CN102731258A - Method for preparing low carbon polyol by internal circulating catalysis and conversion of carbohydrate - Google Patents
Method for preparing low carbon polyol by internal circulating catalysis and conversion of carbohydrate Download PDFInfo
- Publication number
- CN102731258A CN102731258A CN2012101590736A CN201210159073A CN102731258A CN 102731258 A CN102731258 A CN 102731258A CN 2012101590736 A CN2012101590736 A CN 2012101590736A CN 201210159073 A CN201210159073 A CN 201210159073A CN 102731258 A CN102731258 A CN 102731258A
- Authority
- CN
- China
- Prior art keywords
- reaction
- reactor
- catalyst
- active component
- hanging basket
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The present invention relates to a reaction apparatus for preparing a low carbon polyol by catalysis and conversion of a carbohydrate, and a reaction process thereof. The reaction process adopts a high pressure reactor, wherein a catalyst filtering gondola is positioned inside the high pressure reactor, the position of the gondola is higher than the liquid level of the reactant inside the reactor, and the reaction is carried out under a high temperature hydrothermal condition. During the reaction, reactant slurry of the carbohydrate (comprising one or more than two materials selected from cellulose, hemicellulose, sucrose, glucose, fructose, xylose, soluble xylooligosaccharide and starch) flows from the bottom of the reactor, is driven to flow back to the reactor by a high pressure liquid pump, then is injected into the gondola to perform a catalytic reaction with the catalyst inside the gondola, and flows and accumulates on the bottom of the reactor, and the reaction is circulated. With the process, catalyst poisoning and deactivation can be effectively reduced, such that the reaction selectivity and the catalyst life can be improved.
Description
Technical field
The present invention relates to select to prepare the preparation method of terepthaloyl moietie or Ucar 35, specifically a kind of glucide internal recycle one step shortening the degrade device and reaction process process thereof of preparing ethylene glycol optionally or Ucar 35 reaction of being used for.
Background technology
Terepthaloyl moietie and Ucar 35 are the important energy liquid fuels; Also be very important polyester synthesis material, for example, terepthaloyl moietie can be used for polyethyleneterephthalate (PET); PEN (PEN) can also be used as frostproofer, lubricant, softening agent, tensio-active agent etc.; 1, the 2-Ucar 35 can be used for producing unsaturated polyester, epoxy resin, urethane resin, in food, medicine and cosmetic industry, also is widely used as moisture adsorbent, antifreezing agent, lubricant and solvent.They all are broad-spectrum Organic Chemicals.
At present, the industrial production of terepthaloyl moietie mainly is to adopt the petroleum route, promptly obtains oxyethane behind the ethylene epoxidizing; Hydration obtains terepthaloyl moietie [document 1: Cui Xiaoming, domestic and international terepthaloyl moietie production development overview, chemical industry then; 2007,25, (4); 15-21. document 2:Process for preparing ethanediol by catalyzing epoxyethane hydration, Patent No.CN1463960-A; CN1204103-C].
In recent years, along with the thriving demand to terepthaloyl moietie such as trevira, polyester plastics and deicing fluid, people begin to be devoted to the research-and-development activity of the new synthetic technology of terepthaloyl moietie.Shell company, UCC company, Moscow Mendelyeev chemical engineering institute etc. have developed catalyzing epoxyethane hydration legal system terepthaloyl moietie production technology in succession; Companies such as Halcon-SD, UCC, Dow chemistry, Japanese catalyst chemistry and Mitsubishi Chemical have developed NSC 11801 legal system terepthaloyl moietie production technology in succession; In addition, because the shortage and the natural gas source of world petroleum resource are abundant relatively, companies such as U.S. UCC and Ube Industries Ltd. have also carried out by coal based synthetic gas preparing ethylene glycol The Study on New Technology and development.
Present 1, the suitability for industrialized production technology part of 2-Ucar 35 is the raw material production route with the propylene oxide, is mainly propylene oxide direct hydration method, the indirect hydration method of propylene oxide; A part is the raw material production route with the propylene, is mainly the direct catalytic oxidation of propylene; Produce route with biomass material, comprise glycerine hydrogenation evaporation, sorbyl alcohol high temperature hydrogenation cracking process; Other is methylcarbonate/Ucar 35 co-production method.Compound method depends on non-renewable petroleum resources, and comprises selective oxidation or epoxidation step in the production process, and technical difficulty is big, and efficient is low, and by product is many, the midbody poisonous and harmful, and material consumption is high and seriously polluted.
The biomass that utilization has recyclability prepare terepthaloyl moietie and Ucar 35, can reduce human dependence to the fossil energy material, help realizing environmental friendliness and sustainable economic development.Glucide comprises that Mierocrystalline cellulose, starch, semicellulose, glucose, sucrose, fructose, Polylevulosan, wood sugar, solubility xylooligosaccharides are widespread in nature.Along with agrotechnical development, its output is growing.Development prepares terepthaloyl moietie and Ucar 35 with glucide, not only can reduce the dependence to petroleum resources to a certain extent, simultaneously, helps to realize deep processing of farm products system high added value chemical.At present; Technology [document 3:Process for the preparation of lower polyhydric alcohols with glucide system polyvalent alcohol; Patent; No.US5107018. document 4:Preparation of lower polyhydric alcohols; Patent, No.US5210335 document 5: a kind of novel process of producing terepthaloyl moietie, CN200610068869.5 document 6: a kind of method of producing divalent alcohol and polyvalent alcohol by cracking sorbierite; CN200510008652.0] generally comprise three steps: (1) starch obtains glucose (2) glucose through gelatinization, enzyme liquefaction, enzyme glycolysis process and obtains sorbyl alcohol (3) sorbyl alcohol hydrogenolysis generation product polyvalent alcohol under HTHP through noble ruthenium or nickel catalyzator hydrogenation, is mainly Ucar 35, USP Kosher, terepthaloyl moietie.Wherein, the yield of terepthaloyl moietie is in the 10-30% scope, and the yield of Ucar 35 is in the 30-60% scope.Reaction process is loaded down with trivial details.
An other preparation approach is to transform preparation of cellulose terepthaloyl moietie [document 7:Direct catalytic conversion of cellulose into ethylene glycol using nickel-promoted tungsten carbide catalysts through shortening under the hydrothermal condition; Angew.Chem.Int.Ed.2008; 47,8510 – 8513.Document 8:transition metal – tungsten bimetallic catalysts for the conversion of cellulose into ethylene glycol, ChemSusChem 2010,3,63 – 66.】。This method is with tungsten carbide catalyst, and perhaps the promoted tungsten catalyzer of transition metal carries out catalyzed conversion to Mierocrystalline cellulose, thereby obtains terepthaloyl moietie.The terepthaloyl moietie yield can reach 60-75%.Similarly; The dual-component catalyst that adopts oxidation state tungsten and hydrogenation metal to constitute can realize also that under the condition of hydro-thermal hydrogenation Mierocrystalline cellulose, starch etc. contain sugar compounds highly-selective preparation terepthaloyl moietie, Ucar 35 [document 9: a kind of method WO2011113281A of preparing ethanediol from polyhydroxy compounds].
On the other hand; When being used for the cellulosic conversion of higher concentration (greater than 5wt%) and preparing terepthaloyl moietie, Ucar 35 with the method for document 7-9; Owing to there is side reaction to a certain degree in the reaction process; Make catalyzer that intoxicating phenomenon take place gradually, cause reaction preference to descend, thereby influence the yield and the life of catalyst of title product.
Method provided by the invention is through the novel design to structure of reactor and technical process; Solved the easy problem of poisoning of catalyzer effectively; Improved the target product yield of reaction process; Prolong catalyst life simultaneously, improved the economy of reaction process, thereby had good using value.
Summary of the invention
The object of the present invention is to provide a kind of reaction unit and reaction process process thereof that is used for glucide preparing ethylene glycol or Ucar 35.
Reaction raw materials is glucide (comprising Mierocrystalline cellulose, starch, semicellulose, sucrose, glucose, fructose, Polylevulosan, wood sugar, solubility xylooligosaccharides); Through a step shortening degradation process, high yield, optionally prepare terepthaloyl moietie or Ucar 35.
For realizing above-mentioned purpose, the technical scheme that the present invention takes is:
In reactor drum, under nitrogen atmosphere, in the concentration 3-80wt% glucide reaction raw materials aqueous solution, under catalyst action, carry out the polyvalent alcohol product that hydrocracking production comprises terepthaloyl moietie, 1,2 Ucar 35; The reaction raw materials slurries are in the state of continuous flow; From the reactor bottom outflow reactor; Flow back in the reactor drum by reactor head through the pressure liquid pump driving, be injected into the filtration hanging basket that is filled with solid catalyst, filter in the catalyzer that is loaded in the hanging basket and contain catalytic active component A; The catalyst filtration hanging basket is positioned at reactor drum, and the position is higher than reaction raw materials slurry liquid level, and the reaction solution that is flowed back to by the reactor head solid catalyst in the hanging basket of flowing through falls back in the slurries of reaction raw materials of reactor bottom afterwards; In the reaction process, the volume of the reaction raw materials slurries of reactor bottom remains on the 1/5-2/3 interval of reactor volume; Be added with catalyzer in the reaction raw materials slurry liquid of reactor bottom, wherein contain catalytic active component B at least, under stirring action, carry out catalyzed reaction;
Reaction process adopts dual-active property component catalyst; Comprise catalytic active component A and catalytic active component B; Active component A and active ingredient B both can be supported on the common carrier; Said carrier is one or more a complex carrier of gac, mesoporous carbon, CNT, Graphene, aluminum oxide, silicon oxide, zirconium white, zinc oxide, titanium oxide, also can in reaction process, the form with mechanically mixing constitute mixed catalyst; Catalytic active component A comprises a kind of in the transition metal iron, cobalt, nickel, ruthenium, rhodium, palladium, iridium, platinum of the 8th, 9,10 families with Catalytic Hydrogenation Properties or more than two kinds; Catalytic active component B comprises one or more in mineral compound, organic cpds, complex compound or the tungsten simple substance of tungsten, is specially in the carbide, nitride, phosphide of oxyhydroxide, tungsten bronze(s), wolframic acid, tungstate, metatungstic acid, metatungstate, para-tungstic acid, para-tungstate, peroxide wolframic acid, peroxide tungstate, heteropoly tungstic acid, tungsten, the tungsten of muriate, the tungsten of sulfide, the tungsten of oxide compound, the tungsten of tungsten one or more;
Active component A and active ingredient B both can be supported on the common carrier, or also can in reaction process, the form with mechanically mixing constitute mixed catalyst; An active component A and an active ingredient B part are in the hanging basket, and another part is in the reaction raw materials slurry liquid;
It is non-loading type that active component A and active ingredient B are supported on carrier or active component A and active ingredient B respectively, and active component A is a part of or all be in the hanging basket; An active ingredient B part or all be in the reaction raw materials slurry liquid;
Said carrier is one or more a complex carrier of gac, mesoporous carbon, CNT, Graphene, aluminum oxide, silicon oxide, zirconium white, zinc oxide, titanium oxide.
The carrier of catalyst activity component A and/or B is selected from one or more in gac with vesicular structure, aluminum oxide, silicon oxide, silit, zirconium white, zinc oxide, the titanium oxide; The content of activity component metal on catalyzer is at 0.05-60wt%;
Perhaps catalyst A be unsupported, with the skeleton metal catalyst of active ingredient as catalyst backbone, Raney's nickel etc. for example.
The amount of catalyst activity component A and the weight ratio scope of reaction raw materials are 1/1000-1/2; The concentration of catalyst activity B component in reactor drum is counted 10ppm-50000ppm with tungsten; The proportionlity of the amount of catalyst activity component A and B (weight ratio of hydrogenation metal and tungsten) scope is 0.01-100.
Quality and active component A the quality ratio in reactor bottom reaction solution of catalyst activity component A in the catalyzer hanging basket is greater than 0.1.
The catalyst filtration hanging basket bottom and/or the side wall surface that are positioned at reaction liquid level top are provided with screen cloth or orifice plate,, can make the reaction solution of the backflow beds of flowing through, prevent the loss of solid catalyst simultaneously.
Reactor bottom is equipped with screen cloth, can make partial reaction liquid give off reactor drum and carry out round-robin simultaneously, and solid reactant and solid catalyst are retained in the reaction solution of reactor bottom.
Hydrocracking reaction is operated under 1-15MPa; Thermolysis does not take place with product and is as the criterion in temperature of reaction >=120 ° C, upper temperature limit.Preferable reaction temperature is 180-260 ° of C; Preferred hydrogen pressure 5-12MPa.
Said carbohydrate raw material is a kind of in Mierocrystalline cellulose, semicellulose, sucrose, glucose, fructose, Polylevulosan, wood sugar, solubility xylooligosaccharides, the starch or more than two kinds.
The consumption of reaction raw materials glucide and water partially or completely serves as liquid getting final product with reaction mass under the reaction conditions, stirs with this understanding, and reactant is heated evenly, avoids the too high raw material that causes of local temperature to burn the phenomenon generation.The consumption of composite catalyst is a catalytic amount.
Preferable condition is that the mass ratio of reaction raw materials glucide and water is 1:20-1:1, and the mass ratio of glucide and composite catalyst active component A+B is 1:5-100:1.
Below listed embodiment embodied beneficial effect of the present invention, but do not get rid of, to obtain better reaction result through further optimization to structure of reactor involved in the present invention and reaction process parameter.
For accomplishing these reaction links, adopted the reaction process shown in the Figure of description 1.
The present invention has following advantage; Through novel design, make the oily by product that generates in the reaction process because density is low and be in all the time the upper strata of reaction solution in the reactor drum, and reaction solution is derived and is turned back to catalyst activity component A and carries out catalyzed reaction from reactor bottom to structure of reactor and technical process; Avoided of the direct contact of oily by product to active component A in the catalyzer; Thereby solved the problem of poisoning of catalyst effectively, improved the target product yield of reaction process, prolonged catalyst life; Improve the economy of reaction process, had good using value and application prospect.
Through specific embodiment the present invention is elaborated below, but these embodiment do not constitute restriction to content of the present invention.
Description of drawings
Fig. 1 is the reaction process schematic flow sheet.
Embodiment
Embodiment 1
Metal catalyst Ni/AC, Ni/TiO
2, Pt/AC, the preparation of Ru/AC: respectively with nickelous nitrate, Platinic chloride, ruthenium trichloride aqueous solution impregnated activated carbon carrier; Behind the dry 12h of 120 ° of C, in 450 ° of C nitrogen atmosphere, reduce 1h, obtain catalyst n i/AC (50wt%Ni) respectively; Pt/AC (0.5wt%Pt), Ru/AC (5wt%Ru).Activity carbon carrier is changed to SiO
2, can make Ni/TiO with quadrat method
2(15wt%Ni) catalyzer.
Embodiment 2
Reference Angew.Chem.Int.Ed.2008,47,8510 – 8513, preparation Ni-W
2The C/AC catalyzer: is that the ratio of 6:1 is processed mixing solutions with metatungstic acid ammonia and nickelous nitrate according to tungsten/nickel weight ratio, and wherein, the mass concentration of metatungstic acid ammonia is 0.4g/ml.Then, with mixing solutions Immesion active carbon carrier (AC).Behind 120 ° of C oven drying 12h, catalyst precursor is placed H
2Carry out temperature programming carbon thermal response in the atmosphere, concrete reaction process is: the 1.0g precursor is warming up to 400 ° of C by room temperature 1h in crystal reaction tube, then be warming up to 700 ° of C and keep 1h to carry out carbonization with 1 ° of C/min, and hydrogen flow rate is 60ml/min.Obtaining the tungsten loading is that 30wt%, nickel loading are the Ni-W of 5wt%
2The C/AC catalyzer is expressed as Ni-W
2C/AC (5wt%Ni-30wt%W
2C).
Embodiment 3
The catalyzed conversion experiment: with the 10.0g Mierocrystalline cellulose, 0.1g Ru/AC (5wt%Ru) catalyzer, 0.03g tungstic acid catalyst and 100ml water join in the 200ml reaction kettle; 0.2g joining, filters in the hanging basket by Ru/AC (5wt%Ru) catalyzer; After feeding three gases of hydrogen exchange, fill hydrogen, be warming up to 240 ℃ to 5MPa; The flow velocity of reaction solution with 10ml/min refluxed through pressure liquid pump, and the reaction times is 60min.After reaction finishes, reduce to room temperature, get the supernatant liquid after centrifugal, on performance liquid chromatography calcium type ion exchange column, separate and detect with differential refractometer detector.Only title product terepthaloyl moietie, Ucar 35 and hexavalent alcohol (comprising sorbyl alcohol, N.F,USP MANNITOL) are calculated in the product yield, other product liquids comprise butantetraol, ethanol, not principal component, and gaseous product (CO
2, CH
4, C
2H
6Deng) do not calculate its yield.
The comparative example 1
The experiment of intermittent reaction catalyzed conversion: with the 10.0g Mierocrystalline cellulose, 0.3g Ru/AC (5wt%Ru) catalyzer, 0.03g tungstic acid catalyst and 100ml water join in the 200ml reaction kettle; After feeding three gases of hydrogen exchange; Fill hydrogen to 5MPa, be warming up to 240 ° of C, the reaction times is 60min.The analytical procedure of reaction product is with embodiment 3.
Embodiment 4
The catalyzed conversion experiment: with the 15.0g Mierocrystalline cellulose, 0.4g Ni/AC (50wt%Ni) catalyzer, 0.1g tungstic acid catalyst and 100ml water join in the 200ml reaction kettle; 0.3g Ru/AC (5wt%Ru) catalyzer joins in the catalyzer basket; After feeding three gases of hydrogen exchange, fill hydrogen, be warming up to 240 ℃ to 5MPa; The flow velocity of reaction solution with 15ml/min refluxed through pressure liquid pump, and the reaction times is 80min.The analytical procedure of reaction product is with embodiment 3.
The comparative example 2
The experiment of intermittent reaction catalyzed conversion: with the 15.0g Mierocrystalline cellulose, 0.4g Ni/AC (50wt%Ni) catalyzer, 0.3g Ru/AC (5wt%Ru) catalyzer; 0.1g tungstic acid catalyst and 100ml water join in the 200ml reaction kettle; Join in the catalyzer basket, behind three gases of feeding hydrogen exchange, fill hydrogen to 8MPa; Be warming up to 240 ° of C, the reaction times is 80min.The analytical procedure of reaction product is with embodiment 3.
Embodiment 5
The catalyzed conversion experiment: with the 18.0g Mierocrystalline cellulose, 0.5g Ni-W
2C/AC (5wt%Ni-30wt%W
2C) and 100ml water join in the 200ml reaction kettle 2.5g Ni-W
2C/AC (5wt%Ni-30wt%W
2C) catalyzer joins in the catalyzer basket, behind three gases of feeding hydrogen exchange, fills hydrogen to 6MPa, is warming up to 240 ° of C, and the flow velocity of reaction solution with 12ml/min refluxed through HPP, and the reaction times is 90min.The analytical procedure of reaction product is with embodiment 3.
The comparative example 3
The experiment of intermittent reaction catalyzed conversion: with the 18.0g Mierocrystalline cellulose, 3.0g Ni-W
2C/AC (5wt%Ni-30wt%W
2C) catalyzer, 100ml water join in the 200ml reaction kettle, behind three gases of feeding hydrogen exchange, fill hydrogen to 6MPa, are warming up to 240 ° of C, and the reaction times is 90min.The analytical procedure of reaction product is with embodiment 3.
The result of Mierocrystalline cellulose catalyzed conversion among table one, embodiment 3-5, the comparative example 1-3
Shown in table one, Mierocrystalline cellulose can related in the present invention catalytic process in, on the different composite catalyzer, be converted into terepthaloyl moietie with high yield.Be higher than the terepthaloyl moietie yield that obtains in the conventional batch reactor significantly.
Embodiment 6
The catalytic conversion reaction of different glucide: Mierocrystalline cellulose is changed to various biomass, and other reaction conditionss are with embodiment 3.
The result of the catalyzed conversion of table two, various glucide
Shown in table two, various glucide can be converted into terepthaloyl moietie and Ucar 35 in the related in the present invention catalytic process with high yield, and total recovery can reach 50-70%.
Claims (10)
1. a glucide internal recycle catalyzed conversion prepares the method for low-carbon (LC) polyvalent alcohol, it is characterized in that:
1) in reactor drum, under nitrogen atmosphere, in the concentration 3-80wt% glucide reaction raw materials aqueous solution, under catalyst action, carries out the polyvalent alcohol product that hydrocracking production comprises terepthaloyl moietie, 1,2 Ucar 35; The reaction raw materials slurries are in the state of continuous flow; Raw slurry is from the reactor bottom outflow reactor; Flow back in the reactor drum by reactor head through the pressure liquid pump driving; And be injected in the filtration hanging basket that places the reactor drum middle and upper part, filter in the hanging basket and be filled with solid catalyst, contain part catalytic active component A in the catalyzer that this hanging basket loaded at least;
2) the filtration hanging basket that is filled with solid catalyst is positioned at reactor drum; Position height is more than reaction raw materials slurry liquid level; The reaction solution that is flowed back to by the reactor head solid catalyst in the hanging basket of flowing through falls back in the slurries of reaction raw materials of reactor bottom afterwards;
3) in the reaction process, the volume of the reaction raw materials slurries of reactor bottom remains on the 1/5-2/3 scope of reactor volume;
3) adding has catalyzer in the reaction raw materials slurry liquid of reactor bottom, wherein contains part catalytic active component B at least, under stirring action, carries out catalyzed reaction;
4) adopt dual-active property component catalyst in the reaction process; Comprise catalytic active component A and catalytic active component B; Catalytic active component A comprises a kind of in the transition metal iron, cobalt, nickel, ruthenium, rhodium, palladium, iridium, platinum of the 8th, 9,10 families with Catalytic Hydrogenation Properties or more than two kinds, and catalytic active component B comprises one or more in mineral compound, organic cpds, complex compound or the tungsten simple substance of tungsten;
The amount of said catalyst activity component A and the weight ratio scope of reaction raw materials are 1/1000-1/2; The concentration of catalyst activity B component in reactor drum is counted 10ppm-50000ppm with tungsten; The proportionlity of the amount of catalyst activity component A and B (weight ratio of hydrogenation metal and tungsten) scope is 0.01-100.
2. according to the described method of claim 1, it is characterized in that:
Active component A and active ingredient B both can be supported on the common carrier, or also can in reaction process, the form with mechanically mixing constitute mixed catalyst; An active component A and an active ingredient B part are in the hanging basket, and another part is in the reaction raw materials slurry liquid;
It is non-loading type that active component A and active ingredient B are supported on carrier or active component A and active ingredient B respectively, and active component A is a part of or all be in the hanging basket; An active ingredient B part or all be in the reaction raw materials slurry liquid;
Said carrier is one or more a complex carrier of gac, mesoporous carbon, CNT, Graphene, aluminum oxide, silicon oxide, zirconium white, zinc oxide, titanium oxide.
3. according to the described method of claim 1, it is characterized in that: quality and active component A the quality ratio in reactor bottom reaction solution of said catalyst activity component A in the catalyzer hanging basket is greater than 0.1.
4. according to claim 1 or 2 described methods; It is characterized in that: the said catalyst filtration hanging basket that is positioned at reaction liquid level top is meant in the bottom and/or the side wall surface of hanging basket and is provided with screen cloth or orifice plate; The reaction solution of backflow is flowed through in hanging basket, flow out behind the beds, prevent the loss of the solid catalyst in the hanging basket simultaneously.
5. according to claim 1 or 2 described methods, it is characterized in that: reactor bottom is equipped with screen cloth, can make partial reaction liquid give off reactor drum and carry out round-robin simultaneously, and solid reactant and solid catalyst are retained in the reaction solution of reactor bottom.
6. according to the described method of claim 1, it is characterized in that: said hydrocracking reaction is operated under 1-15MPa; Thermolysis does not take place with product and is as the criterion in temperature of reaction >=120 ° C, upper temperature limit.
7. according to the described method of claim 1, it is characterized in that: said hydrogen cracking preferable reaction temperature is 180-260 ° of C; Preferred hydrogen pressure 5-12MPa.
8. according to the described method of claim 1, it is characterized in that: said carbohydrate raw material is a kind of in Mierocrystalline cellulose, semicellulose, sucrose, glucose, fructose, Polylevulosan, wood sugar, solubility xylooligosaccharides, the starch or more than two kinds.
9. according to the described method of claim 1; It is characterized in that: the consumption of reaction raw materials glucide and water partially or completely serves as liquid getting final product with reaction mass under the reaction conditions; Stir with this understanding; Reactant is heated evenly, avoids the too high raw material that causes of local temperature to burn the phenomenon generation; The consumption of composite catalyst is a catalytic amount.
10. according to the described method of claim 1, it is characterized in that: the mass ratio of reaction raw materials glucide and water is 1:20-1:1, and the mass ratio of glucide and composite catalyst active component A+B is 1:5-100:1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210159073.6A CN102731258B (en) | 2012-05-21 | 2012-05-21 | Method for preparing low carbon polyol by internal circulating catalysis and conversion of carbohydrate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210159073.6A CN102731258B (en) | 2012-05-21 | 2012-05-21 | Method for preparing low carbon polyol by internal circulating catalysis and conversion of carbohydrate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102731258A true CN102731258A (en) | 2012-10-17 |
| CN102731258B CN102731258B (en) | 2014-07-23 |
Family
ID=46987651
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210159073.6A Active CN102731258B (en) | 2012-05-21 | 2012-05-21 | Method for preparing low carbon polyol by internal circulating catalysis and conversion of carbohydrate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102731258B (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103386483A (en) * | 2013-07-05 | 2013-11-13 | 谭彬 | Nano-graphene composite material and preparing method thereof |
| WO2016045583A1 (en) * | 2014-09-28 | 2016-03-31 | 长春美禾科技发展有限公司 | Method for preparing diol |
| CN105517983A (en) * | 2013-08-26 | 2016-04-20 | 国际壳牌研究有限公司 | Process for preparation of glycols |
| WO2017097847A1 (en) | 2015-12-09 | 2017-06-15 | Shell Internationale Research Maatschappij B.V. | Process for the preparation of glycols |
| CN107406359A (en) * | 2015-01-13 | 2017-11-28 | 阿凡田知识中心有限公司 | The technique for preparing ethylene glycol from carbohydrate |
| CN107406358A (en) * | 2015-01-13 | 2017-11-28 | 阿凡田知识中心有限公司 | The continuous processing of ethylene glycol is prepared from carbohydrate |
| WO2018233677A1 (en) | 2017-06-22 | 2018-12-27 | 长春美禾科技发展有限公司 | Acid-resistant alloy catalyst |
| US10556226B2 (en) | 2014-09-28 | 2020-02-11 | The Coca-Cola Company | Acid-resistant alloy catalyst |
| CN110882710A (en) * | 2018-09-07 | 2020-03-17 | 中国石油化工股份有限公司 | Carbide-based catalyst, preparation method thereof and glycerol hydrogenolysis method |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101723802A (en) * | 2008-10-24 | 2010-06-09 | 中国科学院大连化学物理研究所 | Method for preparing ethylene glycol from cellulose |
-
2012
- 2012-05-21 CN CN201210159073.6A patent/CN102731258B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101723802A (en) * | 2008-10-24 | 2010-06-09 | 中国科学院大连化学物理研究所 | Method for preparing ethylene glycol from cellulose |
Cited By (33)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103386483B (en) * | 2013-07-05 | 2016-03-30 | 谭彬 | A kind of nano-graphene composite and preparation method thereof |
| CN103386483A (en) * | 2013-07-05 | 2013-11-13 | 谭彬 | Nano-graphene composite material and preparing method thereof |
| CN105517983A (en) * | 2013-08-26 | 2016-04-20 | 国际壳牌研究有限公司 | Process for preparation of glycols |
| AU2020204171B2 (en) * | 2014-09-28 | 2021-08-19 | Changchun Meihe Science And Technology Development Co., Ltd | Method for preparing diol |
| US10556226B2 (en) | 2014-09-28 | 2020-02-11 | The Coca-Cola Company | Acid-resistant alloy catalyst |
| EA035720B1 (en) * | 2014-09-28 | 2020-07-30 | Чанчунь Мэйхэ Сайэнс Энд Текнолоджи Девелопмент Ко., Лтд | Method for preparing diol |
| KR20170097606A (en) * | 2014-09-28 | 2017-08-28 | 장춘 메이허 과기발전 유한공사 | Method for preparing diol |
| US11104629B2 (en) | 2014-09-28 | 2021-08-31 | The Coca-Cola Company | Methods for preparing diol |
| WO2016045583A1 (en) * | 2014-09-28 | 2016-03-31 | 长春美禾科技发展有限公司 | Method for preparing diol |
| EP3653595A1 (en) | 2014-09-28 | 2020-05-20 | Changchun Meihe Science and Technology Development Co., Ltd. | Method for preparing diol |
| KR102601107B1 (en) * | 2014-09-28 | 2023-11-10 | 장춘 메이허 과기발전 유한공사 | Method for preparing diol |
| CN105523890A (en) * | 2014-09-28 | 2016-04-27 | 长春美禾科技发展有限公司 | Method for preparing dihydric alcohol |
| RU2698724C2 (en) * | 2014-09-28 | 2019-08-29 | Чанчунь Мэйхэ Сайэнс Энд Текнолоджи Девелопмент Ко., Лтд | Method of producing diol |
| US10464870B2 (en) | 2014-09-28 | 2019-11-05 | The Coca-Cola Company | Methods for preparing diol |
| US20220055974A1 (en) * | 2014-09-28 | 2022-02-24 | Changchun Meihe Science And Technology Development Co., Ltd | Methods for Preparing Diol |
| US11746074B2 (en) | 2014-09-28 | 2023-09-05 | Changchun Meihe Science And Technology Development Co., Ltd | Methods for preparing diol |
| AU2015320134B2 (en) * | 2014-09-28 | 2020-03-26 | Changchun Meihe Science And Technology Development Co., Ltd | Method for preparing diol |
| CN111606781B (en) * | 2014-09-28 | 2023-11-28 | 长春美禾科技发展有限公司 | Method for preparing dihydric alcohol |
| CN111545213B (en) * | 2014-09-28 | 2023-08-04 | 长春美禾科技发展有限公司 | Acid-resistant alloy catalyst |
| CN111545213A (en) * | 2014-09-28 | 2020-08-18 | 长春美禾科技发展有限公司 | Acid-resistant alloy catalyst |
| CN111606781A (en) * | 2014-09-28 | 2020-09-01 | 长春美禾科技发展有限公司 | Method for preparing dihydric alcohol |
| CN105523890B (en) * | 2014-09-28 | 2021-04-16 | 长春美禾科技发展有限公司 | Method for preparing dihydric alcohol |
| US10940465B2 (en) | 2014-09-28 | 2021-03-09 | The Coca-Cola Company | Acid-resistant alloy catalyst |
| CN107406358B (en) * | 2015-01-13 | 2020-12-08 | 阿凡田知识中心有限公司 | Continuous process for the preparation of ethylene glycol from a carbohydrate source |
| CN107406358A (en) * | 2015-01-13 | 2017-11-28 | 阿凡田知识中心有限公司 | The continuous processing of ethylene glycol is prepared from carbohydrate |
| CN107406359A (en) * | 2015-01-13 | 2017-11-28 | 阿凡田知识中心有限公司 | The technique for preparing ethylene glycol from carbohydrate |
| US10294181B2 (en) | 2015-12-09 | 2019-05-21 | Shell Oil Company | Process for the preparation of glycols |
| WO2017097847A1 (en) | 2015-12-09 | 2017-06-15 | Shell Internationale Research Maatschappij B.V. | Process for the preparation of glycols |
| EP3386630B1 (en) * | 2015-12-09 | 2023-08-30 | Shell Internationale Research Maatschappij B.V. | Process for the preparation of glycols |
| CN108367266A (en) * | 2015-12-09 | 2018-08-03 | 国际壳牌研究有限公司 | The method for being used to prepare glycol |
| WO2018233677A1 (en) | 2017-06-22 | 2018-12-27 | 长春美禾科技发展有限公司 | Acid-resistant alloy catalyst |
| CN110882710B (en) * | 2018-09-07 | 2022-10-21 | 中国石油化工股份有限公司 | Carbide-based catalyst, preparation method thereof and glycerol hydrogenolysis method |
| CN110882710A (en) * | 2018-09-07 | 2020-03-17 | 中国石油化工股份有限公司 | Carbide-based catalyst, preparation method thereof and glycerol hydrogenolysis method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102731258B (en) | 2014-07-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102731258B (en) | Method for preparing low carbon polyol by internal circulating catalysis and conversion of carbohydrate | |
| CN103420796B (en) | Method of a high metal loading catalyst for preparing glycol from carbohydrate | |
| CN102190562B (en) | Method for preparing ethylene glycol from polyols | |
| CN102675045A (en) | Method for preparing ethylene glycol and 1,2-propylene glycol by using saccharide solution | |
| CN103420797B (en) | Method of low metal loading catalyst for preparing glycol from carbohydrate | |
| CN101723802B (en) | Method for preparing ethylene glycol from cellulose | |
| CN103420795B (en) | Produced the method for dibasic alcohol by carbohydrate in a kind of lower boiling organic phase | |
| CN102731257B (en) | A kind of method of sugary compound selective propylene glycol | |
| CN101648140B (en) | Tungsten carbide catalyst, preparation thereof and application thereof in reaction for preparing glycol from cellulose | |
| CN101735014B (en) | Method for preparing ethanediol from polyhydroxy compounds | |
| CN102643164B (en) | Method for producing ethylene glycol and 1,2-propylene glycol by continuously hydrocracking cellulose | |
| CN102049273B (en) | Mesoporous carbon-supported tungsten carbide catalyst and preparation and application thereof | |
| CN106694009B (en) | Method for preparing low-carbon dihydric alcohol by using alloy catalyst for catalyzing carbohydrate | |
| Qiu et al. | High-efficient preparation of gasoline-ranged C5–C6 alkanes from biomass-derived sugar polyols of sorbitol over Ru-MoO3− x/C catalyst | |
| CN103420798A (en) | Process for highly efficient catalytic conversion of cellulose raw material to dihydric alcohol | |
| CN104098439A (en) | Biomass glycol refining method | |
| CN102746117B (en) | Method for catalytic conversion preparation of hexahydric alcohol from jerusalem artichoke as raw material | |
| CN101269331B (en) | Process for producing high-stability central-hole material Cu-Zn-Al2O3, and application of the same in producing mellow wine dehydrogenating catalyst | |
| CN102600851A (en) | Preparation method of catalyst for synthesizing methanol by carbon dioxide hydrogenation | |
| CN103159587A (en) | Application for catalyst in hydrocracking for biological polyol | |
| CN104119207A (en) | Method for preparation of ethylene glycol by catalytic conversion of carbohydrate | |
| Yuan et al. | Reaction mechanisms and catalysis in the one-step synthesis of methylal via methanol oxidation | |
| CN103420787B (en) | Method of preparing small molecule polyol from carbohydrate under near-critical or supercritical conditions | |
| CN106914247A (en) | The preparation and application of a kind of nickel-base catalyst for carbon dioxide methanation | |
| CN103420788A (en) | Method of preparing small molecule alcohol from carbohydrate in two-phase solvent |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |