CN103608320A - Generation of polyols from saccharides - Google Patents

Generation of polyols from saccharides Download PDF

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Publication number
CN103608320A
CN103608320A CN201280028835.7A CN201280028835A CN103608320A CN 103608320 A CN103608320 A CN 103608320A CN 201280028835 A CN201280028835 A CN 201280028835A CN 103608320 A CN103608320 A CN 103608320A
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China
Prior art keywords
carbohydrate
compound
loading type
catalyst system
raw material
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Pending
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CN201280028835.7A
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Chinese (zh)
Inventor
J·Q·陈
T·N·卡尔奈斯
J·A·科贾尔
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Honeywell UOP LLC
Universal Oil Products Co
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Universal Oil Products Co
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Priority claimed from US13/192,970 external-priority patent/US8222462B2/en
Priority claimed from US13/192,907 external-priority patent/US20110312487A1/en
Application filed by Universal Oil Products Co filed Critical Universal Oil Products Co
Publication of CN103608320A publication Critical patent/CN103608320A/en
Pending legal-status Critical Current

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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
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/18—Carbon
    • 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
    • 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
    • B01J23/6527—Tungsten
    • 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
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/88—Molybdenum
    • B01J23/883—Molybdenum and nickel
    • 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
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/88—Molybdenum
    • B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8871—Rare earth metals or actinides
    • 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
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/888—Tungsten
    • 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
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/888—Tungsten
    • B01J23/8885—Tungsten containing also molybdenum
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
    • B01J27/19—Molybdenum
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/16—Reducing
    • B01J37/18—Reducing with gases containing free hydrogen
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)
  • Saccharide Compounds (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

A process for generating at least one polyol from a feedstock comprising saccharide is performed in a continuous or batch manner. The process involves, contacting, hydrogen, water, and a feedstock comprising saccharide, with a catalyst system to generate an effluent stream comprising at least one polyol and recovering the polyol from the effluent stream. The catalyst system comprises at least one unsupported component and at least one supported component.

Description

By carbohydrate, produce polyvalent alcohol
Prioity claim
The application's case requires the U. S. application the 13/192nd of submitting on July 28th, 2011, No. 907 and the U. S. application the 13/192nd submitted on July 28th, 2011, the right of priority of No. 970, its content all by reference full text be incorporated herein.
Invention field
The present invention relates to catalyst system and use this catalyst system by the method for at least one polyvalent alcohol of raw material production that contains carbohydrate.The method comprises that the raw material that makes hydrogen, water and comprise carbohydrate contacts to produce the effluent that comprises at least one polyvalent alcohol with catalyst system, and from effluent, reclaims polyvalent alcohol.Catalyst system comprise non-loading type catalyst component and supported catalyst component the two.
Background of invention
Polyvalent alcohol is the valuable material for the manufacture of cold weather fluid, makeup, polyester and many other sinteticses.By carbohydrate, replacing the derivative olefin production polyvalent alcohol of fossil oil can be that environment is more friendly and have more the method for economic attractiveness.In the past, by polyol, produced polyvalent alcohol, referring to WO2006/092085 and US2004/0175806.Recently, the catalyzed conversion that changes into ethylene glycol by carbohydrate under the effect of load type carbon compound catalyst is disclosed in Catalysis Today, and 147, in (2009) 77-85.US2010/0256424, US2010/0255983 and WO2010/060345 have instructed by carbohydrate and have prepared the method for ethylene glycol and the tungsten carbide catalyst of this reaction of catalysis.At Angew.Chem.Int.Ed2008,47,8510-8513 and support information and Chem.Commun., announced the successfully batch mode direct catalytic conversion to ethylene glycol for carbohydrate of tungsten carbide catalyst in 2010,46,862-864.At ChemSusChem2010, in 3,63-66, a small amount of nickel is added in tungsten carbide catalyst.Openly for Mierocrystalline cellulose directly being changed into other reference of the catalyzer known in the art of ethylene glycol or propylene glycol, comprise WO2010/060345; US7,767,867; Chem.Commun., 2010,46,6935-6937; Chin.J.Catal., 2006,27 (10): 899-903; And Apcseet UPC20097 thasia Pacific Congress on Sustainable Energy and EnvironmentalTechnologies, " One-pot Conversion of Jerusalem Artichoke Tubers into Polyols ".
Yet, still need effectively carbohydrate directly to be changed into the new catalyst system of polyvalent alcohol, especially need to be more suitable for the catalyst system of fairly large production or continuous production.The catalyst system that comprises at least one non-loading type component and at least one loading type component at least one polyvalent alcohol of raw material production by containing carbohydrate described herein solves this demand.
Summary of the invention
One embodiment of the invention are for changing at least one carbohydrate the catalyst system of polyvalent alcohol, this catalyst system comprises non-loading type component and loading type component, the compound that non-loading type component comprises the group of selecting free tungsten compound, molybdenum compound and its any combination composition, loading type component comprises the active metal component of the group of selecting free Pt, Pd, Ru, Rh, Ni, Ir and combination composition thereof on solid catalyst carrier.Solid catalyst carrier selects free carbon, Al 2o 3, ZrO 2, SiO 2, MgO, Ce xzrO y, TiO 2, the group that forms of SiC, silica alumina (silica alumina), zeolite, clay and combination thereof.The mass ratio of non-loading type component and loading type component is 1:100 to 100:1, the activated metal that wherein loading type component comprises 0.05 quality % to 30 quality %.0.001 quality % to the 20 quality % that in reaction mixture, the concentration of unsupported catalyst component is reaction mixture, 0.001 quality % to the 20 quality % that in reaction mixture, the concentration of loaded catalyst component is reaction mixture.The group that the optional free wolframic acid of non-loading type component of catalyst system, molybdic acid, ammonium metawolframate, the heteropolymer of tungsten, the heteropolymer of the heteropolymer of molybdenum, wolframic acid, the heteropolymer of molybdic acid and combination thereof form.
One embodiment of the invention are the methods by least one polyvalent alcohol of raw material production that comprises carbohydrate, wherein the method comprises and makes hydrogen, water contacts to produce the effluent that comprises at least one polyvalent alcohol with catalyst system with the raw material that comprises at least one carbohydrate, wherein catalyst system comprises non-loading type component and loading type component, non-loading type component comprises selects free tungsten compound, the compound of the group that molybdenum compound and any combination thereof form, loading type component comprises on solid catalyst carrier selects free Pt, Pd, Ru, Rh, Ni, the carried-type active metal component of the group that Ir and combination thereof form, and from effluent, reclaim polyvalent alcohol.The method can batch mode or is operated with continuous-mode operation.
Another embodiment of the invention is the continuation method by least one polyvalent alcohol of raw material production that comprises at least one carbohydrate.The method comprises that the raw material that makes in a continuous manner hydrogen, water and comprise at least one carbohydrate contacts to produce the outflow streams that comprises at least one polyvalent alcohol with catalyst system, and reclaims polyvalent alcohol from flow out streams.Hydrogen, water and raw material flow in a continuous manner.Flowing out streams flows in a continuous manner.The method is the catalysis process that adopts the catalyst system that comprises non-loading type component and loading type component, the compound that non-loading type component comprises the group of selecting free tungsten compound, molybdenum compound and any combination composition thereof, loading type component comprises the carried-type active metal component of the group of selecting free Pt, Pd, Ru, Rh, Ni, Ir and combination composition thereof on solid catalyst carrier.
In one embodiment, contact occurs in the reaction zone at least with the first input material stream and the second input material stream, and the first input material flow to and comprises less the raw material that contains at least one carbohydrate, and the second input material stream comprises hydrogen.The first input material stream can pressurize before entering reaction zone, and the second input material stream can pressurize and heat before entering reaction zone.The first input material stream can pressurize and be heated to the temperature lower than the temperature of carbohydrate thermolysis before entering reaction zone, and the second input material stream can pressurize and heat before entering reaction zone.The first input material stream and the second input material stream further comprise water.
In another embodiment of the invention, the polyvalent alcohol producing is at least ethylene glycol or propylene glycol.Also can produce by product as alcohols, organic acid, aldehydes, monose, disaccharides, oligosaccharide kind, polyose, phenol system compound, hydro carbons, glycerine, depolymerization xylogen and protein.In one embodiment, can be before contacting with catalyzer by for example following technical finesse raw material: sizing, be dried, grinding, hot-water cure, steam treatment, hydrolysis, pyrolysis, thermal treatment, chemical treatment, biological treatment, catalytic treatment or its combination.
Can in following reactor assembly for example, make at least loading type component Continuous Contact of raw material and catalyst system: boiling catalyst bed reactor system, the immobilized catalyst reactor assembly with catalyst channels, pre-reactor system (augured reactor system) and slurry reactor system.The example of operational condition comprises the temperature of 100 ℃ to 350 ℃ and is greater than the hydrogen pressure of 150psig.In one embodiment, the temperature in reactor assembly can be 150 ℃ to 350 ℃, and in another embodiment, the temperature in reactor assembly can be 200 ℃ to 280 ℃.In the reactor assembly that can operate, make raw material and catalyst system Continuous Contact under following condition for example: the weight ratio of water and the raw material that comprises carbohydrate is 1 to 100, the weight ratio of catalyst system (non-loading type component loading type component) and the raw material that comprises carbohydrate is greater than 0.005, pH be less than 10 and the residence time be greater than 5 minutes.In another embodiment, catalyzer is greater than 0.01 with the weight ratio of the raw material that comprises carbohydrate.Can be in the reaction zone operating under the condition of liquid phase, to make hydrogen, water and raw material contact with catalyzer being enough at least to maintain a part of water.
Outflow streams from reactor assembly can further comprise catalyst system, this catalyst system for example can use following technology with flow out material flow point from: direct filtration, sedimentation subsequent filtration, wet cyclone, fractionation, centrifugal, use flocculation agent, precipitation, liquid extraction, absorption, evaporation and combination thereof.Depend on application, loaded catalyst component, unsupported catalyst component or the two can with flow out material flow point from.
Accompanying drawing explanation
Fig. 1 is the basic pattern of the flow scheme of one embodiment of the invention.Do not illustrate and understand the present invention's unwanted equipment of institute and treatment step.
Fig. 2 is the basic pattern of the flow scheme of another embodiment of the invention, the optionally supported type catalyst component disengaging zone that it shows optional pretreating zone and has the recirculation of optionally supported type catalyst component.Do not illustrate and understand the present invention's unwanted equipment of institute and treatment step.
Detailed Description Of The Invention
The present invention relates to catalyst system and for the method for at least one polyvalent alcohol of raw material production by comprising at least one carbohydrate.Catalyst system comprises non-loading type component and loading type component, the compound that non-loading type component comprises the group of selecting free tungsten compound, molybdenum compound and any combination composition thereof, loading type component comprises the active metal component of the group of selecting free Pt, Pd, Ru, Rh, Ni, Ir and combination composition thereof on solid catalyst carrier.The example of suitable solid catalyst carrier comprises carbon, Al 2o 3, ZrO 2, SiO 2, MgO, Ce xzrO y, TiO 2, SiC, silica alumina, zeolite, clay and combination thereof.The method comprises that the raw material that makes hydrogen, water and comprise at least one carbohydrate contacts to produce the effluent that comprises at least one polyvalent alcohol with catalyst system, wherein catalyst system comprises non-loading type component and loading type component, the compound that non-loading type component comprises the group of selecting free tungsten compound, molybdenum compound and any combination composition thereof, loading type component comprises the carried-type active metal component of the group of selecting free Pt, Pd, Ru, Rh, Ni, Ir and combination composition thereof on solid catalyst carrier; And from effluent, reclaim polyvalent alcohol.The method can batch mode or is operated with continuous-mode operation.When with continuous-mode operation, the method comprises that with high yield and highly selective, the flow stock that comprises carbohydrate being flowed to continuous catalysis changes into ethylene glycol or propylene glycol.
Raw material packet is containing at least one carbohydrate, and it can and can be edible, not edible, amorphous or crystallization for any class in monose, disaccharides, oligosaccharide kind and polyose in essence.In one embodiment, raw material packet is containing by one or some polyoses consisting of the monose of glycosidic link combination.The example of polyose comprises glycogen, Mierocrystalline cellulose, hemicellulose, starch, chitin and combination thereof.Term used herein " carbohydrate " is intended to comprise the carbohydrate of all the above-mentioned types, comprises polyose.
When carbohydrate is Mierocrystalline cellulose, hemicellulose or its combination, can realize other advantages.Hemicellulose is generally understood as several more complicated and not as any one in the carbohydrate of Mierocrystalline cellulose complexity than sugar.Mierocrystalline cellulose and hemicellulose be take to economized form, and to be converted into useful products can be sustainable method, and it reduces fossil energy consumption and does not supply direct competitive with human food prods.Mierocrystalline cellulose and hemicellulose are to have various attractive sources as the residue from agriculture production or from the extensive renewable resource of the refuse of forestry or Forest products.Because the mankind can not digest cellulose and hemicellulose, therefore use Mierocrystalline cellulose and/or hemicellulose not to reduce provand as raw material.In addition, Mierocrystalline cellulose and hemicellulose can be low-cost refuse type raw materials, and it changes into high value products if polyvalent alcohol is as ethylene glycol and propylene glycol in this article.
The raw material that comprises carbohydrate of the method can be derived from source as farm crop, forest biomass, waste materials, recycled materials.Example comprises paper pulp, W-Gum, sugarcane, cereal, beet, the glycogen of forest in short felling cycle, industrial Wood waste, forest residue, agriculture residue, energy crop, trade effluent, city waste water, paper, cardboard, fabric, biomass derived and comprises molecular unit structure C m(H 2o) nother molecules and combination thereof.Can use multiple material as associating raw material.About biomass, raw material can be complete biomass or treated biomass, complete biomass comprise Mierocrystalline cellulose, xylogen and hemicellulose, and treated biomass are the wherein at least part of depolymerization of polyose or wherein xylogen, hemicellulose or treated biomass that the two removes at least partly from complete biomass.
The inventive method can batch mode and is operated, or can continuous-mode operation and operate.In batch mode, necessary reactant is combined with catalyst system and it is reacted.After for some time, from reactor, remove reaction mixture separated to reclaim product.Autoclave reaction is the common example of batch reactions.Although the method can batch mode, with continuous mode, while especially operating with fairly large operation, there is advantage.Below explanation will focus on continuous-mode operation, but the focus of following explanation does not limit the scope of the invention.
Be different from batch system operation, in continuation method, raw material introduced in reaction zone continuously as the material stream that flows, and taken out the product that comprises polyvalent alcohol continuously.Material must transfer to reaction zone from low pressure source, and product must transfer to product recovery zone from reaction zone.Depending on operator scheme, residual solids (if existence) must be able to be removed from reaction zone.
In pressurized hydrogen environment, pack processing is that raw material may be soluble solid containing the challenge of the raw material of carbohydrate.Therefore, can carry out pre-treatment to promote the continuous transmission of raw material to raw material.Suitable pretreatment operation can comprise sizing, dry, grinding, hot-water cure, steam treatment, hydrolysis, pyrolysis, thermal treatment, chemical treatment, biological treatment, catalytic treatment and combination thereof.Sizing, grind or dryly can produce solids, these solids have and can in whole continuation method, use liquid stream or air-flow or mechanical system to flow or mobile size.Chemically treated example is the weak acid hydrolysis of polysaccharide.The example of catalytic treatment is the catalytic hydrolysis of polysaccharide, the catalytic hydrogenation of polysaccharide or the two, and the example of biological treatment is enzymically hydrolyse.Hot-water cure, steam treatment, thermal treatment, chemical treatment, biological treatment or catalytic treatment can produce lower molecular weight carbohydrate and the depolymerization xylogen more easily transmitting than untreated carbohydrate.Suitable preconditioning technique is referring to " Catalytic Hydrogenation of Corn Stalk to Ethylene Glycol and 1; 2-Propylene Glycol " Jifeng Pang, Mingyuan Zheng, Aiqin Wang and Tao Zhang Ind.Eng.Chem.Res.DOI:10.1021/ie102505y, date of publication (network): on April 20th, 2011.Also can be referring to US2002/0059991.
Pack processing is that carbohydrate has thermo-sensitivity containing another challenge of the raw material of carbohydrate.What before contacting with catalyzer, be exposed to that superheated can cause carbohydrate does not expect that thermal response is as the charing of carbohydrate.In one embodiment of the invention, with the input material stream separating with main hydrogen stream, the raw material that comprises carbohydrate is provided to the reaction zone of containing catalyzer.In this embodiment, reaction zone has at least two input material streams.The first input material flow to and comprises less the raw material that contains carbohydrate, and the second input material flow to and comprises less hydrogen.Water can be present in the first input material stream, the second input material stream or these two input material streams.Some hydrogen also can be present in the first input material stream with the raw material that comprises carbohydrate.By the raw material that comprises carbohydrate and hydrogen being divided into two independently input material streams, hydrogen stream can be heated to surpass temperature of reaction, and can be not simultaneously by the heating raw materials that comprises carbohydrate to temperature of reaction.The temperature that at least comprises the first input material stream of the raw material that contains carbohydrate can be through controlling to be no more than the temperature of not expecting hot side reaction.For example, the first input that at least comprises the raw material that contains carbohydrate expects that the temperature of stream can be through controlling to be no more than the decomposition temperature of carbohydrate or the carbonization temperature of carbohydrate.The first input material stream, the second input material stream or the two are forced into reaction pressure before can be in being introduced into reaction zone.
Processing continuously in embodiment, after any pre-treatment, the raw material that comprises carbohydrate is being introduced in catalytic reaction zone continuously as the material stream that flows.Water and hydrogen, two kinds of reactants are all present in reaction zone.As discussed above and depending on specific embodiments, the raw material that comprises carbohydrate can separately be introduced and be independent of at least a portion hydrogen, maybe can and be introduced into together reaction zone by any combination of reactant (comprising the raw material that comprises carbohydrate) combination.Due to the mixed phase that may be present in reaction zone, the reactor assembly of preferred particular type.For example, suitable reactor assembly comprises boiling catalyst bed reactor system, the immobilized catalyst reactor assembly with catalyst channels, pre-reactor system, fluidized bed reactor system, mechanically mixing reactor assembly and slurry reactor system, also referred to as three-phase bubble column system.
In addition, the metallurgy of reactor assembly is compatible with expectation product with reactant in selecting with the scope in operational condition.The metallurgical example that is suitable for reactor assembly comprises titanium, zirconium, stainless steel, have the carbon steel of resistance to hydrogen embrittlement coating, have the carbon steel of corrosion-resistant finishes.In one embodiment, the metallurgy of reactive system comprises zirconium coating or coated carbon steel.
In reaction zone and under operational condition, reactant experience catalytic conversion reaction is to produce at least one polyvalent alcohol.The polyvalent alcohol of expectation comprises ethylene glycol and propylene glycol.Also can produce by product, it comprises that compound is as alcohols, organic acid, aldehydes, monose, carbohydrate, phenol system compound, hydro carbons, glycerine, depolymerization xylogen, carbohydrate and protein.Except product polyvalent alcohol, by product can have value recyclable.Reaction can continue to, or some reactants can retain with form of mixtures with intermediate product together with product.The intermediate product comprising as a by product part herein can comprise that compound is as depolymerizing cellulose, xylogen and hemicellulose.Unreacted hydrogen, water and carbohydrate also can be present in the effluent of reaction zone together with product and by product.Unreacted material and/or intermediate product are recyclable and be recycled to reaction zone.
Reaction is that catalyzed reaction and reaction zone comprise at least one catalyst system.The catalyst system that carbohydrate is changed into at least one polyvalent alcohol comprises non-loading type component and loading type component, the compound that non-loading type component comprises the group of selecting free tungsten compound, molybdenum compound and any combination composition thereof, loading type component comprises the active metal component of the group of selecting free Pt, Pd, Ru, Rh, Ni, Ir and combination composition thereof on solid catalyst carrier.Various active metal can be present on solid catalyst carrier.The example of suitable non-loading type component comprises wolframic acid, molybdic acid, ammonium tungstate, ammonium metawolframate, ammonium paratungstate, the tungstate compound that comprises at least one Huo II family of I family element, the metatungstate compound that comprises at least one Huo II family of I family element, the para-tungstate compound, the heteropolymer of tungsten, the heteropolymer of molybdenum, tungsten oxide, molybdenum oxide and the combination thereof that comprise at least one Huo II family of I family element.One or more unsupported catalyst components can be used together with one or more loaded catalyst components.Catalyst system also can be considered multicomponent catalyst, and this term is used interchangeably in this article.
The loaded catalyst component of catalyst system needs solid catalyst carrier.Carrier can be powder shape or concrete shape as spheroid, extrudate, pill, particle, lozenge, irregularly shaped particle, single chip architecture, catalyst-coated pipe or catalyst-coated heat exchanger surface.Active metal can any suitable method known in the art as by co-precipitation together with carrier, coextrusion, or dipping is added on catalytic carrier.Active metal can be reduction form.Can use refractory oxide support of the catalyst and other carriers.The example of high-temperature inorganic oxide carrier includes but not limited to silicon-dioxide, aluminum oxide, silica-alumina, titanium oxide, zirconium white, magnesium oxide, clay, zeolite, molecular sieve etc.Should point out, silica-alumina is not the mixture of silicon-dioxide and aluminum oxide, but means the acid amorphous material of cogelled or co-precipitation.Also can adopt carbon and gac as carrier.Concrete suitable carrier comprises carbon, gac, Al2O3, ZrO2, SiO2, MgO, CexZrOy, TiO2, SiC, silica alumina, zeolite, clay and combination thereof.Certainly, can use the combination of material as carrier.Active metal can form 0.05 quality % to 30 quality % of loaded catalyst component.In another embodiment of the invention, active metal can form 0.3 quality % to 15 quality % of loaded catalyst component, and in another embodiment of the invention, active metal can form 0.5 quality % to 7 quality % of loaded catalyst component.
In the method, the amount of used catalyst system can be 0.005 quality % to 0.4 quality % of the raw material that comprises carbohydrate.In other embodiments, in the method, the amount of used catalyst system can be 0.01 quality % to 0.25 quality % of the raw material that comprises carbohydrate.In other embodiment, in the method, the amount of used catalyst system can be 0.02 quality % to 0.15 quality % of the raw material that comprises carbohydrate.The reaction occurring is multi-step reaction, and can control by the component of different relative quantities in the catalyst system of difference amount or catalyst system the speed of differential responses.About the relative quantity of component in the amount of catalyst system or used catalyst system, indivedual application can have different requirements.In reaction mixture, the concentration of unsupported catalyst component is 0.001 quality % to 20 quality %, and in reaction mixture, the concentration of loaded catalyst component is 0.001 quality % to 20 quality %.In catalyst system, the mass ratio of non-loading type component and loading type component is 1:100 to 100:1, as measured by ICP or other common wet chemical process.In another embodiment, the mass ratio of non-loading type component and loading type component is 1:20 to 50:1, and the mass ratio of non-loading type component and loading type component is 1:10 to 10:1.
In one embodiment of the invention, unsupported catalyst component can be for dissolving in reaction mixture or dissolving at least partly the solid of reaction mixture under reaction conditions, and this reaction mixture at least comprises water and raw material.The unsupported catalyst of significant quantity should dissolve in reaction mixture.Different application and different unsupported catalyst component will cause the significant quantity of unsupported catalyst component required in reaction mixture solution different.In another embodiment of the invention, unsupported catalyst component be can be with reaction mixture miscible or miscible liquid at least partly.As solid unsupported catalyst component, the liquid unsupported catalyst of significant quantity should be miscible in reaction mixture.Again, different application and different unsupported catalyst component need the significant quantity of miscible unsupported catalyst component in reaction mixture different by causing.Conventionally, the amount of mixed unsupported catalyst component soluble in water is 1% to 100%, in another embodiment 10% to 100% and in another embodiment 20% to 100%.
Multicomponent catalyst of the present invention can provide several to be better than the advantage of more traditional one-component catalyzer.For example, can reduce the manufacturing cost of catalyzer, this is because less active ingredient need to be added on solid catalyst carrier.Can reduce running cost, this be because expection by the less catalyst make-up of needs and can use and have more optionally treatment step for recovery and the recirculation of catalyzer.Other advantages comprise: improved catalyst stability, and this makes, and catalyst consumption is lower and per unit polyvalent alcohol product cost is lower; And improve the selectivity of ethylene glycol and propylene glycol and reduce azeotropic impurity as the potentiality of the generation of butyleneglycol.
In some embodiments, catalyst system can be contained in reaction zone, and in other embodiments, catalyzer can be continuously or off and on through reaction zone, and in other embodiment, can there are two kinds of situations in catalyst system, wherein at least one catalyst system component is present in reaction zone, and other catalyst system component are passed reaction zone continuously or with gap.Suitable reactor assembly comprises boiling catalyst bed reactor system, the immobilized catalyst reactor assembly with catalyst channels, pre-reactor system, fluidized bed reactor system, mechanically mixing reactor assembly and slurry reactor system, also referred to as three-phase bubble column system, and combination.
The example of the operational condition in reactor assembly comprises the temperature of 100 ℃ to 350 ℃ and is greater than the hydrogen pressure of 150psig.In one embodiment, the temperature in reactor assembly can be 150 ℃ to 350 ℃, and in another embodiment, the temperature in reactor assembly can be 200 ℃ to 280 ℃.Can in reactor assembly, make under the following conditions the raw material and the catalyst system Continuous Contact that comprise at least one carbohydrate: the weight ratio of water and raw material is 1 to 100, the weight ratio of catalyzer (non-loading type component+loading type component) and raw material is greater than 0.005, pH be less than 10 and the residence time be greater than 5 minutes.In another embodiment, the weight ratio of water and raw material be 1 to 20 and the weight ratio of catalyzer and raw material be greater than 0.01.In a further embodiment, the weight ratio of water and raw material be 1 to 5 and the weight ratio of catalyzer and raw material be greater than 0.1.
In one embodiment of the invention, catalytic reaction system adopts slurry reactor.Slurry reactor is also referred to as three-phase bubble column.Slurry reactor system is known in the art, and the example of slurry reactor system is set forth in US5,616,304 and specialist paper Slurry Reactor Design Studies, DOE plans in DE-AC22-89PC89867 Reactor Cost Comparisons, and it can be referring to http://www.fischer-tropsch.org/DOE/DOE_reports/91005752/de91005 752_t oc.htm.Catalyst system can mix to form slurry with water and the raw material that comprises carbohydrate, and this slurry is guided to slurry reactor.Reaction occurs in slurry reactor, and catalyzer transmits and leaves reactor assembly together with flowing out streams.Slurry reactor system can operate under listed condition above.In another embodiment, catalytic reaction system adopts ebullated bed reactor.Ebullated bed reactor system is known in the art, and the example of ebullated bed reactor system is set forth in US6, in 436,279.
From the outflow material of reaction zone, flow to and contain less product polyvalent alcohol, also can contain unreacted water, hydrogen, carbohydrate, by product if phenol system compound and glycerine and intermediate product are as depolymerization polyose and xylogen.Depending on selected catalyzer and catalytic reaction system used, flow out streams and also can at least contain some catalyst system.Flowing out streams can be the catalyst system of liquid phase containing some, or a part is the catalyst system of solid phase.In some embodiments, it may be favourable before or after reclaiming expectation product or by product, from flow out streams, removing solid-phase catalyst component.Can use one or more for example following technology from flow out streams, to remove solid-phase catalyst component: direct filtration, sedimentation subsequent filtration, wet cyclone, fractionation, centrifugal, use flocculation agent, precipitation, extraction, evaporation or its combination.In one embodiment, can be by separated catalyst recycle to reaction zone.
Referring to Fig. 1, via material stream 122, catalyst system, water and the raw material that comprises carbohydrate are guided to reaction zone 124.Mixture in material stream 122 for example has the weight ratio of the weight ratio of 5 water and the raw material that comprises carbohydrate and 0.05 catalyst system and the raw material that comprises carbohydrate.Via material stream 125, incite somebody to action at least hydrogen and guide to reaction zone 124.Reaction zone 124 operates under the residence time of for example hydrogen pressure, 7 pH of temperature, 1200psig of 250 ℃ and 8 minutes.Before in introducing reaction zone 124, make catalyzer, water and the raw material that comprises carbohydrate in material stream 122 and expect that the hydrogen in stream 125 reaches the pressure of 1800psig, under the pressure in identical with reaction zone 124.Yet, only the material stream 125 that at least comprises hydrogen is increased to at least 250 ℃, at the temperature with the temperature in being more than or equal to reaction zone 124.To at least containing the mixture of carbohydrate in material stream 122, carry out temperature control, to remain on lower than at the decomposition of carbohydrate or the temperature of carbonization temperature.In reaction zone 124, carbohydrate is catalytically converted into at least ethylene glycol or propylene glycol.Reaction zone effluent 126 at least contains glycol product or propylene glycol.Reaction zone effluent 126 also can contain alcohols, organic acid, aldehydes, monose, polyose, phenol system compound, hydro carbons, glycerine, depolymerization xylogen and protein.Reaction zone effluent 126 is guided to product recovery zone 134, the separated and recovery in steam 136 by the diol product of expectation in product recovery zone 134.From product recovery zone 134, in material stream 138, remove all the other components of reaction zone effluent 126.
Referring to Fig. 2, water and the raw material 210 that comprises polysaccharide are introduced to pretreatment units 220, carbohydrate is ground to the little size of particles to be enough to use as slurry legacy equipment pumping together with water in pretreatment unit 220.By the catalyst system combination in the water in pretreating raw material and pipeline 219 and pipeline 223, and combination stream 227 is guided to reaction zone 224.Combination stream 227 for example has weight ratio and 0.1 catalyst system and the weight ratio of carbohydrate of 20 water and the raw material that comprises carbohydrate.Via material stream 225, incite somebody to action at least hydrogen and guide to reaction zone 224.Can be before reaction zone 224 by some hydrogen and 227 combinations of material stream, as by as shown in optional dotted line 221.Reaction zone 224 operates under the residence time of for example hydrogen pressure, 7 pH of temperature, 200psig of 280 ℃ and 8 minutes.Before in being introduced into reaction zone 224, making catalyst system, water and the pretreating raw material that comprises carbohydrate in material stream 227 and expect that the hydrogen in stream 225 reaches the pressure of 1800psig, at the temperature in identical with reaction zone 224.Yet, only the material stream 225 that at least comprises hydrogen is increased to at least 250 ℃, at the temperature of temperature in being more than or equal to reaction zone 224.To at least containing the mixture of carbohydrate in material stream 227, carry out temperature control, to remain on lower than at the decomposition of polysaccharide or the temperature of carbonization temperature.In reaction zone 224, carbohydrate is catalytically converted into at least ethylene glycol or polyoxyethylene glycol.
Reaction zone effluent 226 at least contains glycol product or propylene glycol and catalyzer.Reaction zone effluent 226 also can contain alcohols, organic acid, aldehydes, monose, polyose, phenol system compound, hydro carbons, glycerine, depolymerization xylogen and protein.Reaction zone effluent 226 is guided to and in pipeline 232 removal separated with reaction zone effluent 226 by catalyst component in 228， recovery zone, optional catalyst system recovery zone 228.Can optionally make catalyst component recirculation in pipeline 232 with pipeline 223 combinations or be recycled to reaction zone 224, as by as shown in optional dotted line 229.The reaction zone effluent 230 of poor catalyst component is guided to product recovery zone 234, the separated and recovery in steam 236 by the diol product of expectation in product recovery zone 234.From product recovery zone 234, in material stream 238, remove all the other components of effluent 230.
Embodiment
According to following program, carry out 17 experiments.1 gram of raw material that contains carbohydrate and 100 grams of deionized waters are added in 300ml Parr autoclave reactor.The catalyzer that contains loading type and non-loading type component of significant quantity is added in reactor.The details of raw material and the type of catalyzer and amount are shown in table 1.By autoclave sealing and with N2 purging, with H2, purge subsequently, and finally at room temperature utilize H2 to be forced into 6MPa.Autoclave is heated to 245 ℃ and remain at temperature 30 minutes under the lasting stirring of 1000rpm.After 30 minutes, autoclave is cooled to room temperature, and reclaims product liquid and use HPLC to analyze by filtration.From Sigma-Aldrich, obtain Microcrystalline Cellulose.Using just wet technology to be stored in Ni nitrate in water by use impregnated in the Ni of difference amount on absorbent charcoal carrier Norit-CA1, to prepare the Ni catalyzer on Norit CA-1.Then will be through impregnated carrier dried overnight under nitrogen purging in baking oven at 40 ℃, and at 750 ℃, in H2, reduce 1hr.5%Pd/C and %Pt/C are purchased from Johnson Matthey.With the quality of the ethylene glycol that produced or propylene glycol divided by raw materials used quality and be multiplied by 100 yields of measuring ethylene glycol and propylene glycol.
Figure BDA0000435743520000131

Claims (10)

1. by a method at least one polyvalent alcohol of raw material production, it comprises:
A) raw material that makes hydrogen, water and comprise at least one carbohydrate contacts to produce the outflow streams that comprises at least one polyvalent alcohol with catalyst system, wherein catalyst system comprises non-loading type component and loading type component, the compound that non-loading type component comprises the group of selecting free tungsten compound, molybdenum compound and any combination composition thereof, loading type component comprises the carried-type active metal component of the group of selecting free Pt, Pd, Ru, Rh, Ni, Ir and combination composition thereof on solid catalyst carrier; With
B) from flow out streams, reclaim polyvalent alcohol.
2. according to the process of claim 1 wherein that described method is to select the pattern operation of the group of free batch mode and continuous-mode operation composition.
3. according to the process of claim 1 wherein that contact occurs in the reaction zone that at least comprises the first input material stream and the second input material stream, wherein the first input material flow to and comprises less the flow stock and the second input that contain carbohydrate and expect that stream comprises flowing hydrogen.
4. according to the method for claim 3, wherein the first input material stream pressurization optionally heating to temperature and second input material stream of the decomposition temperature lower than carbohydrate before entering reaction zone pressurizeed and heats before entering reaction zone.
According to the process of claim 1 wherein the raw material choosing forest in freely short felling cycle that comprises carbohydrate, industrial waste wood, forest residue, agriculture residue, energy crop, trade effluent, city waste water, paper, cardboard, fabric, biomass derived paper pulp, W-Gum, sugarcane, cereal, beet, glycogen, comprise molecular unit structure C m(H 2o) nmolecule and the group that forms of combination thereof.
6. according to the process of claim 1 wherein that outflow material flows to a step and comprises the by product that at least one selects the group of free alcohols, organic acid, aldehydes, monose, polyose, phenol system compound, hydro carbons, glycerine, depolymerization xylogen and protein composition.
7. a catalyst system, it comprises:
A) non-loading type component, the compound that it comprises the group of selecting free tungsten compound, molybdenum compound and any combination composition thereof; And
B) loading type component, it comprises the active metal component of the group of selecting free Pt, Pd, Ru, Rh, Ni, Ir and combination composition thereof on solid catalyst carrier.
8. according to the catalyst system of claim 7, wherein solid catalyst carrier selects free carbon, Al 2o 3, ZrO 2, SiO 2, MgO, Ce xzrO y, TiO 2, the group that forms of SiC, silica alumina, zeolite, clay and combination thereof.
9. according to the catalyst system of claim 7, wherein non-loading type component is selected the compound of the group of free wolframic acid, molybdic acid, ammonium tungstate, ammonium metawolframate, ammonium paratungstate, the tungstate compound that comprises at least one Huo II family of I family element, the metatungstate compound that comprises at least one Huo II family of I family element, the para-tungstate compound that comprises at least one Huo II family of I family element, the heteropolymer of tungsten, the heteropolymer of molybdenum, tungsten oxide, the oxidation of molybdenum thing and combination composition thereof.
10. according to the catalyst system of claim 7, wherein active metal is reduction form.
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