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 PDFInfo
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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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- 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
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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
- C07C29/132—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
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
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- 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
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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
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
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
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
Claims (10)
1. continuous hydrogenation cracking sugar transforms and produces terepthaloyl moietie and 1, and the method for 2-Ucar 35 is characterized in that:
1) in reactor drum, under nitrogen atmosphere, in the concentration 5-80 wt% glycogen material aqueous solution, under catalyst action, carries out the polyvalent alcohol product that hydrocracking production comprises terepthaloyl moietie, 1,2 Ucar 35; Hydrogen, water, glycogen material are in the state of continuous flow, and hydrogen, the glycogen material aqueous solution is inflow reactor from the feed(raw material)inlet; The mixture of reaction process is from the reactor outlet outflow reactor, and it is a reactor effluent; Reactor effluent is gas, liquid, perhaps is gas, liquid, solid two or three states material;
Keep the interior liquor capacity of reactor drum to account for the 1/5-2/3 of reactor volume in the reaction process;
2) 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 product that comprises terepthaloyl moietie, 1,2 Ucar 35; Another part flowing liquid directly turns back to reactor drum;
3) 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;
4) 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;
5) 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;
6) 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.
2. according to the described method of claim 1, it is characterized in that: the weight ratio scope of glycogen material is 1/1000-1/2 in amount and the reactor drum of said catalyst activity component A in reactor drum; The concentration of catalyst activity B component in reactor drum is counted 10ppm-50000 ppm 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.
3. according to the described method of claim 1, it is characterized in that: said reactor drum is gas-liquid-solid three-phase slurry bed, liquid bed or fluidized-bed reactor; Said refining separation system is a rectifying tower.
4. according to claim 1 or 2 described methods, it is characterized in that: when needs controlling reactor elute includes only gas-liquid two phase times, can realize, adopt screen cloth to stop the outflow of solid materials through screen cloth is set at reactor exit.
5. according to the described method of claim 1, it is characterized in that: 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.
6. according to the described method of claim 1, it is characterized in that: said separator flowing liquid separated into two parts, a part is sent to refining separation system, another part and directly turns back in the reactor drum, and rectifying and backflow two portions volume ratio are 10/1 to 1/2.
7. according to the described method of claim 1; It is characterized in that: said separator flowing liquid separated into two parts; A part is sent to refining separation system, a part and directly turns back in the reactor drum, and rectifying and backflow two portions preferred volume ratio are 6/1 to 1/1.
8. according to the described method of claim 1, it is characterized in that: said hydrocracking reaction is operated under 1-15MPa; Temperature of reaction>=120
oThermolysis does not take place with product and is as the criterion in C, upper temperature limit.
9. according to the described method of claim 1, it is characterized in that: said hydrogen cracking preferable reaction temperature is 180-260
oC; Preferred hydrogen pressure 5-12 MPa.
10. according to the described method of claim 1, it is characterized in that: said glycogen material is a kind of in sucrose, glucose, fructose, Polylevulosan, wood sugar, solubility xylooligosaccharides, the starch or more than two kinds.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110176786.9A CN102643165B (en) | 2011-06-28 | 2011-06-28 | Method for producing ethylene glycol and 1,2-propylene glycol through continuous hydrocrackin of sugars |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110176786.9A CN102643165B (en) | 2011-06-28 | 2011-06-28 | Method for producing ethylene glycol and 1,2-propylene glycol through continuous hydrocrackin of sugars |
Publications (2)
| Publication Number | Publication Date |
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| CN102643165A true CN102643165A (en) | 2012-08-22 |
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Citations (3)
| 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 |
| CN101735014A (en) * | 2008-11-26 | 2010-06-16 | 中国科学院大连化学物理研究所 | Method for preparing ethanediol from polyhydroxy compounds |
| CN101830774A (en) * | 2010-04-13 | 2010-09-15 | 郸城财鑫糖业有限责任公司 | Method for preparing C2-4 dihydric alcohol and polyalcohol from starch raw materials |
-
2011
- 2011-06-28 CN CN201110176786.9A patent/CN102643165B/en active Active
Patent Citations (3)
| 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 |
| CN101735014A (en) * | 2008-11-26 | 2010-06-16 | 中国科学院大连化学物理研究所 | Method for preparing ethanediol from polyhydroxy compounds |
| CN101830774A (en) * | 2010-04-13 | 2010-09-15 | 郸城财鑫糖业有限责任公司 | Method for preparing C2-4 dihydric alcohol and polyalcohol from starch raw materials |
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