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CN102643165A - Method for producing ethylene glycol and 1,2-propylene glycol through continuous hydrocrackin of sugars - Google Patents

Method for producing ethylene glycol and 1,2-propylene glycol through continuous hydrocrackin of sugars Download PDF

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CN102643165A
CN102643165A CN2011101767869A CN201110176786A CN102643165A CN 102643165 A CN102643165 A CN 102643165A CN 2011101767869 A CN2011101767869 A CN 2011101767869A CN 201110176786 A CN201110176786 A CN 201110176786A CN 102643165 A CN102643165 A CN 102643165A
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CN102643165B (en
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张涛
陈曙光
郑明远
王爱琴
于婷婷
丁玉龙
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Dalian Institute of Chemical Physics of CAS
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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
    • C07C29/60—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by elimination of -OH groups, e.g. by dehydration
    • 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
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/46—Ruthenium, rhodium, osmium or iridium
    • B01J23/462—Ruthenium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/652—Chromium, molybdenum or tungsten
    • B01J23/6525—Molybdenum

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Abstract

The invention relates to a continuous reaction process flow for producing ethylene glycol and 1, 2-propylene glycol through continuous hydrocrackin of sugars and provides a method for producing the ethylene glycol and the 1,2-propylene glycol through continuous hydrocrackin of sugars. In the process flow, sugars (comprising one or more than two of sugar, glucose, fructose, xylose, soluble xylo-oligosaccharide and starch) are hydrocracked in the presence of a catalyst in a reactor and the hydrocracked product enters a separating system. Hydrogen gas in a gas phase is recycled by separating and recovering; a liquid phase product partially reflows to the reactor and other liquid phase products are refined and separated to form the ethylene glycol, the propylene glycol and other polyhydric alcohols; and concentrated soluble catalyst components in the refined and separated residual component liquid phase are partially returned to the reactor.

Description

Continuous hydrogenation cracking sugar transforms terepthaloyl moietie and 1, the method for 2-Ucar 35 of producing
Technical field
The present invention relates to a kind of sugar soln preparing ethylene glycol, 1, the technological process of 2-Ucar 35, specifically a kind of shortening cracking carbohydrate transforms the continuous reaction technological process of producing terepthaloyl moietie and 1,2 Ucar 35.
Background technology
Terepthaloyl moietie (being called for short EG) has another name called glycol, ethylene glycol; It is a kind of important petrochemical complex basic organic material; Be mainly used in and produce trevira, frostproofer, unsaturated polyester resin, lubricant, softening agent, nonionogenic tenside and explosive etc., can be used for industries such as coating, soup, brake fluid and printing ink in addition, as the solvent and the medium of ammonium pertorate; Be used to produce special solvent glycol ether etc., purposes very extensively.
It is the legal operational path of pressurized water that the suitability for industrialized production of present domestic and international large-scale terepthaloyl moietie all adopts the oxyethane direct hydration; Production technology is controlled [document 1: Cui Xiaoming by English lotus Shell, U.S. Halcon-SD and U.S. UCC three companies basically; Domestic and international terepthaloyl moietie production development overview, chemical industry, 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.
1, the 2-Ucar 35 is a raw material of making unsaturated polyester resin, epoxy resin, urethane resin; It also is the midbody of producing tensio-active agent such as emulsifying agent and emulsion splitter; Because its toxicity is little, therefore also can be used as the solvent of food color, spices, makeup; Also can make tobacco wetting agent, mould inhibitor and the fruit sanitas that accelerates the ripening; On medicine industry, it is mainly used in the auxiliary and the water-soluble ointment of injection; Aspect paint, pigment, detergents and cosmetic, Ucar 35 is raw material, solvent and tackifier (as being used for toothpaste) etc. of producing softening agent.
1,2-Ucar 35 (PG) is used to make unsaturated polyester resin (being used for topcoating and galss fiber reinforced resin) and accounts for 27%; System functional fluid (deicing fluid, the agent of change ice, heat transfer liquid) accounts for 2%; System food, medicine and makeup account for 20%; The system liquid washing agent accounts for 17%; System paint and coating account for 5%; Tobacco curing grass wetting Agent for Printing Inks accounts for 2%; Other purposes comprises softening agent, accounts for 9%.The application of Ucar 35 aspect makeup and liquid washing agent increases still very fast, and annual growth is respectively 3% and 3.5%.Cosmetics production merchant is with its skin moisten composition as the individual health care article, and these healthcare products have antiperspirant, reodorant, sunblock lotion, shaving cream and beauty cream.In liquid washing agent, Ucar 35 plays the effect of enzyme stabilizers and solvent.
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.
Along with fossil energy resource (comprising oil, coal, Sweet natural gas etc.) is more and more deficienter, adopt the status of the main chemical of renewable resources production more and more important.Carbohydrate is a kind of renewable energy source, comprises but is not limited to, a kind of in sucrose, glucose, fructose, wood sugar, solubility xylooligosaccharides, the starch or more than two kinds, it can be supplied raw materials for some chemical (like terepthaloyl moietie, 1, the 2-Ucar 35).[document 3:Process for the preparation of lower polyhydric alcohols; 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 document 7: a kind of method of preparing ethanediol from polyhydroxy compounds, CN200810229065.8].
At present, utilize the direct catalytic conversion preparing ethylene glycol of carbohydrate, the reaction of Ucar 35 in step reaction kettle, to carry out [document 7: a kind of method of preparing ethanediol from polyhydroxy compounds, CN200810229065.8].From the angle of large-scale industrial application, batch operation is not only consuming time, operation inconvenience, and wastes energy and material.Thereby, use for ease of heavy industrialization, reduce running cost, improve reaction efficiency, development of high efficient continuous reaction technological process is most important.
Summary of the invention
The object of the present invention is to provide a kind of shortening cracking carbohydrate to transform the continuous reaction process process of producing terepthaloyl moietie and 1,2 Ucar 35.
Be to realize above-mentioned purpose, the technical scheme that the present invention adopts is: reaction process comprise reaction-ure feeding, catalyzed reaction, reactor stream go out the gas liquid solids constituent from, gas recovery, soluble catalyst reclaim, reaction solution refluxes, the product purification several links.
For accomplishing these reaction links, adopted the reaction process shown in the Figure of description 1.
The glycogen material is a kind of in sucrose, glucose, fructose, Polylevulosan, wood sugar, solubility xylooligosaccharides, the starch or more than two kinds.Glycogen material concentration of aqueous solution is 5-80wt% in the reactor drum, and the glycogen material under nitrogen atmosphere, carries out the polyvalent alcohol product that hydrocracking production comprises terepthaloyl moietie, 1,2 Ucar 35 with the successive reactive mode under the aqueous phase, catalyst action; Hydrogen, water, sugared reaction raw materials are in the state of continuous flow; Reactor effluent is gas, liquid, perhaps is gas, liquid, solid two or three states material.When needs controlling reactor elute includes only gas-liquid two phase times, can realize through screen cloth is set at reactor exit, adopt screen cloth to stop the outflow of solid materials.If comprise solid in the reactor effluent, it is a solid-phase catalyst, turns back to reactor drum behind the solid-phase catalyst process separation that exists in the reactor effluent, the activating and regenerating.Reactor drum is gas-liquid-solid three-phase slurry bed, liquid bed or fluidized-bed reactor.
Keep the interior liquor capacity of reactor drum to account for the 1/5-2/3 of reactor volume in the reaction process.Reactor effluent separates through three-phase (gas, liquid, solid) separator or gas-liquid separator; The separator eluting gas is sent into film separation unit, and film separation unit is isolated high concentration of hydrogen entraining air stream thigh and speeded the bleed flow thigh, and the hydrogen gas stream thigh is the Returning reactor recycle from the feed(raw material)inlet; If comprise solid in the reactor effluent, it be a solid-phase catalyst, and separator outflow solid is recycle in the Returning reactor again after separation;
Separator flowing liquid separated into two parts, a part of flowing liquid is sent to refining separation system, obtains the highly purified polyvalent alcohol product that comprises terepthaloyl moietie, 1,2 Ucar 35, and said refining separation system is a rectifying tower; Another part flowing liquid directly turns back to reactor drum.Rectifying and backflow two portions volume ratio are 10/1 to 1/2, and the preferred volume ratio is 6/1 to 1/1.
The reaction liquid of Returning reactor is used for the diluting effect to fresh reactant glycogen material; Thereby avoid the sintering phenomenon of high concentration sugar raw material in reaction to take place, and, realized the pump circulation of reaction solution; Increase the mass-and heat-transfer effect of material, and be convenient to the drag-out of control catalyst;
After reactor drum flowing liquid entering distillation system is isolated the polyvalent alcohol product, have at least part heavy constituent polyvalent alcohol and unreacted carbohydrate Returning reactor to carry out further hydrocracking reaction in the residue heavy constituent product, another partly emits; The heavy constituent polyvalent alcohol of Returning reactor and unreacted carbohydrate reflux mass ratio be limited to 1/10 to 4/5 up and down; Heavy constituent polyvalent alcohol and unreacted carbohydrate turn back to the process of recycle in the reactor drum and be in the residue heavy constituent product: the direct backflow through residue heavy constituent product is accomplished; And/or after will being present in the polyvalent alcohol and unreacted carbohydrate process Separation and Recovery in the residue heavy constituent product, turn back to recycle in the reactor drum whole or in part.
The catalyst activity B component exists solubility and insolubility two states when reaction is initial.Yet along with the prolongation in reaction times, the active ingredient B of insolubility can dissolve gradually equally and be lost in the reaction solution.The active ingredient B of this The dissolved still has catalytic activity.Thereby; After reactor drum flowing liquid entering distillation system is isolated the polyvalent alcohol product; The soluble catalyst active ingredient B that is present in the residue heavy constituent product turns back to recycle in the reactor drum at least in part, soluble catalyst active ingredient B reflux mass ratio be limited to 1/10 to 4/5 up and down;
Soluble catalyst active ingredient B turns back to the process of recycle in the reactor drum and is in the residue heavy constituent product: the direct backflow through residue heavy constituent product is accomplished; And/or after will being present in the soluble catalyst active ingredient B process Separation and Recovery in the residue heavy constituent product, turn back to recycle in the reactor drum whole or in part; The new benefit of reactive system is gone into soluble catalyst active ingredient B, and its amount is suitable with the amount of the catalyst activity B component that emits with distillation system separating heavy product.
Said employing dual-active property component catalyst comprises catalytic active component A and catalytic active component B, and active component A and active ingredient B both can be supported on the common carrier, 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, and catalytic active component B comprises one or more in mineral compound, organic cpds, complex compound or the tungsten simple substance of tungsten; The catalyzer that adds in the reactor drum comprises catalytic active component A; If catalytic active component B is a solid, it also adds in the reactor drum with catalytic active component A equally in advance; If catalytic active component B is a liquid, can before charging, all or partly add reactor drum in advance in advance, also can all or partly add by pump with the reaction raw materials sugar soln.
In the reaction process, the weight ratio scope of glycogen material is 1/1000-1/2 in amount and the reactor drum of catalyst activity component A in reactor drum; 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.
Hydrocracking reaction is operated under 1-15MPa; Temperature of reaction >=120 ℃, thermolysis does not take place with product and is as the criterion in upper temperature limit.The hydrogen cracking preferable reaction temperature is 180-260 ℃; Preferred hydrogen pressure 5-12MPa.
The invention has the beneficial effects as follows:
1) realized the continuous input of reactant feed; The continuous output of terepthaloyl moietie, propanediol product; Compare with the intermittent reaction process, the reaction process of having avoided periodical operation to cause stops, and has significantly improved production efficiency on the one hand; Practice thrift hydrogen consumption and energy expenditure on the other hand, thereby reduced production cost on the whole.
2) way through adopting partial reaction liquid to reflux is utilized the diluting effect of back flow reaction liquid to the fresh reactant raw material, has avoided the sintering phenomenon of high concentration sugar raw material in reaction to take place.Simultaneously, realized the pump circulation of reaction solution, increased the mass-and heat-transfer effect of material, reduced the reaction dead angle and exist, and be convenient to the drag-out of control catalyst.
3) through reclaiming and partial reflux soluble catalyst active ingredient B, reduce the consumption of catalyzer, practiced thrift the catalyzer use cost, also solved catalyst activity component losing issue simultaneously.
4), increased carrying out degree, having improved the total recovery of product of reaction to the backflow of partial reaction liquid and polyvalent alcohol and sugar component and secondary response again.
5) solid-phase catalyst has adopted external circulation mode, is convenient in process of production activating and regenerating and periodic replacement that stopped reaction not can be realized catalyzer.
Description of drawings
Fig. 1 is a process flow sheet of the present invention.
Embodiment
Embodiment further specifies the present invention below in conjunction with accompanying drawing
Embodiment 1
The glucose of 50wt% and the ammonium metawolframate 0.1wt% of The dissolved (in the tungsten weight) aqueous solution are got into hydrogenator by HPP; (weight ratio of ruthenium and tungsten is 1: 10 to be filled with Ru/AC and the tungstic acid catalyst of slurry attitude in the reactor drum; Be solvent submergence catalyzer with water when reacting initial); The weight ratio of glycogen material and catalyzer (ruthenium and W elements weight sum) is between 450: 1 to 460: 1, and volume space velocity is 2 to 3.The temperature of reactor drum is 220-230 ℃, and hydrogen pressure is 5MPa.Hydrogen is got into by reactor bottom, and stirs catalyst slurry.Reaction solution gets into reactor drum and exports discharging through the reaction back by the reactor drum middle and upper part, together discharges with 1wt% solid catalyst (Ru/AC), hydrogen partial and gaseous product simultaneously.Reactor effluent entering separator separates goes out gas, liquid and solid three parts subsequently.
The gas part that separator separates goes out is further isolated pure hydrogen by film separating system, mixes with the fresh hydrogen of replenishing after return hydrocracking reactor after the recycle gas compressor compression.The discharging of hydro carbons such as remaining hydrogen in the membrane sepn residual gas and a small amount of carbon monoxide that comprises, methane, ethane, propane is burnt or is used for heat supply.
After the solid catalyst process regenerated from washing activation that separator separates goes out, in the Returning reactor.
The liquid 9/10 that separator separates goes out gets into the rectifying separation system, isolates terepthaloyl moietie, 1, and 2-Ucar 35, other polyvalent alcohols comprise the 1-propyl alcohol, and 1,2-butyleneglycol, 1,3 butylene glycol, glycerine etc.The sugar that the remaining heavy constituent of rectifying separation system comprise sorbyl alcohol, N.F,USP MANNITOL, do not transform fully, and the tungstate ion of dissolved catalyst activity B component wherein in 4/5 Returning reactor, carry out further catalyzed conversion.Tungstate ion in the remaining 1/5 rectifying heavy constituent reclaims through the method for deposition and IX.
Other 1/10 liquid of the liquid that separator separates goes out directly is back to reactor drum, reducing the concentration of glycogen material at the feed entrance place, thereby avoids the coking polymery of sugared reaction raw materials.
Listed the result data of reaction in the table 1.This result has embodied in the continous way sugar catalytic conversion process, and reaction has high sugared transformation efficiency and high terepthaloyl moietie and 1,2-Ucar 35 yield.
Table 1 tandem reaction sequence sugar catalyzed conversion preparing ethylene glycol Ucar 35 reaction result
Figure BDA0000071708410000051
Embodiment 2
The glucose of 40wt% and the ammonium metawolframate 0.05wt% of The dissolved (in the tungsten weight) aqueous solution are got into hydrogenator by HPP; (weight ratio of ruthenium and tungsten is 1: 5 to be filled with Ru/AC and the tungstic acid catalyst of slurry attitude in the reactor drum; Be solvent submergence catalyzer with water when reacting initial); The weight ratio of glycogen material and catalyzer (ruthenium and W elements weight sum) is between 800: 1 to 750: 1, and volume space velocity is 10 to 20.The temperature of reactor drum is 250-260 ℃, and hydrogen pressure is 6MPa.Hydrogen is got into by reactor bottom, and stirs catalyst slurry.Reaction solution gets into reactor drum and exports discharging through the reaction back by the reactor drum middle and upper part, together discharges with hydrogen partial and gaseous product simultaneously.Reactor effluent entering separator separates goes out gas, liquid portion subsequently.
The gas part that separator separates goes out is further isolated pure hydrogen by film separating system, mixes with the fresh hydrogen of replenishing after return hydrocracking reactor after the recycle gas compressor compression.The discharging of hydro carbons such as remaining hydrogen in the membrane sepn residual gas and a small amount of carbon monoxide that comprises, methane, ethane, propane is burnt or is used for heat supply.
The liquid 1/2 that separator separates goes out gets into the rectifying separation system, isolates terepthaloyl moietie, 1, and 2-Ucar 35, other polyvalent alcohols comprise the 1-propyl alcohol, and 1,2-butyleneglycol, 1,3 butylene glycol, glycerine etc.The sugar that the remaining heavy constituent of rectifying separation system comprise sorbyl alcohol, N.F,USP MANNITOL, do not transform fully, and the tungstate ion of dissolved catalyst activity B component wherein in 4/5 Returning reactor, carry out further catalyzed conversion.Tungstate ion in the remaining 1/5 rectifying heavy constituent reclaims through the method for deposition and IX.
Other 1/2 liquid of the liquid that separator separates goes out directly is back to reactor drum, reducing the concentration of glycogen material at the feed entrance place, thereby avoids the coking polymery of sugared reaction raw materials.
Listed the result data of reaction in the table 2.This result has embodied in the continous way sugar catalytic conversion process, and reaction has high sugared transformation efficiency and high terepthaloyl moietie and 1,2-Ucar 35 yield.
Table 2 tandem reaction sequence sugar catalyzed conversion preparing ethylene glycol Ucar 35 reaction result
Figure BDA0000071708410000061
Figure BDA0000071708410000071
Embodiment 3
The glucose of 60wt% and the ammonium metawolframate 0.2wt% of The dissolved (in the tungsten weight) aqueous solution are got into hydrogenator by HPP; (weight ratio of ruthenium and tungsten is 1: 1 to be filled with Ru/AC and the tungstic acid catalyst of slurry attitude in the reactor drum; Be solvent submergence catalyzer with water when reacting initial); The weight ratio of glycogen material and catalyzer (ruthenium and W elements weight sum) is 150: 1, and volume space velocity is 70 to 80.The temperature of reactor drum is 240-250 ℃, and hydrogen pressure is 10MPa.Hydrogen is got into by reactor bottom, and stirs catalyst slurry.Reaction solution gets into reactor drum and exports discharging through the reaction back by the reactor drum middle and upper part, together discharges with part (0.5-2wt%) solid catalyst (Ru/AC), hydrogen partial and gaseous product simultaneously.Reactor effluent entering separator separates goes out gas, liquid and solid three parts subsequently.
The gas part that separator separates goes out is further isolated pure hydrogen by film separating system, mixes with the fresh hydrogen of replenishing after return hydrocracking reactor after the recycle gas compressor compression.The discharging of hydro carbons such as remaining hydrogen in the membrane sepn residual gas and a small amount of carbon monoxide that comprises, methane, ethane, propane is burnt or is used for heat supply.
After the solid catalyst process regenerated from washing activation that separator separates goes out, in the Returning reactor.
The liquid 3/5 that separator separates goes out gets into the rectifying separation system, isolates terepthaloyl moietie, 1, and 2-Ucar 35, other polyvalent alcohols comprise the 1-propyl alcohol, and 1,2-butyleneglycol, 1,3 butylene glycol, glycerine etc.The sugar that the remaining heavy constituent of rectifying separation system comprise sorbyl alcohol, N.F,USP MANNITOL, do not transform fully, and the tungstate ion of dissolved catalyst activity B component wherein in 1/2 Returning reactor, carry out further catalyzed conversion.Tungstate ion in the remaining 1/2 rectifying heavy constituent reclaims through the method for deposition and IX.
Other 2/5 liquid of the liquid that separator separates goes out directly is back to reactor drum, reducing the concentration of glycogen material at the feed entrance place, thereby avoids the coking polymery of sugared reaction raw materials.
Listed the result data of reaction in the table 3.This result has embodied in the continous way sugar catalytic conversion process, and reaction has high sugared transformation efficiency and high terepthaloyl moietie and 1,2-Ucar 35 yield.
Table 3 tandem reaction sequence sugar catalyzed conversion preparing ethylene glycol Ucar 35 reaction result
Figure BDA0000071708410000072
Figure BDA0000071708410000081

Claims (10)

1.连续加氢裂解糖转化生产乙二醇及1,2-丙二醇的方法，其特征在于： 1. The method for continuous hydrocracking sugar conversion to produce ethylene glycol and 1,2-propanediol, characterized in that: 1）于反应器中，在氢气氛下，浓度5-80 wt%糖原料水溶液中，在催化剂作用下进行加氢裂解生产包括乙二醇、1,2丙二醇的多元醇产品；氢气、水、糖原料处于连续流动的状态，氢气、糖原料水溶液从原料入口流入反应器；反应过程的混合物料从反应器出口流出反应器，其为反应器流出物；反应器流出物为气体、液体，或者为气体、液体、固体的两种或三种状态物质； 1) In a reactor, under a hydrogen atmosphere, in an aqueous solution of sugar raw materials with a concentration of 5-80 wt%, carry out hydrocracking under the action of a catalyst to produce polyol products including ethylene glycol and 1,2 propanediol; hydrogen, water, The sugar raw material is in a state of continuous flow, hydrogen gas and sugar raw material aqueous solution flow into the reactor from the raw material inlet; the mixed material in the reaction process flows out of the reactor from the reactor outlet, which is the reactor effluent; the reactor effluent is gas, liquid, or Substances in two or three states of gas, liquid, and solid; 反应过程中保持反应器内溶液体积占反应器体积的1/5-2/3； During the reaction process, keep the volume of the solution in the reactor accounting for 1/5-2/3 of the reactor volume; 2）反应器流出物通过三相（气体、液体、固体）分离器或气液分离器进行分离； 2) The reactor effluent is separated by a three-phase (gas, liquid, solid) separator or a gas-liquid separator; 分离器流出气体送入膜分离单元，膜分离单元分离出高浓度氢气气流股和驰放气流股，氢气气流股从原料入口返回反应器循环利用； The effluent gas from the separator is sent to the membrane separation unit, and the membrane separation unit separates the high-concentration hydrogen gas stream and the purge gas stream, and the hydrogen gas stream returns to the reactor from the raw material inlet for recycling; 若反应器流出物中包含固体，其为固相催化剂，分离器流出固体在分离后重新返回反应器中循环利用； If the reactor effluent contains solids, it is a solid-phase catalyst, and the solids effluent from the separator are separated and returned to the reactor for recycling; 分离器流出液体分成两部分，一部分流出液体送入到精制分离系统，得到高纯度的包括乙二醇、1,2丙二醇的多元醇产品产品；另一部分流出液体直接返回到反应器； The effluent liquid from the separator is divided into two parts, one part of the effluent liquid is sent to the refining separation system to obtain high-purity polyol products including ethylene glycol and 1,2 propylene glycol; the other part of the effluent liquid is directly returned to the reactor; 3）反应器流出液体进入精馏系统分离出多元醇产品后，剩余重组分产物中至少有部分重组分多元醇及未反应的糖类返回反应器进行进一步加氢裂化反应，另一部份排放掉；返回反应器的重组分多元醇及未反应的糖类回流质量比例的上下限为1/10至4/5； 3) After the effluent liquid from the reactor enters the rectification system to separate the polyol products, at least part of the heavy component polyols and unreacted sugars in the remaining heavy component products are returned to the reactor for further hydrocracking reaction, and the other part is discharged drop; the upper and lower limits of the mass ratio of heavy component polyols and unreacted sugar reflux returned to the reactor are 1/10 to 4/5; 剩余重组分产物中重组分多元醇及未反应的糖类返回到反应器中循环利用的过程为：通过剩余重组分产物的直接回流完成，和/或将存在于剩余重组分产物中的多元醇及未反应的糖类经过分离回收后，全部或部分地返回到反应器中循环利用； The process of returning the heavy component polyols and unreacted sugars in the remaining heavy component products to the reactor for recycling is: through the direct reflux of the remaining heavy component products, and/or the polyols present in the remaining heavy component products After separation and recovery of unreacted sugars, all or part of them are returned to the reactor for recycling; 4）反应器流出液体进入精馏系统分离出多元醇产品后，存在于剩余重组分产物中的可溶性催化剂活性组分B至少部分地返回到反应器中循环利用，可溶性催化剂活性组分B回流质量比例的上下限为1/10至4/5； 4) After the effluent liquid from the reactor enters the rectification system to separate the polyol product, the soluble catalyst active component B present in the remaining heavy component product is at least partially returned to the reactor for recycling, and the soluble catalyst active component B reflux quality The upper and lower limits of the ratio are 1/10 to 4/5; 剩余重组分产物中可溶性催化剂活性组分B返回到反应器中循环利用的过程为：通过剩余重组分产物的直接回流完成，和/或将存在于剩余重组分产物中的可溶性催化剂活性组分B经过分离回收后，全部或部分地返回到反应器中循环利用； The process of returning the soluble catalyst active component B in the remaining heavy component product to the reactor for recycling is: through the direct reflux of the remaining heavy component product, and/or the soluble catalyst active component B present in the remaining heavy component product After separation and recovery, all or part of it is returned to the reactor for recycling; 5）反应系统新补入可溶性催化剂活性组分B，其量与随精馏系统分离重组分产物排放掉的催化剂活性组分B的量相当； 5) The reaction system is newly supplemented with soluble catalyst active component B, and its amount is equivalent to the amount of catalyst active component B discharged with the separation of heavy component products in the rectification system; 6）所述采用双活性组分催化剂，包括催化活性组分A和催化活性组分B，活性组分A和活性组分B既可以担载在共同载体上，也可以于反应过程中以机械混合的形式构成混合型催化剂；催化活性组分A包括具有催化加氢性能的第8、9、10族的过渡金属铁、钴、镍、钌、铑、钯、铱、铂中的一种或二种以上，催化活性组分B包括钨的无机化合物、有机化合物、络合物或钨单质中的一种或两种以上；反应器中加入的催化剂包括催化活性组分A；如果催化活性组分B为固体，其也与催化活性组分A同样预先加入反应器中；如果催化活性组分B为液体，可以在进料前预先全部或部份预先加入反应器，也可以全部或部份随反应原料糖溶液由泵加入。 6) The dual-active component catalyst is used, including catalytic active component A and catalytic active component B. Active component A and active component B can be loaded on a common carrier, or mechanically The mixed form constitutes a mixed catalyst; the catalytically active component A includes one or more of the transition metal iron, cobalt, nickel, ruthenium, rhodium, palladium, iridium, and platinum of the 8th, 9th, and 10th groups with catalytic hydrogenation properties More than two, the catalytically active component B includes one or more of tungsten inorganic compounds, organic compounds, complexes or tungsten simple substances; the catalyst added to the reactor includes catalytically active component A; if the catalytically active component Component B is a solid, which is also pre-added to the reactor like the catalytically active component A; if the catalytically active component B is a liquid, it can be added to the reactor in advance in whole or in part before feeding, or it can be fully or partially Along with the reaction raw material sugar solution is added by the pump. 2.按照权利要求1所述的的方法，其特征在于：所述催化剂活性组分A在反应器中的量与反应器中糖原料的重量比范围为1/1000-1/2；催化剂活性组分B在反应器中的浓度以钨计为10ppm-50000 ppm ；催化剂活性组分A与B的量的比例关系（加氢金属和金属钨的重量比）范围为0.01-100。 2. according to the described method of claim 1, it is characterized in that: the weight ratio scope of the amount of described catalyst active component A in the reactor and sugar raw material in the reactor is 1/1000-1/2; The concentration of component B in the reactor is 10ppm-50000ppm in terms of tungsten; the proportional relationship between the amount of catalyst active component A and B (weight ratio of hydrogenation metal to metal tungsten) ranges from 0.01-100. 3.按照权利要求1所述的的方法，其特征在于：所述反应器为气液固三相淤浆床、沸腾床或流化床反应器；所述精制分离系统为精馏塔。 3. The method according to claim 1, characterized in that: the reactor is a gas-liquid-solid three-phase slurry bed, ebullating bed or fluidized bed reactor; the refining separation system is a rectification tower. 4.按照权利要求1或2所述的的方法，其特征在于：当需要控制反应器流出物只包括气液二相时，可通过在反应器出口处设置筛网实现，采用筛网阻止固体物料的流出。 4. according to the described method of claim 1 or 2, it is characterized in that: when it is necessary to control the reactor effluent to only include gas-liquid two-phase, it can be realized by setting a screen at the outlet of the reactor, and the screen is used to stop the solid material outflow. 5.按照权利要求1所述的的方法，其特征在于：若反应器流出物中包含固体，其为固相催化剂，反应器流出物中存在的固相催化剂经过分离、活化再生后返回到反应器。 5. according to the described method of claim 1, it is characterized in that: if comprise solid in the reactor effluent, it is solid-phase catalyst, the solid-phase catalyst that exists in the reactor effluent returns to reaction after separation, activation and regeneration. device. 6.按照权利要求1所述的的方法，其特征在于：所述分离器流出液体分成两部分，一部分送入到精制分离系统、另一部分直接返回到反应器中，精馏与回流两部分体积比例在10/1至1/2。 6. according to the described method of claim 1, it is characterized in that: described separator effluent liquid is divided into two parts, and a part is sent to refining separation system, and another part is directly returned in the reactor, rectification and reflux two parts volumes The ratio is 10/1 to 1/2. 7.按照权利要求1所述的的方法，其特征在于：所述分离器流出液体分成两部分，一部分送入到精制分离系统、一部分直接返回到反应器中，精馏与回流两部分优选体积比例在6/1至1/1。 7. according to the described method of claim 1, it is characterized in that: described separator effluent liquid is divided into two parts, and a part is sent to refining separation system, and a part is directly returned in the reactor, rectification and reflux two parts preferably volume The ratio is 6/1 to 1/1. 8.按照权利要求1所述的的方法，其特征在于：所述加氢裂化反应在1-15MPa下操作；反应温度≥120 oC，温度上限以产物不发生热分解为准。 8. The method according to claim 1, characterized in that: the hydrocracking reaction is operated at 1-15 MPa; the reaction temperature is ≥120 o C, and the upper limit of the temperature is subject to the fact that the product does not undergo thermal decomposition. 9.按照权利要求1所述的的方法，其特征在于：所述加氢裂化优选反应温度为180-260 oC；优选氢气压力5-12 MPa。 9. The method according to claim 1, characterized in that: the preferred reaction temperature of the hydrocracking is 180-260 o C; the preferred hydrogen pressure is 5-12 MPa. 10.按照权利要求1所述的的方法，其特征在于：所述糖原料为蔗糖、葡萄糖、果糖、果聚糖、木糖、可溶性低聚木糖、淀粉中的一种或二种以上。 10. The method according to claim 1, characterized in that: the sugar raw material is one or more of sucrose, glucose, fructose, fructan, xylose, soluble xylooligosaccharides, and starch.
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