CN104557461B - A kind of metal hydro-thermal to reduce carbohydrate is prepared the method for 1,2-PD - Google Patents

A kind of metal hydro-thermal to reduce carbohydrate is prepared the method for 1,2-PD Download PDF

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CN104557461B
CN104557461B CN201410854044.0A CN201410854044A CN104557461B CN 104557461 B CN104557461 B CN 104557461B CN 201410854044 A CN201410854044 A CN 201410854044A CN 104557461 B CN104557461 B CN 104557461B
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carbohydrate
thermal
metal
catalyst
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CN104557461A (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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    • 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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Abstract

The present invention relates to a kind of metal hydro-thermal to reduce carbohydrate and prepare the method for 1,2-PD; Be (0.01～0.03) in molar ratio by catalyst, reducing agent, carbohydrate: (1～9): 1 adds in reactor, controlling filling rate is 25～60%, reaction temperature is 200～400 DEG C, reaction pressure for saturated vapor pressure corresponding to reaction temperature with react produced Hydrogen Vapor Pressure sum (2MPa～30MPa), reaction 15～90min, carbohydrate can be converted into 1,2-PD. Method of the present invention has well selective, and carbohydrate used is the renewable resource that nature extensively exists, and has avoided the consumption of a large amount of fossil fuels in traditional processing technology, and the preparation of complicated catalyst. This technique makes water as hydrogen source and reaction dissolvent simultaneously, and simple to operate, environmental pollution is little, has huge development potentiality.

Description

A kind of metal hydro-thermal to reduce carbohydrate is prepared the method for 1,2-PD
Technical field
The present invention relates to a kind of method of preparing 1,2-PD, especially relate to a kind of metal hydro-thermal to reduce carbohydratePrepare the method for 1,2-PD.
Background technology
Along with day by day highlighting and CO of global energy problem2Excessive emissions, the reproducible biomass resource of Efficient Conversion is newClean energy resource caused various countries scientists' extensive concern. And as 1 of carbohydrate reductive cleavage product, 2-the third twoAlcohol has important application at chemical field, is a kind of very important industrial chemicals. It not only can be used as a kind of syntheticImportant monomer when polyester or polyethers, but also can be used as antifreezing agent, plasticizer and solvent. Meanwhile, at food, medicineWith on cosmetics, also have good application. In addition, 1,2-PD also can be used as a kind of well clean fuel, for replacingIn generation, is exhaustion and with serious pollution petroleum resources day by day.
The production of current industrial 1,2-PD is mainly using the derivative of oil as raw material. The industrial propylene that mainly passes throughSelective oxidation and hydrolysis and obtaining. Propylene is mainly derived from non-renewable petroleum resources. And in production processMiddle energy consumption is high, pollutes large. So seek wide material sources, renewable resource replaces fossil fuel, and development environment close friend, environmental protection and economic new method prepare 1,2-PD and seem particularly important. And carbohydrate is as natureThe widest with the distribution at most class organic compound existing in boundary, mainly comprises glucose, fructose, starch and cellulose etc.It is wide material sources not only, and are a kind of renewable resources, can be endlessly by nature synthesized. So exploitation withCarbohydrate is that raw material Efficient Conversion is that the method for 1,2-PD not only can effectively be alleviated serious to petroleum resourcesRely on, simultaneously because its raw material is renewable, thereby realized the sustainable development of producing. And taking carbohydrate as raw materialCan effectively reduce taking oil as raw material pollution on the environment, there is good application prospect.
Summary of the invention
The object of the present invention is to provide a kind of new and effective metal hydro-thermal to reduce carbohydrate to prepare 1,2-PDMethod. The method transformation efficiency is high, and good product selectivity is without using complicated catalyst, simple to operate, makes to use water asSolvent and hydrogen source environmental pollution are little, and energy consumption is low, is conducive to suitability for industrialized production. Product 1,2-PD is a kind of importantIntermediate chemical and solvent, can be widely used in producing antifreezing agent, cleaning agent, Biodegradable polyester fiber, plasticiser,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 to reduce carbohydrate and prepare the method for 1,2-PD, described method comprise withLower step: be (0.01～0.03) in molar ratio by catalyst, reducing agent, carbohydrate: (1～9): 1 addsIn reactor, controlling filling rate is 25～60%, under 200～400 DEG C, air-proof condition, reacts 15～90min, can be byCarbohydrate is converted into 1,2-PD; Described reaction pressure is produced with reacting by saturated vapor pressure corresponding to reaction temperatureRaw Hydrogen Vapor Pressure sum.
As preferred version, described carbohydrate is selected from glucose, fructose, cellulose and starch. In the present invention, carbon waterCompound wide material sources, are mainly glucose, fructose, cellulose and starch etc., are a kind of renewable resources.
As preferred version, described catalyst is selected from the transition metal of metal oxide or carbon load.
As preferred version, described catalyst is selected from Ni2O3、CuO、Fe3O4、Fe2O3、Al2O3, Pt/C, Ru/C or Pd/C.
As preferred version, described reducing agent is the metal simple-substance powder with reproducibility.
As preferred version, described in there is reproducibility metal simple-substance powder be selected from Mg, Al, Mn, Zn or Fe.
As preferred version, described reaction pressure is 2MPa～30MPa.
As preferred version, described reaction also comprises steps such as 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 butanediol simultaneously;Can obtain by filtering the 1,2-PD aqueous solution that purity is higher. Described filtration is specially the filter membrane that adopts 0.45 μ mFilter.
Compared with prior art, the present invention has following beneficial effect:
(1) the present invention uses carbohydrate to make raw material 1,2-PD processed, and carbohydrate distributes as occurring in natureAn extensive and most important class organic compound (coming from corn, stalk, trees and potato etc. that nature extensively exists),Wide material sources, renewable. So taking carbohydrate as raw material without consume fossil energy, can nowadays global face of partial rcsponseThe energy problem facing;
(2) the present invention makes to use water as reaction dissolvent. Make reducing agent, palladium carbon, ruthenium carbon or metal oxygen with metal cheap and easy to getCompound, as catalyst, without the complicated noble metal catalyst of preparation, transforms into carbohydrate under hydrothermal conditionThis high added value organic matter of 1,2-PD, realizes the conversion organic resource of clean and effective low consumption.
(3) the present invention, without additionally passing into high-purity hydrogen, has greatly reduced in energy consumption of reaction and hydrogen transport storing processCost, and environmental protection more, pollution on the environment is little;
(4) product ZnO can be recovered as other purposes (as being reduced to simple substance Zn by solar energy), also can in additionTo adopt the discarded metal producing in process of metal working as reducing agent, therefore cost is cheaper, has valuable economyBenefit;
(5) selectivity of product is high, and liquid product chief component is 1,2-PD, by controlling reaction condition, 1,2-Propane diols productive rate can reach 33.3%, is easy to separating-purifying.
Brief description of the drawings
By reading the detailed description of non-limiting example being done with reference to the following drawings, further feature of the present invention,It is more obvious that object and advantage will become:
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.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described in detail. Following examples will contribute to those skilled in the artFurther understand the present invention, but do not limit in any form the present invention. It should be pointed out that the ordinary skill people to this areaMember, without departing from the inventive concept of the premise, can also make some distortion and improvement. These all belong to the present inventionProtection domain.
Embodiment 1
The present embodiment relates to the method that a kind of metal simple-substance (Zn powder) and Pd/C hydrothermal conversion glucose are prepared 1,2 propane diols,Reaction equation is as follows:
Described method comprises the steps:
Pack glucose (1.11mmol), palladium carbon (0.03mmol) and zinc powder (6.9mmol) into SUS316 reactionGuan Zhong, makes filling rate reach 50%, by reaction tube sealing, puts into 300 DEG C of salt baths, and pressure is corresponding saturated vapor pressureWith react produced Hydrogen Vapor Pressure sum, reaction 30min, reaction take out after mixture filter and can obtain 1,2-the third twoAlcohol solution.
To after reaction, product be carried out to qualitative (seeing Fig. 1) and HPLC quantitative analysis (seeing Fig. 2) with GC/MS, GC/MS is fixedProperty analysis shows, 1,2-PD is primary product, and productive rate is 31%. In commercial Application, adopt suitable hydro-thermal by demandReactor, can control reaction temperature is 200～400 DEG C, reaction 15～90min. By this reaction, can be by glucoseBe converted in a large number 1,2-PD, easy to operation and selectively good. The ZnO that reaction produces can reclaim as otherPurposes.
Embodiment 2
The present embodiment relates to the method that a kind of metal simple-substance (Zn powder) and Pd/C hydrothermal conversion fructose are prepared 1,2 propane diols,Reaction equation is as follows:
Described method comprises the steps:
Pack fructose (1.11mmol), Pd/C (0.01mmol) and Zn powder (2.0mmol) into SUS316 reactionGuan Zhong, makes filling rate reach 60%, by reaction tube sealing, puts into 300 DEG C of salt baths, and pressure is corresponding saturated vapor pressureWith the Hydrogen Vapor Pressure sum that produces of reaction, reaction 90min, reaction take out after mixture filter and can obtain 1,2-the third twoAlcohol solution.
To after reaction, product be carried out to qualitative (seeing Fig. 3) and HPLC quantitative analysis (seeing Fig. 4) with GC/MS, GC/MS is fixedProperty analysis shows, 1,2-PD is primary product, and productive rate is 30%. In commercial Application, adopt suitable hydro-thermal by demandReactor, can control reaction temperature is 200～400 DEG C, reaction 15～90min. By this reaction, can fructose is largeAmount is converted into 1,2-PD, easy to operation and selectively good. The ZnO that reaction produces can reclaim as other useOn the way.
Embodiment 3
The present embodiment relates to the method that a kind of metal simple-substance (Zn powder) and Ru/C hydrothermal conversion cellulose are prepared 1,2 propane diols,Reaction equation is as follows:
Described method comprises the steps:
Pack cellulose (1.11mmol), Ru/C (0.02mmol) and Zn powder (9.0mmol) into SUS316 anti-Ying Guanzhong, makes filling rate reach 30%, by reaction tube sealing, puts into 300 DEG C of salt baths, and pressure is corresponding saturated vaporPress and react produced Hydrogen Vapor Pressure sum, reaction 70min, rear mixture filtration is taken out in reaction can obtain 1,2-thirdTwo alcohol solutions.
To after reaction, product be carried out to qualitative (seeing Fig. 5) and HPLC quantitative analysis (seeing Fig. 6) with GC/MS, GC/MS is fixedProperty analysis shows, 1,2-PD is primary product, and productive rate is 25%. In commercial Application, adopt suitable hydro-thermal by demandReactor, can control reaction temperature is 200～400 DEG C, reaction 15～90min. By this reaction, can be by celluloseBe converted in a large number 1,2-PD, easy to operation and selectively good. The ZnO that reaction produces can reclaim as otherPurposes.
Above specific embodiments of the invention are described. It will be appreciated that, the present invention is not limited to above-mentioned specificEmbodiment, those skilled in the art can make various distortion or amendment within the scope of the claims, and this does not affect thisEssence of an invention content.

Claims (2)

1. metal hydro-thermal to reduce carbohydrate is prepared a method for 1,2-PD, it is characterized in that, described method bagDraw together following steps: be (0.01～0.03) ︰ (1～9) ︰ 1 in molar ratio by catalyst, reducing agent, carbohydrateAdd in reactor, controlling filling rate is 25～60%, reacts 15～90min, under 200～400 DEG C, air-proof conditionCarbohydrate can be converted into 1,2-PD; The pressure of described reaction is that saturated vapor pressure corresponding to reaction temperature is with anti-Answer produced Hydrogen Vapor Pressure sum;
Described carbohydrate is selected from glucose, fructose, cellulose or starch;
Described catalyst is selected from Ni2O3、CuO、Fe3O4、Fe2O3、Al2O3, Pt/C, Ru/C or Pd/C;
Described reducing agent is the metal simple-substance powder with reproducibility, described in there is reproducibility metal simple-substance powder be selected from Mg,Al, Mn, Zn or Fe.
2. metal hydro-thermal to reduce carbohydrate according to claim 1 is prepared the method for 1,2-PD, its featureBe, described reaction pressure is 2MPa～30MPa.
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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
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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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
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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

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