wherein the reaction temperature is 200-400 DEG C, the reaction pressure is the sum (2 MPa-30 MPa) of saturated vapor pressure corresponding to the reaction temperature and the hydrogen pressure generated by the reaction, and the reaction lasts for 15-90 min; converting the carbohydrate into 1,2-propylene glycol. The method provided by the invention has better selectivity, avoids consumption of plenty of fossil fuel and preparation of complicated catalyst in the traditional production technology as the carbohydrate, being a widespread renewable resource in nature is adopted; besides, in the technology, water is used as a hydrogen source and a reaction solvent, so that the operation is simple, little pollution is caused to the environment, and huge development potential is achieved.

Description

A kind of metal hydro-thermal reduced carbohydrate prepares the method for 1,2-PD
Technical field
The present invention relates to a kind of method preparing 1,2-PD, especially relate to a kind of method that metal hydro-thermal reduced carbohydrate prepares 1,2-PD.
Background technology
Along with day by day highlighting and CO of global energy problem 2excessive emissions, the reproducible biomass resource of Efficient Conversion is the extensive concern that new clean energy causes various countries scientist.And have important application as the 1,2-PD of carbohydrate reductive cleavage product at chemical field, be a kind of very important industrial chemicals.It not only as a kind of important monomer when synthesizing polyester or polyethers, but also can be used as frostproofer, softening agent and solvent.Meanwhile, food, medicine and makeup also there is good application.In addition, 1,2-PD also can as the good clean fuel of one, for substituting day by day exhausted and with serious pollution petroleum resources.
The production of current industrial 1,2-PD is mainly using the derivative of oil as raw material.The industrial selective oxidation mainly through propylene and hydrolysis and obtain.Propylene is then mainly derived from non-renewable petroleum resources.And energy consumption is high in process of production, pollute large.So seek wide material sources, renewable resources to replace fossil oil, and development environment close friend, the novel method of environmental protection and economy prepares 1,2-PD and then seems particularly important.And the class organic compound the widest with distribution at most that carbohydrate exists as occurring in nature, mainly comprise glucose, fructose, starch and Mierocrystalline cellulose etc.It is wide material sources not only, and are a kind of renewable resourcess, can endlessly synthesized by nature.So the method that exploitation is raw material Efficient Conversion with carbohydrate is 1,2-PD not only effectively can alleviate the heavy dependence to petroleum resources, simultaneously because its raw material is renewable, thus achieve the Sustainable development of production.And be that raw material can effectively reduce with oil with carbohydrate be raw material pollution on the environment, there is good application prospect.
Summary of the invention
A kind of new and effective metal hydro-thermal reduced carbohydrate is the object of the present invention is to provide to prepare the method for 1,2-PD.The method transformation efficiency is high, good product selectivity, without the need to using complicated catalyzer, simple to operate, use water as solvent and hydrogen source environmental pollution little, energy consumption is low, is conducive to suitability for industrialized production.Product 1,2-PD is a kind of important intermediate chemical and solvent, can be widely used in producing frostproofer, sanitising agent, Biodegradable polyester fiber, fluidizer, pharmacy etc.
The object of the invention is to be achieved through the following technical solutions:
The present invention relates to a kind of metal hydro-thermal reduced carbohydrate and prepare 1, the method of 2-propylene glycol, said method comprising the steps of: be (0.01 ~ 0.03) in molar ratio by catalyzer, reductive agent, carbohydrate: (1 ~ 9): 1 adds in reactor, controlling filling ratio is 25 ~ 60%, at 200 ~ 400 DEG C, reaction 15 ~ 90min under air-proof condition, can by carbohydrate-modifying be 1,2-PD; Described reaction pressure for saturated vapor pressure corresponding to temperature of reaction with react the hydrogen pressure sum produced.
Preferably, described carbohydrate is selected from glucose, fructose, Mierocrystalline cellulose and starch.In the present invention, carbohydrate source is extensive, and being mainly glucose, fructose, Mierocrystalline cellulose and starch etc., is a kind of renewable resources.
Preferably, described catalyzer is selected from the transition metal of metal oxide or carbon load.
Preferably, described catalyzer is selected from Ni 2o 3, CuO, Fe 3o 4, Fe 2o 3, Al 2o 3, Pt/C, Ru/C or Pd/C.
Preferably, described reductive agent is the metal simple-substance powder with reductibility.
Preferably, the metal simple-substance powder described in reductibility is selected from Mg, Al, Mn, Zn or Fe.
Preferably, described reaction pressure is 2MPa ~ 30MPa.
Preferably, described reaction also comprises steps such as reaction product filtrations.
The product of method gained of the present invention is mainly 1,2-PD, generates with a small amount of ethylene glycol and butyleneglycol simultaneously; The higher 1,2-PD aqueous solution of purity can be obtained by filtering.The filter membrane that described filtration is specially employing 0.45 μm filters.
Compared with prior art, the present invention has following beneficial effect:
(1) the present invention uses carbohydrate to make raw material system 1,2-propylene glycol, carbohydrate is as the most extensive and most important class organic compound of occurring in nature distribution (coming from corn that nature extensively exists, stalk, trees and potato etc.), wide material sources, renewable.So with carbohydrate be raw material without the need to consuming fossil energy, can the partial rcsponse nowadays energy problem that faces of the whole world;
(2) the present invention makes to use water as reaction solvent.Reductive agent is made with metal cheap and easy to get, palladium carbon, ruthenium carbon or metal oxide, as catalyzer, without the need to preparing complicated noble metal catalyst, become 1 by carbohydrate-modifying under hydrothermal conditions, this high added value organism of 2-propylene glycol, realizes the conversion organic resource of clean and effective low consumption.
(3) the present invention is without the need to additionally passing into high-purity hydrogen, significantly reduces the cost in energy consumption of reaction and hydrogen transport storage process, and environmental protection more, pollution on the environment is little;
(4) reaction product ZnO can be recovered as other purposes (as being reduced to simple substance Zn by sun power), also the discarded metal produced in process of metal working can be adopted in addition as reductive agent, therefore cost is cheaper, has valuable economic benefit;
(5) selectivity of product is high, and liquid product mainly consists of 1,2-PD, and by controlling reaction conditions, 1,2-PD productive rate can reach 33.3%, is easy to separating-purifying.
Accompanying drawing explanation
By reading the detailed description done non-limiting example with reference to the following drawings, other features, objects and advantages of the present invention will become more obvious:
Fig. 1 is the GC/MS spectrogram of product in embodiment 1;
Fig. 2 is the HPLC spectrogram of product in embodiment 1;
Fig. 3 is the GC/MS spectrogram of product in embodiment 2;
Fig. 4 is the HPLC spectrogram of product in embodiment 2;
Fig. 5 is the GC/MS spectrogram of product in embodiment 3;
Fig. 6 is the HPLC spectrogram of product in embodiment 3.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in detail.Following examples will contribute to those skilled in the art and understand the present invention further, but not limit the present invention in any form.It should be pointed out that to those skilled in the art, without departing from the inventive concept of the premise, some distortion and improvement can also be made.These all belong to protection scope of the present invention.
embodiment 1
The present embodiment relates to a kind of metal simple-substance (Zn powder) and Pd/C hydrothermal conversion glucose prepares 1, the method for 2 propylene glycol, and reaction equation is as follows:
Described method comprises the steps:
Glucose (1.11mmol), palladium carbon (0.03mmol) and zinc powder (6.9mmol) are loaded in SUS316 reaction tubes, filling ratio is made to reach 50%, reaction tubes is sealed, put into 300 DEG C of salt baths, the hydrogen pressure sum that pressure produces with reaction for corresponding saturated vapor pressure, reaction 30min, rear mixture filtration is taken out in reaction can obtain the 1,2-PD aqueous solution.
Carry out qualitative (see Fig. 1) and HPLC quantitative analysis (see Fig. 2) by after reaction to product GC/MS, GC/MS qualitative analysis shows, 1,2-PD is primary product, and productive rate is 31%.Industrial application adopts suitable hydrothermal reactor by demand, and can control temperature of reaction is 200 ~ 400 DEG C, reaction 15 ~ 90min.By this reaction, glucose can be converted into 1,2-PD in a large number, easy to operation and selectivity good.The ZnO that reaction produces can reclaim as other purposes.
embodiment 2
The present embodiment relates to a kind of metal simple-substance (Zn powder) and Pd/C hydrothermal conversion fructose prepares 1, the method for 2 propylene glycol, and reaction equation is as follows:
Described method comprises the steps:
Fructose (1.11mmol), Pd/C (0.01mmol) and Zn powder (2.0mmol) are loaded in SUS316 reaction tubes, filling ratio is made to reach 60%, reaction tubes is sealed, put into 300 DEG C of salt baths, pressure is for corresponding saturated vapor pressure and react the hydrogen pressure sum produced, reaction 90min, rear mixture filtration is taken out in reaction can obtain the 1,2-PD aqueous solution.
Carry out qualitative (see Fig. 3) and HPLC quantitative analysis (see Fig. 4) by after reaction to product GC/MS, GC/MS qualitative analysis shows, 1,2-PD is primary product, and productive rate is 30%.Industrial application adopts suitable hydrothermal reactor by demand, and can control temperature of reaction is 200 ~ 400 DEG C, reaction 15 ~ 90min.By this reaction, fructose can be converted into 1,2-PD in a large number, easy to operation and selectivity good.The ZnO that reaction produces can reclaim as other purposes.
embodiment 3
The present embodiment relates to a kind of metal simple-substance (Zn powder) and Ru/C hydrothermal conversion Mierocrystalline cellulose prepares 1, the method for 2 propylene glycol, and reaction equation is as follows:
Described method comprises the steps:
Mierocrystalline cellulose (1.11mmol), Ru/C (0.02mmol) and Zn powder (9.0mmol) are loaded in SUS316 reaction tubes, filling ratio is made to reach 30%, reaction tubes is sealed, put into 300 DEG C of salt baths, the hydrogen pressure sum that pressure produces with reaction for corresponding saturated vapor pressure, reaction 70min, rear mixture filtration is taken out in reaction can obtain the 1,2-PD aqueous solution.
Carry out qualitative (see Fig. 5) and HPLC quantitative analysis (see Fig. 6) by after reaction to product GC/MS, GC/MS qualitative analysis shows, 1,2-PD is primary product, and productive rate is 25%.Industrial application adopts suitable hydrothermal reactor by demand, and can control temperature of reaction is 200 ~ 400 DEG C, reaction 15 ~ 90min.By this reaction, Mierocrystalline cellulose can be converted into 1,2-PD in a large number, easy to operation and selectivity good.The ZnO that reaction produces can reclaim as other purposes.
Above specific embodiments of the invention are described.It is to be appreciated that the present invention is not limited to above-mentioned particular implementation, those skilled in the art can make various distortion or amendment within the scope of the claims, and this does not affect flesh and blood of the present invention.

Claims (7)

1. a metal hydro-thermal reduced carbohydrate prepares 1, the method of 2-propylene glycol, it is characterized in that, said method comprising the steps of: be (0.01 ~ 0.03) in molar ratio by catalyzer, reductive agent, carbohydrate: (1 ~ 9): 1 adds in reactor, controlling filling ratio is 25 ~ 60%, at 200 ~ 400 DEG C, reaction 15 ~ 90min under air-proof condition, can by carbohydrate-modifying be 1,2-PD; The pressure of described reaction for saturated vapor pressure corresponding to temperature of reaction with react the hydrogen pressure sum produced.
2. metal hydro-thermal reduced carbohydrate according to claim 1 prepares the method for 1,2-PD, it is characterized in that, described carbohydrate is selected from glucose, fructose, Mierocrystalline cellulose and starch.
3. metal hydro-thermal reduced carbohydrate according to claim 1 prepares the method for 1,2-PD, it is characterized in that, described catalyzer is selected from the transition metal of metal oxide or carbon load.
4. metal hydro-thermal reduced carbohydrate according to claim 3 prepares the method for 1,2-PD, it is characterized in that, described catalyzer is selected from Ni 2o 3, CuO, Fe 3o 4, Fe 2o 3, Al 2o 3, Pt/C, Ru/C or Pd/C.
5. metal hydro-thermal reduced carbohydrate according to claim 1 prepares the method for 1,2-PD, it is characterized in that, described reductive agent is the metal simple-substance powder with reductibility.
6. metal hydro-thermal reduced carbohydrate according to claim 5 prepares the method for 1,2-PD, it is characterized in that, described in there is reductibility metal simple-substance powder be selected from Mg, Al, Mn, Zn or Fe.
7. metal hydro-thermal reduced carbohydrate according to claim 1 prepares the method for 1,2-PD, it is characterized in that, described reaction pressure is 2MPa ~ 30MPa.
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Cited By (2)

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Publication number Priority date Publication date Assignee Title
CN104860794A (en) * 2015-05-26 2015-08-26 苏州鸿洋医药科技有限公司 Method for producing low-molecular-weight polyhydric alcohol through cracking of pentitol
CN106866362A (en) * 2015-12-12 2017-06-20 中国科学院大连化学物理研究所 Application of the ruthenium tin catalyst in saccharide compound catalyzed conversion prepares propane diols

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CN102675045A (en) * 2011-03-15 2012-09-19 中国科学院大连化学物理研究所 Method for preparing ethylene glycol and 1,2-propylene glycol by using saccharide solution
CN102452896B (en) * 2010-10-26 2013-12-25 同济大学 Method of preparing methanol through metal hydrothermal reduction of formic acid
WO2014070583A1 (en) * 2012-10-31 2014-05-08 Shell Oil Company Methods and systems for processing lignin during hydrothermal digestion of cellulosic biomass solids while producing a monohydric alcohol feed

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CN1683293A (en) * 2005-03-01 2005-10-19 大成多元醇投资有限公司 Process for producing diatomic alcohol and polyol from cracking sorbierite
CN102452896B (en) * 2010-10-26 2013-12-25 同济大学 Method of preparing methanol through metal hydrothermal reduction of formic acid
CN102675045A (en) * 2011-03-15 2012-09-19 中国科学院大连化学物理研究所 Method for preparing ethylene glycol and 1,2-propylene glycol by using saccharide solution
WO2014070583A1 (en) * 2012-10-31 2014-05-08 Shell Oil Company Methods and systems for processing lignin during hydrothermal digestion of cellulosic biomass solids while producing a monohydric alcohol feed

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104860794A (en) * 2015-05-26 2015-08-26 苏州鸿洋医药科技有限公司 Method for producing low-molecular-weight polyhydric alcohol through cracking of pentitol
CN104860794B (en) * 2015-05-26 2016-07-20 苏州鸿洋医药科技有限公司 The method that the cracking of a kind of pentitol produces low molecular weight polyols
CN106866362A (en) * 2015-12-12 2017-06-20 中国科学院大连化学物理研究所 Application of the ruthenium tin catalyst in saccharide compound catalyzed conversion prepares propane diols
CN106866362B (en) * 2015-12-12 2020-07-31 中国科学院大连化学物理研究所 Application of ruthenium-tin catalyst in preparation of propylene glycol through catalytic conversion of carbohydrate

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