CN102643165B - 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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- 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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- C07—ORGANIC CHEMISTRY
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- 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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- B01J23/38—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
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- 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
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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 the technological process of a kind of sugar soln preparing ethylene glycol, 1,2-PD, specifically a kind of shortening cracking carbohydrate transforms the continuous reaction technological process of producing ethylene glycol and 1,2 propylene glycol.
Background technology
Ethylene glycol (being called for short EG) has another name called glycol, ethylene glycol, it is a kind of important petrochemical complex basic organic material, mainly for the production of trevira, frostproofer, unsaturated polyester resin, lubricant, softening agent, nonionogenic tenside and explosive etc., can be used in addition the industries such as coating, soup, brake fluid and ink, as solvent and the medium of ammonium pertorate, for the production of special solvent glycol ether etc., purposes is very extensive.
It is the legal operational path of pressurized water that the suitability for industrialized production of current domestic and international large-scale ethylene glycol all adopts oxyethane direct hydration, production technology is controlled [document 1: Cui little Ming by English lotus Shell, U.S. Halcon-SD and U.S. UCC tri-companies substantially, Ethylene Glycol 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 ethylene glycol such as trevira, polyester plastics and deicing fluid, people start to be devoted to the research-and-development activity of the new synthetic technology of ethylene glycol.Shell company, UCC company, Moscow Mendelyeev chemical engineering institute etc. have developed catalyzing epoxyethane hydration legal system ethylene glycol production technology in succession; The companies such as Halcon-SD, UCC, Dow chemistry, Japanese catalyst chemistry and Mitsubishi Chemical have developed NSC 11801 legal system ethylene glycol production technology in succession; In addition, because the shortage of world petroleum resource is relative with natural gas source abundant, the companies such as U.S. UCC and Ube Industries Ltd. have also carried out the research-and-development activity by coal based synthetic gas preparing ethylene glycol novel process.
1,2-PD is the raw material of manufacturing unsaturated polyester resin, epoxy resin, urethane resin; Also be to produce tensio-active agent as the intermediate of 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 auxiliary and the water-soluble ointment of injection; Aspect paint, pigment, detergents and cosmetic, propylene glycol is raw material, solvent and the tackifier (as for toothpaste) etc. of producing softening agent.
1,2-PD (PG) accounts for 27% for unsaturated polyester resin processed (for topcoating and galss fiber reinforced resin); Functional fluid processed (deicing fluid, the agent of change ice, heat transfer liquid) accounts for 2%; Food processed, medicine and makeup account for 20%; Liquid washing agent processed accounts for 17%; Liquefaction paint and coating account for 5%; Tobacco humectant processed accounts for 2%; Other purposes, comprises softening agent, accounts for 9%.The application of propylene glycol aspect makeup and liquid washing agent increases still very fast, and annual growth is respectively 3% and 3.5%.Cosmetics production business is the moisturizing composition as individual health care product by it, and these healthcare products have antiperspirant, reodorant, sunblock lotion, shaving cream and beauty cream.In liquid washing agent, propylene glycol plays the effect of enzyme stabilizers and solvent.
An Industrialized processing technique part for 1,2-PD, take propylene oxide as raw material production route, is mainly propylene oxide direct hydration method, the indirect hydration method of propylene oxide at present; A part, take propylene as raw material production route, is mainly propylene Direct Catalytic Oxidation method; With biomass material production line, comprise glycerine hydrogenation evaporation, sorbyl alcohol high temperature hydrogenation cracking process; Other is methylcarbonate/propylene glycol co-production method.
Along with fossil energy resource (comprising oil, coal, Sweet natural gas etc.) is more and more deficienter, adopt renewable resources to produce the status of main chemical more and more important.Carbohydrate is a kind of renewable energy source, including but not limited to, one or two or more kinds in sucrose, glucose, fructose, wood sugar, solubility xylo-oligosaccharide, starch, it can be supplied raw materials for some chemical (as ethylene glycol, 1,2-PD).[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 ethylene glycol, CN200610068869.5 document 6: a kind of method of being produced dibasic 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 propylene glycol in step reactor, 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 consuming time, operation inconvenience not only, and waste energy and material.Thereby, for ease of heavy industrialization application, reduce running cost, improve reaction efficiency, develop efficient continuous reaction technological process 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 ethylene glycol and 1,2 propylene glycol.
For achieving the above object, the technical solution used in the present invention is: reaction process comprises that reaction-ure feeding, catalyzed reaction, reactor stream go out the separation of gas liquid solid, gas recovery, soluble catalyst recovery, reaction solution backflow, the several links of product purification.
For completing these reaction links, adopt the reaction process shown in Figure of description 1.
Glycogen material is one or two or more kinds in sucrose, glucose, fructose, Polylevulosan, wood sugar, solubility xylo-oligosaccharide, starch.In reactor, glycogen material concentration of aqueous solution is 5-80wt%, and glycogen material, in water, carries out hydrocracking and produces the polyvalent alcohol product that comprises ethylene glycol, 1,2 propylene glycol with continuous reactive mode under nitrogen atmosphere under catalyst action; Hydrogen, water, the state of sugared reaction raw materials in continuous flow; Reactor effluent is gas, liquid, or is the two or three states material of gas, liquid, solid.In the time that needs are controlled reactor effluent and are only included gas-liquid two-phase, can realize by screen cloth is set at reactor exit, adopt screen cloth to stop the outflow of solid materials.If comprise solid in reactor effluent, it is solid-phase catalyst, and the solid-phase catalyst existing in reactor effluent turns back to reactor after separation, activating and regenerating.Reactor is gas-liquid-solid three-phase slurry bed, ebullated bed or fluidized-bed reactor.
In reaction process, keep the interior liquor capacity of reactor to account for the 1/5-2/3 of reactor volume.Reactor effluent separates by three-phase (gas, liquid, solid) separator or gas-liquid separator; Separator eluting gas is sent into film separation unit, and film separation unit is isolated high concentration of hydrogen entraining air stream thigh and the bleed flow thigh of speeding, and hydrogen gas stream thigh is from feed(raw material)inlet Returning reactor recycle; If comprise solid in reactor effluent, it is solid-phase catalyst, and separator flows out solid and after separation, returns to recycle in reactor;
Separator flowing liquid is divided into two portions, and a part of flowing liquid is sent to refining separation system, obtains the highly purified polyvalent alcohol product that comprises ethylene glycol, 1,2 propylene glycol, and described refining separation system is rectifying tower; Another part flowing liquid directly turns back to reactor.Rectifying and backflow two portions volume ratio are 10/1 to 1/2, and preferred volume ratio is 6/1 to 1/1.
The reaction liquid of Returning reactor is for the diluting effect to fresh reactant glycogen material, thereby avoid the sintering phenomenon of high concentration sugar raw material in reaction to occur, and, realize the pump circulation of reaction solution, increase the mass-and heat-transfer effect of material, and be convenient to control the drag-out of catalyzer;
Reactor flowing liquid enters distillation system and isolates after polyvalent alcohol product, has at least part heavy constituent polyvalent alcohol and unreacted carbohydrate Returning reactor to carry out further hydrocracking reaction in residual gravity component product, and another part emits; The heavy constituent polyvalent alcohol of Returning reactor and unreacted carbohydrate reflux mass ratio be limited to up and down 1/10 to 4/5; In residual gravity component product, heavy constituent polyvalent alcohol and unreacted carbohydrate turn back to the process of recycle in reactor and are: the direct backflow by residual gravity component product completes, and/or by being present in polyvalent alcohol in residual gravity component product and unreacted carbohydrate after Separation and Recovery, turn back to whole or in part recycle in reactor.
In the time that reaction is initial, there is solubility and insolubility two states in catalyst activity B component.But, along with the prolongation in reaction times, the active ingredient B of insolubility equally gradually loss by dissolution in reaction solution.The active ingredient B of this solubilised state still has catalytic activity.Thereby, reactor flowing liquid enters distillation system and isolates after polyvalent alcohol product, the soluble catalyst active ingredient B being present in residual gravity component product turns back to recycle in reactor at least in part, soluble catalyst active ingredient B reflux mass ratio be limited to up and down 1/10 to 4/5;
In residual gravity component product, soluble catalyst active ingredient B turns back to the process of recycle in reactor and is: the direct backflow by residual gravity component product completes, and/or by being present in soluble catalyst active ingredient B in residual gravity component product after Separation and Recovery, turn back to whole or in part recycle in reactor; Reactive system newly fills into soluble catalyst active ingredient B, and its amount is suitable with the amount of the catalyst activity B component emitting with distillation system separating heavy product.
Described employing double activated 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 common carrier, also can in reaction process, the form with mechanically mixing form mixed catalyst; Catalytic active component A comprises one or two or more kinds in the transition metal iron, cobalt, nickel, ruthenium, rhodium, palladium, iridium, platinum of the 8th, 9,10 families with Catalytic Hydrogenation Properties, and catalytic active component B comprises one or more in mineral compound, organic compound, complex compound or the tungsten simple substance of tungsten; The catalyzer adding in reactor comprises catalytic active component A; If catalytic active component B is solid, it is in advance add in reactor same with catalytic active component A also; If catalytic active component B is liquid, can before charging, all or partly add in advance in advance reactor, also can all or partly be added by pump with reaction raw materials sugar soln.
In reaction process, in the amount of catalyst activity component A in reactor and reactor, the weight ratio scope of glycogen material is 1/1000-1/2; The concentration of catalyst activity B component in reactor is counted 10ppm-50000ppm with tungsten; Proportionlity (weight ratio of hydrogenation metal and the tungsten) scope of the amount of catalyst activity component A and B is 0.01-100.
Hydrocracking reaction operates under 1-15MPa; Temperature of reaction >=120 ℃, there is not thermolysis with product and are as the criterion in upper temperature limit.Hydrocracking preferable reaction temperature is 180-260 ℃; Preferably hydrogen pressure 5-12MPa.
The invention has the beneficial effects as follows:
1) realized the continuous input of reactant feed, the continuous output of ethylene glycol, propanediol product, compare with intermittent reaction process, the reaction process of having avoided periodical operation to cause stops, significantly improve on the one hand production efficiency, save on the other hand hydrogen consumption and energy expenditure, thereby reduced on the whole production cost.
2) by the way that adopts partial reaction liquid to reflux, utilize the diluting effect of back flow reaction liquid to fresh reactant raw material, avoided the sintering phenomenon of high concentration sugar raw material in reaction to occur.Meanwhile, realize the pump circulation of reaction solution, increased the mass-and heat-transfer effect of material, reduced reaction dead angle and exist, and be convenient to control the drag-out of catalyzer.
3) by reclaiming and partial reflux soluble catalyst active ingredient B, reduce the consumption of catalyzer, saved catalyzer use cost, also solved catalyst activity component losing issue simultaneously.
4) backflow to partial reaction liquid and polyvalent alcohol and sugar component and again secondary response, increased carrying out degree, having improved the total recovery of product of reaction.
5) solid-phase catalyst has adopted the mode of outer circulation, is convenient in process of production stopped reaction not and can realizes activating and regenerating and the periodic replacement of catalyzer.
Accompanying drawing explanation
Fig. 1 is process flow sheet of the present invention.
Embodiment
Below in conjunction with accompanying drawing embodiment, the present invention is further described
Embodiment 1
The ammonium metawolframate 0.1wt% of the glucose of 50wt% and solubilised state (with the tungsten weighing scale) aqueous solution is entered to hydrogenator by high-pressure pump, (weight ratio of ruthenium and tungsten is 1: 10 in reactor, to be filled with the slurry Ru/AC of state and tungstic acid catalyst, while reacting initial take water as solvent submergence catalyzer), 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 is 220-230 ℃, and hydrogen pressure is 5MPa.Hydrogen is entered by reactor bottom, and stirs catalyst slurry.Reaction solution enters reactor and is discharged by the outlet of reactor middle and upper part after reaction, together discharges with 1wt% solid catalyst (Ru/AC), hydrogen partial and gaseous product simultaneously.Following reaction device effluent enters separator and isolates gas, liquid and solid three parts.
The isolated gas part of separator is further isolated pure hydrogen by film separating system, after mixing, after recycle gas compressor compression, returns to hydrocracking reactor with supplementary fresh hydrogen.The hydro carbons such as the remaining hydrogen in membrane sepn residual gas and a small amount of carbon monoxide comprising, methane, ethane, propane discharge burning or for heat supply.
The isolated solid catalyst of separator is after regenerated from washing activation, in Returning reactor.
The isolated liquid 9/10 of separator enters rectifying separation system, isolates ethylene glycol, 1,2-PD, other polyvalent alcohols and comprises 1-propyl alcohol, 1,2-butyleneglycol, 1,3 butylene glycol, glycerine etc.The heavy constituent of rectifying separation system spare comprises sorbyl alcohol, N.F,USP MANNITOL, the sugar that do not transform completely, and the tungstate ion of the catalyst activity B component of dissolving, and wherein, in 4/5 Returning reactor, carries out further catalyzed conversion.Tungstate ion in remaining 1/5 rectifying heavy constituent reclaims by the method for precipitation and ion-exchange.
Other 1/10 liquid of the isolated liquid of separator is directly back to reactor, to reduce the concentration of glycogen material at feed entrance place, thereby avoids the coking polymerism of sugared reaction raw materials.
In table 1, list the result data of reaction.This result has embodied in continous way sugar catalytic conversion process, and reaction has high sugared transformation efficiency and high ethylene glycol and 1,2-PD yield.
Table 1 tandem reaction sequence sugar catalyzed conversion preparing ethylene glycol propylene glycol reaction result
Embodiment 2
The ammonium metawolframate 0.05wt% of the glucose of 40wt% and solubilised state (with the tungsten weighing scale) aqueous solution is entered to hydrogenator by high-pressure pump, (weight ratio of ruthenium and tungsten is 1: 5 in reactor, to be filled with the slurry Ru/AC of state and tungstic acid catalyst, while reacting initial take water as solvent submergence catalyzer), 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 is 250-260 ℃, and hydrogen pressure is 6MPa.Hydrogen is entered by reactor bottom, and stirs catalyst slurry.Reaction solution enters reactor and is discharged by the outlet of reactor middle and upper part after reaction, together discharges with hydrogen partial and gaseous product simultaneously.Following reaction device effluent enters separator and isolates gas, liquid portion.
The isolated gas part of separator is further isolated pure hydrogen by film separating system, after mixing, after recycle gas compressor compression, returns to hydrocracking reactor with supplementary fresh hydrogen.The hydro carbons such as the remaining hydrogen in membrane sepn residual gas and a small amount of carbon monoxide comprising, methane, ethane, propane discharge burning or for heat supply.
The isolated liquid 1/2 of separator enters rectifying separation system, isolates ethylene glycol, 1,2-PD, other polyvalent alcohols and comprises 1-propyl alcohol, 1,2-butyleneglycol, 1,3 butylene glycol, glycerine etc.The heavy constituent of rectifying separation system spare comprises sorbyl alcohol, N.F,USP MANNITOL, the sugar that do not transform completely, and the tungstate ion of the catalyst activity B component of dissolving, and wherein, in 4/5 Returning reactor, carries out further catalyzed conversion.Tungstate ion in remaining 1/5 rectifying heavy constituent reclaims by the method for precipitation and ion-exchange.
Other 1/2 liquid of the isolated liquid of separator is directly back to reactor, to reduce the concentration of glycogen material at feed entrance place, thereby avoids the coking polymerism of sugared reaction raw materials.
In table 2, list the result data of reaction.This result has embodied in continous way sugar catalytic conversion process, and reaction has high sugared transformation efficiency and high ethylene glycol and 1,2-PD yield.
Table 2 tandem reaction sequence sugar catalyzed conversion preparing ethylene glycol propylene glycol reaction result
Embodiment 3
The ammonium metawolframate 0.2wt% of the glucose of 60wt% and solubilised state (with the tungsten weighing scale) aqueous solution is entered to hydrogenator by high-pressure pump, (weight ratio of ruthenium and tungsten is 1: 1 in reactor, to be filled with the slurry Ru/AC of state and tungstic acid catalyst, while reacting initial take water as solvent submergence catalyzer), 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 is 240-250 ℃, and hydrogen pressure is 10MPa.Hydrogen is entered by reactor bottom, and stirs catalyst slurry.Reaction solution enters reactor and is discharged by the outlet of reactor middle and upper part after reaction, together discharges with part (0.5-2wt%) solid catalyst (Ru/AC), hydrogen partial and gaseous product simultaneously.Following reaction device effluent enters separator and isolates gas, liquid and solid three parts.
The isolated gas part of separator is further isolated pure hydrogen by film separating system, after mixing, after recycle gas compressor compression, returns to hydrocracking reactor with supplementary fresh hydrogen.The hydro carbons such as the remaining hydrogen in membrane sepn residual gas and a small amount of carbon monoxide comprising, methane, ethane, propane discharge burning or for heat supply.
The isolated solid catalyst of separator is after regenerated from washing activation, in Returning reactor.
The isolated liquid 3/5 of separator enters rectifying separation system, isolates ethylene glycol, 1,2-PD, other polyvalent alcohols and comprises 1-propyl alcohol, 1,2-butyleneglycol, 1,3 butylene glycol, glycerine etc.The heavy constituent of rectifying separation system spare comprises sorbyl alcohol, N.F,USP MANNITOL, the sugar that do not transform completely, and the tungstate ion of the catalyst activity B component of dissolving, and wherein, in 1/2 Returning reactor, carries out further catalyzed conversion.Tungstate ion in remaining 1/2 rectifying heavy constituent reclaims by the method for precipitation and ion-exchange.
Other 2/5 liquid of the isolated liquid of separator is directly back to reactor, to reduce the concentration of glycogen material at feed entrance place, thereby avoids the coking polymerism of sugared reaction raw materials.
In table 3, list the result data of reaction.This result has embodied in continous way sugar catalytic conversion process, and reaction has high sugared transformation efficiency and high ethylene glycol and 1,2-PD yield.
Table 3 tandem reaction sequence sugar catalyzed conversion preparing ethylene glycol propylene glycol reaction result
Claims (10)
1. continuous hydrogenation cracking sugar transforms the method for producing ethylene glycol and 1,2-PD, it is characterized in that:
1), in reactor, under nitrogen atmosphere, in concentration 5-80wt% sugar aqueous solution of raw material, under catalyst action, carry out hydrocracking and produce the polyvalent alcohol product that comprises ethylene glycol, 1,2 propylene glycol; Hydrogen, water, the state of glycogen material in continuous flow, hydrogen, sugared aqueous solution of raw material are from feed(raw material)inlet inflow reactor; The mixture of reaction process is from reactor outlet outflow reactor, and it is reactor effluent; Reactor effluent is gas, liquid, or is the two or three states material of gas, liquid, solid;
In reaction process, keep the interior liquor capacity of reactor to account for the 1/5-2/3 of reactor volume;
2) reactor effluent separates by triphase separator or gas-liquid separator, and described three-phase is gas, liquid, solid;
Separator eluting gas is sent into film separation unit, and film separation unit is isolated high concentration of hydrogen entraining air stream thigh and the bleed flow thigh of speeding, and hydrogen gas stream thigh is from feed(raw material)inlet Returning reactor recycle;
Solid in reactor effluent, it is solid-phase catalyst, separator flows out solid and after separation, returns to recycle in reactor;
Separator flowing liquid is divided into two portions, and a part of flowing liquid is sent to refining separation system, obtains the highly purified polyvalent alcohol product that comprises ethylene glycol, 1,2 propylene glycol; Another part flowing liquid directly turns back to reactor;
3) reactor flowing liquid enters distillation system and isolates after polyvalent alcohol product, has at least part heavy constituent polyvalent alcohol and unreacted carbohydrate Returning reactor to carry out further hydrocracking reaction in residual gravity component product, and another part emits; The heavy constituent polyvalent alcohol of Returning reactor and unreacted carbohydrate reflux mass ratio be limited to up and down 1/10 to 4/5;
In residual gravity component product, heavy constituent polyvalent alcohol and unreacted carbohydrate turn back to the process of recycle in reactor and are: the direct backflow by residual gravity component product completes, and/or by being present in polyvalent alcohol in residual gravity component product and unreacted carbohydrate after Separation and Recovery, turn back to whole or in part recycle in reactor;
4) reactor flowing liquid enters distillation system and isolates after polyvalent alcohol product, the soluble catalyst active ingredient B being present in residual gravity component product turns back to recycle in reactor at least in part, soluble catalyst active ingredient B reflux mass ratio be limited to up and down 1/10 to 4/5;
In residual gravity component product, soluble catalyst active ingredient B turns back to the process of recycle in reactor and is: the direct backflow by residual gravity component product completes, and/or by being present in soluble catalyst active ingredient B in residual gravity component product after Separation and Recovery, turn back to whole or in part recycle in reactor;
5) reactive system newly fills into soluble catalyst active ingredient B, and its amount is suitable with the amount of the catalyst activity B component emitting with distillation system separating heavy product;
6) adopt double activated component catalyst, comprise catalytic active component A and catalytic active component B, active component A and active ingredient B both can be supported on common carrier, also can in reaction process, the form with mechanically mixing form mixed catalyst; Catalytic active component A is one or two or more kinds in the transition metal iron with the 8th, 9,10 families of Catalytic Hydrogenation Properties, cobalt, nickel, ruthenium, rhodium, palladium, iridium, platinum, one or more in mineral compound, organic compound or tungsten simple substance that catalytic active component B is tungsten; The catalyzer adding in reactor comprises catalytic active component A; If catalytic active component B is solid, it is in advance add in reactor same with catalytic active component A also; If catalytic active component B is liquid, can before charging, all or partly add in advance in advance reactor, also can all or partly be added by pump with reaction raw materials sugar soln.
2. it is characterized in that in accordance with the method for claim 1: in the amount of described catalyst activity component A in reactor and reactor, the weight ratio scope of glycogen material is 1/1000-1/2; The concentration of catalyst activity B component in reactor is counted 10ppm-50000ppm with tungsten; The part by weight relation extents of catalyst activity component A and B is 0.01-100.
3. it is characterized in that in accordance with the method for claim 1: described reactor is gas-liquid-solid three-phase slurry bed, ebullated bed reactor; Described refining separation system is rectifying tower.
4. according to the method described in claim 1 or 2, it is characterized in that: need to control reactor effluent and only include gas-liquid two-phase, realize by screen cloth is set at reactor exit, adopt screen cloth to stop the outflow of solid materials.
5. in accordance with the method for claim 1, it is characterized in that: in reactor effluent, comprise solid, it is solid-phase catalyst, the solid-phase catalyst existing in reactor effluent turns back to reactor after separation, activating and regenerating.
6. in accordance with the method for claim 1, it is characterized in that: described separator flowing liquid is divided into two portions, a part is sent to refining separation system, another part and directly turns back in reactor, and rectifying and backflow two portions volume ratio are 10/1 to 1/2.
7. in accordance with the method for claim 1, it is characterized in that: described separator flowing liquid is divided into two portions, a part is sent to refining separation system, a part and directly turns back in reactor, and rectifying and backflow two portions volume ratio are 6/1 to 1/1.
8. it is characterized in that in accordance with the method for claim 1: described hydrocracking reaction operates under 1-15MPa; Temperature of reaction >=120 ℃, there is not thermolysis with product and are as the criterion in upper temperature limit.
9. it is characterized in that in accordance with the method for claim 1: described hydrocracking reaction temperature is 180-260 ℃; Hydrogen pressure 5-12MPa.
10. it is characterized in that in accordance with the method for claim 1: described glycogen material is one or two or more kinds in sucrose, glucose, fructose, Polylevulosan, wood sugar, solubility xylo-oligosaccharide, starch.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016114660A1 (en) * | 2015-01-13 | 2016-07-21 | Avantium Knowledge Centre B.V. | Process for preparing ethylene glycol from a carbohydrate source |
| WO2016114659A1 (en) * | 2015-01-13 | 2016-07-21 | Avantium Knowledge Centre B.V. | Process for preparing ethylene glycol from a carbohydrate source |
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