TW201309627A - Generation of polyols from saccharide containing feedstock - Google Patents

Abstract

A process for generating at least one polyol from a feedstock comprising saccharide is performed in a continuous or batch manner using a catalyst system. 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 metal component with an oxidation state greater than or equal to 2+.

Description

Production of polyols from raw materials containing sugars

The present invention relates to a catalyst system and a method of producing at least one polyol from a feedstock comprising at least one sugar using the particular catalyst system. The method includes contacting hydrogen, water, and a saccharide-containing material with a catalyst system to produce an effluent comprising at least one polyol; and recovering the polyol from the effluent. The catalyst system comprises a metal component having an oxidation state greater than or equal to 2+ and a hydrogenation component.

The present application claims the priority of U.S. Application Serial No. 13/193,007, filed on Jul. 28, 2011, and Serial No. 13/193,072, filed on Jul. 28, 2011, the contents of The manner is incorporated herein.

Polyols are valuable materials that can be used to make cold weather fluids, cosmetics, polyesters, and many other synthetic products. The replacement of fossil fuel-derived olefins by sugars to produce polyols is a more environmentally friendly and economically attractive method. Previously, polyols have been produced from polyhydroxy compounds, see WO 2006/092085 and US 2004/0175806. Recently, Catalysis Today, 147, (2009) 77-85. It is revealed that the saccharide is catalytically converted to ethylene glycol on a supported carbide catalyst. US 2010/0256424, US 2010/0255983, and WO 2010/060345 teach a process for preparing ethylene glycol from sugars and a tungsten carbide catalyst for catalyzing the reaction. Angcw. Chem. Int. Ed 2008, 47, 8510-8513 and its supporting information have also disclosed that tungsten carbide catalysts have been successfully used to directly catalyze the conversion of sugars to ethylene glycol in a batch mode. In Chem. Comm. 2010, 46, 862-864, a small amount of nickel is added to the tungsten carbide catalyst. Bimetallic catalysts have been disclosed in ChemSusChem, 2010, 3, 63-66. Other references that disclose catalysts for converting cellulose directly to ethylene glycol or propylene glycol are known in the art, including WO 2010/060345, US 7,767,867, Chem. Commun., 2010, 46, 6935-6937, Chin. J. Catal., 2006, 27(10): 899-903, and Apcseet UPC 2009 7 ^th Asia Pacific Congress on Sustainable Energy and Environmental Technologies, "One-pot Conversion of Jerusalem Artichoke Tubers into Polyols".

However, there is still a need for a novel catalyst system for efficiently converting sugars directly into polyols, and in particular a catalyst system that is more suitable for mass production or commercial production equipment. The present invention provides a method and a catalyst system for producing at least one polyol from a feedstock comprising at least one sugar comprising at least one selected from the group consisting of IUPAC Groups 4, 5 or 6 of the Periodic Table of the Elements and The metal component (M1) having an oxidation state greater than or equal to 2+ and at least one hydrogenation component (M2) selected from Groups 9, 9 or 10 of the IUPAC of the Periodic Table of the Elements. The metal component (M1) is in the form of a non-carbide, nitride or phosphide.

One embodiment of the present invention is a catalyst system useful for converting at least one sugar to a polyol comprising a metal component (M1) having an oxidation state greater than or equal to 2+ and a hydrogenation component (M2). The metal component (M1) is selected from IUPAC Groups 4, 5 and 6 of the Periodic Table of the Elements, and the hydrogenated component (M2) is selected from the group consisting of IUPAC Groups 8, 9 and 10 of the Periodic Table of the Elements. The metal component (M1) may be selected from the group consisting of tungsten, molybdenum, vanadium, niobium, chromium, titanium, zirconium, and any combination thereof. The metal component can be included in the compound. The metal component is in a form other than carbide, nitride or phosphide. The hydrogenation component can comprise, for example, an active metal component selected from the group consisting of Pt, Pd, Ru, Rh, Ni, Ir, and combinations thereof. M1, M2 or M1 and M2 may be unsupported or supported on a solid catalyst support. The solid catalyst carrier is selected from the group consisting of carbon, Al ₂ O ₃ , ZrO ₂ , SiO ₂ , magnesium oxide (MgO), Ce _x ZrO _y , TiO ₂ , lanthanum carbide (SiC), vermiculite, alumina, vermiculite. A group of aluminum, zeolite, clay, and combinations thereof. Based on the element, the mass ratio of M1 to M2 varies from 1:100 to 100:1. If it has a carrier, the M1 component, the M2 component or the M1 and M2 components are 0.05 to 30% by mass based on the element of the carrier. The metal component and the measured values (such as mass ratio, weight ratio, and mass percentage) of the hydrogenated component are herein based on IUPAC Groups 4, 5, and 6 of the Periodic Table of the Elements and IUPAC Groups 8, 9, and 10 The elements are provided.

Another embodiment of the invention is a method of producing at least one polyol from a feedstock comprising at least one sugar, wherein the method comprises contacting hydrogen, water, and a feedstock with a catalyst system to produce an effluent comprising at least one polyol And recovering the polyol from the effluent. The method can be operated in batch mode or continuous mode. The catalyst system comprises a metal component (M1) having an oxidation state greater than or equal to 2+ and a hydrogenation component (M2). The metal component (M1) is selected from IUPAC Groups 4, 5 and 6 of the Periodic Table of the Elements, and the hydrogenated component (M2) is selected from the group consisting of IUPAC Groups 8, 9 and 10 of the Periodic Table of the Elements. The metal component (M1) may be selected from the group consisting of tungsten, molybdenum, vanadium, niobium, chromium, titanium, zirconium, and any combination thereof. The metal component can be included in the compound. The metal component is in a form other than carbide, nitride or phosphide. The hydrogenation component may comprise an active metal component selected from the group consisting of Pt, Pd, Ru, Rh, Ni, Ir, and combinations thereof. The hydrogenation component can be included in the compound. M1, M2 or M1 and M2 may be unsupported or supported on a solid catalyst support. The solid catalyst carrier is selected from the group consisting of carbon, Al ₂ O ₃ , ZrO ₂ , SiO ₂ , magnesium oxide (MgO), Ce _x ZrO _y , TiO ₂ , lanthanum carbide (SiC), vermiculite, alumina, vermiculite. A group of aluminum, zeolite, clay, and combinations thereof. Based on the element, the mass ratio of M1 to M2 varies from 1:100 to 100:1. If it has a carrier, the M1 component, the M2 component or the M1 and M2 components are 0.05 to 30% by mass based on the element of the carrier.

Yet another embodiment of the invention is a continuous process for producing at least one polyol from a feedstock comprising at least one sugar. The method includes continuously contacting hydrogen, water, and a feedstock comprising at least one sugar with a catalyst system to produce an effluent stream comprising at least one polyol; and recovering the polyol from the effluent stream. The hydrogen, water, and feedstock are continuously fed into the reactor. The effluent stream is continuously removed from the reactor. The method utilizes the above-described catalytic method comprising a catalyst system of a metal component (M1) having an oxidation state greater than or equal to 2+ and a hydrogenation component (M2).

In one embodiment, the contacting occurs in a reaction zone having at least a first input stream and a second input stream, the first input stream comprising at least the feedstock comprising at least one sugar and the second input stream comprising hydrogen . The first input stream can be pressurized prior to the reaction zone and the second input stream can be pressurized and heated prior to the reaction zone. The first input stream can be pressurized and heated to a temperature below the thermal decomposition temperature of the sugar prior to the reaction zone, and the second The input stream can be pressurized and heated prior to the reaction zone. The first input stream and the second input stream additionally comprise water.

In another embodiment of the invention, the polyol produced is at least ethylene glycol or propylene glycol. By-products such as alcohols, organic acids, aldehydes, monosaccharides, disaccharides, oligosaccharides, polysaccharides, phenolic compounds, hydrocarbons, glycerol, depolymerized lignin, and proteins can also be produced. In one embodiment, the feedstock may be treated prior to contact with the catalyst by techniques such as sieving, drying, grinding, hot water treatment, steam treatment, hydrolysis, pyrolysis, heat treatment, chemical treatment, biological treatment, Catalytic treatment, or a combination thereof.

The effluent stream from the reactor system may additionally comprise a catalyst which may be separated from the effluent stream by techniques such as direct filtration, post-precipitation filtration, hydrocyclone, fractionation, centrifugation, use of flocculants, precipitation, liquids Extraction, adsorption, evaporation and combinations thereof.

The present invention relates to a catalyst system and method for producing at least one polyol from a feedstock comprising at least one sugar. The catalyst system comprises a metal component (M1) having an oxidation state greater than or equal to 2+ and a hydrogenation component (M2). The metal component (M1) is selected from the IUPAC Groups 4, 5 and 6 of the Periodic Table of the Elements. In a specific embodiment, the metal component (M1) can be selected from the group consisting of tungsten, molybdenum, vanadium, niobium, chromium, titanium, zirconium, and any combination thereof. The metal component can be included in the compound. The metal component is not in the form of a carbide, nitride or phosphide. The hydrogenation component (M2) is selected from the group consisting of Groups 9, 9 and 10 of IUPAC of the Periodic Table of the Elements. The hydrogenation component can be included in the compound. In a particular embodiment, the hydrogenation component can comprise an active metal component selected from the group consisting of Pt, Pd, Ru, Rh, Ni, Ir, and combinations thereof. M1, M2 or M1 and M2 may be unsupported or supported on a solid catalyst support. The solid catalyst carrier is selected from the group consisting of carbon, Al ₂ O ₃ , ZrO ₂ , SiO ₂ , MgO, Ce _x ZrO _y , TiO ₂ , SiC, vermiculite, alumina, vermiculite alumina, zeolite, clay, and combinations thereof. a group of people. Based on the element, the mass ratio of M1 to M2 varies from 1:100 to 100:1. If it has a carrier, the M1 component, the M2 component or the M1 and M2 components are 0.05 to 30% by mass based on the element of the carrier. The metal component and the measured values (such as mass ratio, weight ratio, and mass percentage) of the hydrogenated component are herein based on IUPAC Groups 4, 5, and 6 of the Periodic Table of the Elements and IUPAC Groups 8, 9, and 10 The elements are provided.

The method includes contacting hydrogen, water, and a feedstock comprising at least one sugar with the catalyst system to produce an effluent comprising at least one polyol; and recovering the polyol from the effluent. The method can be operated in batch mode or continuous mode. When operated in a continuous mode, the process comprises continuously catalytically converting the flowing sugar-containing feed stream to ethylene glycol or propylene glycol in high yield and high selectivity.

The material comprises at least one sugar which may be any of the monosaccharides, disaccharides, oligosaccharides and polysaccharides and which may be edible, inedible, amorphous or crystalline. In one embodiment, the feedstock comprises a polysaccharide consisting of one or more monosaccharides linked by a glycosidic linkage. Examples of polysaccharides include glycogen, cellulose, hemicellulose, starch, chitin, and combinations thereof. The term "sugar" as used herein is intended to include all of the above types of sugars (including polysaccharides).

In embodiments in which the sugar is cellulose, hemicellulose, or a combination thereof, Other advantages can be realized. Hemicellulose is generally considered to be any of several polysaccharides that are more complex than sugar. The economical conversion of cellulose and hemicellulose into useful products can be a sustainable way to reduce fossil energy consumption and not directly compete with human food supplies. Cellulose and hemicellulose have a large number of renewable resources from a variety of sources of interest, such as agricultural production residues or forestry or forest product waste. Since humans cannot digest cellulose and hemicellulose, the use of cellulose and/or hemicellulose as raw materials does not reduce our food supply. In addition, cellulose and hemicellulose can be low cost waste-type raw materials, which are converted herein to high value products (eg, polyols such as ethylene glycol and propylene glycol).

The sugary feedstock in the process can be derived from sources such as crops, forest biomass, waste materials, recycled materials. Examples include short-term rotation of forestry, industrial wood waste, forest residues, agricultural residues, energy crops, industrial wastewater, municipal wastewater, paper, cardboard, fabric, biomass pulp, corn starch, sugar cane, cereals, beets, glycogen and others. A molecule comprising a molecular unit structure C _m (H ₂ O) _n , and combinations thereof. A variety of materials can be used as a co-feedstock. In terms of biomass, the feedstock can be a whole biomass or treated biomass comprising cellulose, lignin and hemicellulose (where the polysaccharide is at least partially depolymerized, or wherein the lignin, hemicellulose or both All have been at least partially removed from the whole biomass).

The feedstock can be passed to a reactor system (eg, a boiling catalytic bed reactor system, an immobilized catalytic reactor system with catalyst channels, a pre-reactor system, a fluidized bed reactor system, depending on the catalyst selected). Mechanically mixed reactor system, slurry reactor system (also known as three-phase bubble column reactor system), And combinations thereof are in continuous contact with the catalyst system. Examples of operating conditions within the reactor system include temperatures from 100 ° C to 350 ° C and hydrogen pressures greater than 150 psig. In one embodiment, the temperature within the reactor system can range from 150 °C to 350 °C; in another embodiment, the temperature within the reactor system can range from 200 °C to 280 °C. The feedstock comprising at least one sugar can be continuously contacted with the catalyst system in the reactor system, wherein the weight ratio of water to raw materials is from 1 to 100, and the weight ratio of catalyst (M1+M2) to raw materials is greater than 0.005. The pH is less than 10 and the residence time is greater than 5 minutes. In another embodiment, the weight ratio of catalyst to feedstock is greater than 0.01.

The method of the invention can be operated in a batch mode or can be operated in a continuous mode. In batch mode operation, the desired reactants and catalyst systems are combined and reacted. After a period of time, the reaction mixture was removed from the reactor and the recovered product was isolated. Autoclave reactions are a common example of batch reactions. Although the method can be operated in a batch mode, it is advantageous to operate in a continuous mode (especially in large scale operations). The following description will focus on the continuous mode of operation, but the following description does not limit the scope of the invention.

Unlike batch system operation, in a continuous process, the feedstock is continuously introduced as a flow stream into the reaction zone and the product comprising the polyol is continuously recovered. The material must be transported from the low pressure source to the reaction zone and the product must be transferable from the reaction zone to the product recovery zone. Depending on the mode of operation, residual solids, if any, must be removed from the reaction zone.

The challenge of treating sugary feedstocks in a pressurized hydrogen environment is that the feedstock can be an insoluble solid. Thus, the feedstock can be pretreated to facilitate continuous transfer of the feedstock. Proper pretreatment operations can include sieving, drying, grinding, and heat Water treatment, steam treatment, hydrolysis, pyrolysis, heat treatment, chemical treatment, biological treatment, catalytic treatment, and combinations thereof. Sieving, grinding or drying produces solid particles of a size that can be flowed or moved by a liquid or gas stream or moved through a continuous process. An example of a chemical treatment is weak acid hydrolysis of a polysaccharide. Examples of catalytic treatment are catalytic hydrolysis of polysaccharides, catalytic hydrogenation of polysaccharides or both, and one example of biological treatment is enzymatic hydrolysis of polysaccharides. Hot water treatment, steam treatment, heat treatment, chemical treatment, biological treatment or catalytic treatment can produce lower molecular weight sugars and depolymerized lignin, which are easier to transport than untreated polysaccharides. Suitable pretreatment techniques can be found in "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/ie 102505y, published Date (website): April 20, 2011. See also US 2002/0059991.

Another challenge in handling sugary feedstocks is the sugar system heat sensitivity. Excessive heating prior to contact with the catalyst can cause undesired thermal reactions of the sugar, such as sugar charring. In one embodiment of the invention, the sugar-containing feedstock is provided to the reaction zone containing the catalyst in the form of an input stream separate from the main hydrogen stream. In this embodiment, the reaction zone has at least two input streams. The first input stream comprises at least the sugar-containing feedstock and the second input stream comprises at least hydrogen. Water may be present in the first input stream, the second input stream, or both input streams. Part of the hydrogen may also be present in the first input stream having the sugar-containing feedstock. By separating the sugar-containing feedstock and hydrogen into two separate input streams, the hydrogen stream can be heated above the reaction temperature without simultaneously heating the sugar-containing feedstock to the reaction temperature. Controlling the temperature of the first input stream comprising at least the sugar-containing material Does not exceed the temperature of the unwanted side reaction. For example, the temperature of the first input stream comprising at least the sugar-containing material can be controlled to not exceed the decomposition temperature of the sugar or the carbonization temperature of the sugar. The first input stream, the second input stream, or both may be pressurized to the reaction pressure prior to introduction into the reaction zone.

In a continuous process embodiment, the sugar-containing feedstock is continuously introduced into the catalytic reaction zone as a flowing stream after any pretreatment. Water and hydrogen (both reactants) are present in the reaction zone. As described above and in accordance with particular embodiments, at least a portion of the hydrogen can be introduced separately and independently of the sugar-containing feedstock, or any combination of reactants (including sugar-containing feedstocks) can be combined and introduced together into the reaction zone. A particular type of system is preferred because of the presence of a mixed phase within the reaction zone. For example, suitable systems include a boiling catalytic bed reactor system, an immobilized catalytic reactor system with catalyst channels, a pre-reactor system, a fluidized bed reactor system, a mechanical mixing reactor system, and a slurry reactor system ( Also known as a three-phase bubble column reactor system, and combinations thereof.

In addition, the metallurgical materials of the reactor system are selected to be compatible with the reactants and desired products within the operating conditions. Examples of metallurgical materials suitable for use in the reactor system include titanium, zirconium, stainless steel, carbon steel with a hydrogen embrittlement resistant coating, and carbon steel with a corrosion resistant coating. In one embodiment, the metallurgical material of the reaction system comprises a coating or clad carbon steel.

Within the reaction zone and operating conditions, the reactants undergo a catalytic conversion reaction to produce at least one polyol. The desired polyols include ethylene glycol and propylene glycol. Can also produce by-products and include such as alcohols, organic acids, aldehydes, monosaccharides, polysaccharides, phenolic compounds, hydrocarbons, glycerin, depolymerized wood A compound of protein and protein. Such by-products may be of value and may be recovered in addition to the polyol products. These reactions can be carried out to completion or some of the reactants and intermediates can remain in the mixture containing the product. Intermediates (as part of by-products herein) may include compounds such as depolymerized cellulose, lignin, and hemicellulose. Unreacted hydrogen, water, and polysaccharides may also be present in the reaction zone effluent along with the product and by-products. Unreacted materials and/or intermediates can be recovered and recycled to the reaction zone.

The reactions catalyze the reaction and the reaction zone comprises at least one catalyst system, wherein the catalyst system comprises a metal component (M1) having an oxidation state greater than or equal to 2+ and a hydrogenation component (M2). The metal component (M1) is selected from IUPAC Groups 4, 5 and 6 of the Periodic Table of the Elements, and the hydrogenated component (M2) is selected from the group consisting of IUPAC Groups 8, 9 and 10 of the Periodic Table of the Elements. The catalyst system can also be considered a multi-component catalyst, and such terms are used interchangeably herein.

The metal component (M1) may be present in the catalyst system in any catalytically usable form having a metal component having an oxidation state greater than or equal to 2+. The metal component can be in the form of a compound or can be in a chemical combination with one or more other ingredients in the catalyst system. For example, the metal component (M1) may be selected from the group consisting of tungsten, molybdenum, vanadium, niobium, chromium, titanium, zirconium, and any combination thereof. The metal component can be included in the compound. The metal component is in the form of a non-carbide, nitride or phosphide. The compound comprising the M1 component of the catalyst system may be selected from the group consisting of tungstic acid, molybdic acid, ammonium tungstate, ammonium metatungstate, ammonium paratungstate, a tungstate compound comprising at least one Group I or Group II element, including at least one a metatungstate compound of a Group I or Group II element, a paratungstate compound comprising at least one Group I or Group II element, a heteropoly compound of tungsten, molybdenum Heteropoly compounds, tungsten oxide, molybdenum oxide, vanadium oxide, metavanadate, chromium oxide, chromium sulfate, titanium ethoxide, zirconium acetate, zirconium carbonate, zirconium hydroxide, cerium oxide, cerium oxide, and A group of combinations. The metal component is in the form of a non-carbide, nitride or phosphide. The hydrogenation component (M2) may be present in the catalyst system in any catalytically available form. The hydrogenated component can be in elemental form or can be a compound or can be in a chemical combination with one or more other components of the catalyst system. For example, the hydrogenation component may comprise an active metal component selected from the group consisting of Pt, Pd, Ru, Rh, Ni, Ir, and combinations thereof.

The metal component M1, hydrogenation component M2 or M1 and M2 may be unsupported or supported on one or more solid catalyst supports. A refractory oxide catalyst carrier and other supports can be used. Based on the element, the mass ratio of M1 to M2 varies from 1:100 to 100:1. If it has a carrier, the M1 component, the M2 component or the M1 and M2 components are 0.05 to 30% by mass based on the element of the carrier. The following description relates generally to the catalyst carrier. The general description of the catalyst carrier is not intended to limit the broad scope of the invention to a single catalyst carrier. For example, in one embodiment, the M1 system is loaded on the first catalyst carrier and the M2 system is supported on the second catalyst carrier, and the first catalyst carrier and the second catalyst carrier may have the same or different compositions.

The carrier can be in the form of a powder or a specific shape (eg, spheres, extrudates, pellets, granules, troches, irregular shaped granules, monolithic structures, catalytically coated tubes, or catalytic coating heat exchange surfaces). Examples of refractory inorganic oxide supports include, but are not limited to, vermiculite, alumina, vermiculite alumina, titania, zirconia, magnesia, clay, zeolites, molecular sieves, and the like. It should be noted that vermiculite alumina is not a mixture of vermiculite and alumina, but means acidic and amorphous materials that have been co-gelled or co-precipitated. Carbon and activated carbon can also be used as a carrier. Particularly suitable supports include carbon, activated carbon, Al ₂ O ₃ , ZrO ₂ , SiO ₂ , MgO, Ce _x ZrO _y , TiO ₂ , SiC, vermiculite, alumina, vermiculite alumina, zeolite, clay, and combinations thereof . Of course, a combination of materials can be used as the carrier. The combination of M1, M2, or M1 and M2 can be incorporated into the catalyst support in any suitable manner known in the art (e.g., coprecipitation, coextrusion with a support, or impregnation). The combination of M1, M2, or M1 and M2 may account for 0.05 to 30% by mass of the carrier catalyst based on the element. In another embodiment, the combination of M1, M2, or M1 and M2 may comprise from 0.3 to 15% by mass of the carrier catalyst based on the element. In another embodiment, the combination of M1, M2, or M1 and M2 may comprise from 0.5 to 7% by mass of the carrier catalyst based on the element.

The relative amount of M1 catalyst component to M2 catalyst component can vary from 1:100 to 100:1 as determined by ICP or other common wet chemical analysis methods. In another embodiment, the relative amount of the M1 catalyst component to the M2 catalyst component can vary from 1:20 to 50:1, and in another embodiment, the M1 catalyst component to the M2 touch The relative amount of the media component can vary from 1:10 to 10:1.

The catalyst system used in the method may be contained in an amount of from 0.005 to 0.4% by mass based on the sugar-containing raw material. In another embodiment, the amount of catalyst system used in the process may range from 0.01 to 0.25% by mass of the sugar-containing material. In another embodiment, the amount of the catalyst system used in the process may range from 0.02 to 0.15 mass% of the sugar-containing material. The reaction that occurs is multi-step The relative amounts of the different amounts of the catalyst system or the components of the catalyst system can be utilized to control the rate of the different reactions. Individual applications may have different requirements for the amount of catalyst system or the relative amounts of components of the catalyst system used.

In one embodiment of the invention, the M1 catalyst component can be a solid which is soluble in the reaction mixture or at least partially soluble in the reaction mixture comprising at least water and a feedstock under the reaction conditions. An effective amount of solid M1 catalyst should be soluble in the reaction mixture. Different applications and M1 catalyst components will result in different effective amounts of the M1 catalyst component that need to be dissolved in the reaction mixture. In another embodiment of the invention, the M1 catalyst component is miscible or at least partially miscible with the reaction mixture. As with the solid M1 catalyst component, an effective amount of liquid M1 catalyst should be miscible in the reaction mixture. In addition, different applications and different M1 catalyst components will result in the need for an effective amount of the M1 catalyst component that is miscible in the reaction mixture. Typically, the amount of M1 catalyst component that is miscible in water is from 1 to 100%, in another embodiment from 10 to 100%, and in another embodiment from 20 to 100%.

The multi-component catalyst of the present invention provides several advantages over more conventional one-component catalysts. For example, in some embodiments, the manufacturing cost of the catalyst can be reduced due to the less active components that need to be incorporated on the solid catalyst support. Operating costs can be reduced since it is expected that less catalyst replenishment will be required and the more selective processing steps can be used to recover and recycle the catalyst. Other advantages include increased catalyst stability, which results in less catalyst consumption and lower cost per unit of polyol product; and increased selectivity to ethylene glycol and propylene glycol and reduced azeotropic impurities (eg, butanediol) The possibility of production.

In some embodiments, the catalyst system can be included in the reaction zone; and in other embodiments, the catalyst can pass through the reaction zone continuously or intermittently; and in other embodiments, the catalyst system is two Alternatively, at least one of the catalyst system components will remain in the reaction zone while another catalyst system component will pass through the reaction zone continuously or intermittently. Suitable reactor systems include a boiling catalytic bed reactor system, an immobilized catalytic reactor system with catalyst channels, a pre-reactor system, a fluidized bed reactor system, a mechanical mixing reactor system, a slurry reactor system ( Also known as a three-phase bubble column reactor system) and combinations thereof.

Examples of operating conditions within the reactor system include temperatures from 100 ° C to 350 ° C and hydrogen pressures greater than 150 psig. In one embodiment, the temperature within the reactor system can range from 150 °C to 350 °C; in another embodiment, the temperature within the reactor system can range from 200 °C to 280 °C. The feedstock comprising at least one sugar can be continuously contacted with the catalyst system in the reactor system, wherein the weight ratio of water to raw materials is from 1 to 100, and the weight ratio of catalyst (M1+M2) to raw materials is greater than 0.005. The pH is less than 10 and the residence time is greater than 5 minutes. In another embodiment, the weight ratio of water to feedstock is from 1 to 20 and the weight ratio of catalyst to feedstock is greater than 0.01. In yet another embodiment, the weight ratio of water to feedstock is from 1 to 5 and the weight ratio of catalyst to feedstock is greater than 0.1.

In one embodiment of the invention, the catalytic reaction system uses a slurry reactor. Slurry reactors are also known as three-phase bubble column reactors. Slurry reactor systems are known in the art and one example of a slurry reactor system is described in US 5,616,304 and Topical Report, Slurry Reactor Design Studies, DOE Project No. DE-AC22-89PC89867, Reactor Cost Comparisons (available at http://www.fischer-tropsch.org/DOE/DOE_reports/91005752/de91005752_toc.htm.). The catalyst system can be mixed with water and a sugary feedstock to form a slurry which is introduced into the slurry reactor. The reaction takes place in a slurry reactor and the catalyst is transported out of the reactor system with the effluent stream. The slurry reactor system can be operated under the conditions described above. In another embodiment, the catalytic reaction system uses an ebullated bed reactor. An ebullated bed reactor system is an example of a bubbling bed reactor system known in the art and is described in US 6,436,279.

The effluent stream of the reaction zone comprises at least a product polyol and may also comprise unreacted water, hydrogen, sugars, by-products (such as phenolic compounds and glycerin), and intermediates (such as depolymerized polysaccharides and lignin). The effluent stream may also comprise at least a portion of the catalyst system depending on the catalyst selected and the catalytic reaction system employed. The effluent stream can comprise a portion of a liquid phase catalyst system or a portion of a solid phase catalyst system. In some embodiments, the solid phase catalyst component can be advantageously removed from the effluent stream before or after recovery of the desired product or by-product. The solid phase catalyst group can be removed from the effluent stream using one or more techniques (eg, direct filtration, post-precipitation filtration, hydrocyclone, fractionation, centrifugation, use of flocculant, precipitation, extraction, evaporation, or a combination thereof) Minute. In one embodiment, the separated catalyst can be recycled to the reaction zone.

Referring to Figure 1, the catalyst system, water, and sugary feedstock are introduced to reaction zone 124 via stream 122. In the mixture of streams 122, for example, the weight ratio of water to sugar-containing material is 5 and the weight ratio of catalyst system to sugar-containing material is 0.05. At least hydrogen is introduced into reaction zone 124 via stream 125. Reaction zone 124 is attached to (for example) a temperature of 250 ° C, a hydrogen pressure of 1200 psig, a pH of 7 and a residence time of 8 minutes. The catalyst, water, and sugary feedstock in stream 122 and hydrogen in stream 125 are brought to a pressure of 1800 psig prior to introduction to reaction zone 124 to be at the same pressure as reaction zone 124. However, only the stream 125 comprising at least hydrogen is warmed to a temperature of at least 250 ° C (greater than or equal to the temperature in the reaction zone 124). Control stream 122 contains at least the temperature of the mixture of sugars to maintain a temperature below the decomposition or carbonization temperature of the sugar. In reaction zone 124, the sugar is catalytically converted to at least ethylene glycol or propylene glycol. Reaction zone effluent 126 comprises at least the product ethylene glycol or propylene glycol. Reaction zone effluent 126 may also contain alcohols, organic acids, aldehydes, monosaccharides, polysaccharides, phenolic compounds, hydrocarbons, glycerol, depolymerized lignin, and proteins. The reaction zone effluent 126 is passed to a product recovery zone 134 where the desired diol product is separated and recovered in stream 136. The remaining components of the reaction zone effluent 126 are removed from the product recovery zone 134 as stream 138.

Referring to Figure 2, water and a feedstock 210 comprising a polysaccharide are introduced into a pretreatment unit 220 wherein the sugar is ground to a particle size small enough to be pumped with water as a slurry using conventional equipment. The pretreated feedstock is combined with water in line 219 and the catalyst system in line 223 and combined stream 227 is passed to reaction zone 224. In the combined stream 227, for example, the weight ratio of water to the sugar-containing material is 20 and the weight ratio of the catalyst system to the sugar is 0.1. At least hydrogen is delivered to reaction zone 224 via stream 225. Some of the hydrogen may be combined with stream 227 prior to reaction zone 224 as indicated by optional dashed line 221. Reaction zone 224 is operated at, for example, a temperature of 280 ° C, a hydrogen pressure of 200 psig, a pH of 7 and an 8 minute residence time. Touching in stream 227 before introduction into reaction zone 224 The hydrogen in the media system, water, and pretreated sugar-containing feedstock and stream 225 reaches a pressure of 1800 psig to be the same pressure as reaction zone 224. However, only the stream 225 containing at least hydrogen is warmed to a temperature of at least 250 ° C (greater than or equal to the temperature in reaction zone 224). Control stream 227 contains at least the temperature of the mixture of sugars to maintain a lower decomposition or charring temperature of the polysaccharide. In reaction zone 224, the sugar is catalytically converted to at least ethylene glycol or polyethylene glycol.

Reaction zone effluent 226 comprises at least the product ethylene glycol or propylene glycol and a catalyst. Reaction zone effluent 226 may also contain alcohols, organic acids, aldehydes, monosaccharides, polysaccharides, phenolic compounds, hydrocarbons, glycerin, depolymerized lignin, and proteins. The reaction zone effluent 226 is passed to an optional catalyst system recovery zone 228 where the catalyst component is separated from the reaction zone effluent 226 and removed within line 232. As indicated by the optional dashed line 229, the catalyst component within line 232 can be recycled for combination with or recycled to reaction zone 224 as desired. The lean catalyst component reaction zone effluent 230 is passed to a product recovery zone 234 where the desired diol product is separated and recovered in stream 236. The remaining components of the effluent 230 are removed from the product recovery zone 234 by stream 238.

Instance

Seventeen experiments were performed according to the following steps. One gram of sugary feedstock and 100 grams of deionized water were added to a 300 ml Parr autoclave reactor. An effective amount of a catalyst comprising the M1 and M2 components is added to the reactor. Details of the types and amounts of such materials and catalysts are shown in the table below. The autoclave was sealed and sequentially purged with N ₂ and H ₂ and finally pressurized to 6 MPa with H ₂ at room temperature. While continuing to stir at 1000 rpm, the autoclave was heated to 245 ° C and maintained at this temperature for 30 minutes. After 30 minutes, the autoclave was cooled to room temperature, and the liquid product was recovered by filtration and analyzed using HPLC. Microcrystalline cellulose was purchased from Sigma-Aldrich. A nickel/Norit CA-1 catalyst was prepared by impregnating different amounts of nickel (using a Ni nitrate aqueous solution) onto the activated carbon support Norit CA-1 using an incipient wetness technique. Next, the impregnated support was dried overnight at 40 ° C in a nitrogen purged oven and reduced in H ₂ at 750 ° C for 1 hr. 5% Pd/C and 5% Pt/C were purchased from Johnson Matthey. The yields of ethylene glycol and propylene glycol are determined by dividing the mass of ethylene glycol or propylene glycol produced by the mass of the raw materials used and multiplying by 100.

122‧‧‧ Logistics containing catalyst systems, water and sugary raw materials

124‧‧‧Reaction zone

125‧‧‧ Hydrogen flow

126‧‧‧Reaction zone effluent

134‧‧‧Product recovery area

136‧‧‧Product stream

138‧‧‧Residual component flow

210‧‧‧Water and raw materials containing polysaccharides

219‧‧‧ pipeline

220‧‧‧Pretreatment unit

221‧‧‧Optional dotted line

223‧‧‧ pipeline

224‧‧‧Reaction zone

225‧‧‧ Hydrogen flow

226‧‧‧Reaction zone effluent

227‧‧‧Combined flow

228‧‧‧catalyst system recovery area

229‧‧‧Optional dotted line

230‧‧‧Poor catalyst component reaction zone effluent

232‧‧‧ pipeline

234‧‧‧Product recovery area

236‧‧‧Product stream

238‧‧‧Residual component flow

1 is a basic flow diagram of an embodiment of the present invention. Equipment and processing steps not required to understand the present invention are not depicted.

2 is a basic flow diagram of another embodiment of the present invention showing an optional pretreatment zone and an optional carrier catalyst component separation zone with optional carrier catalyst component recycle. Equipment and processing steps not required to understand the present invention are not depicted.

122‧‧‧ Logistics containing catalyst systems, water and sugary raw materials

124‧‧‧Reaction zone

125‧‧‧ Hydrogen flow

126‧‧‧Reaction zone effluent

134‧‧‧Product recovery area

136‧‧‧Product stream

138‧‧‧Residual component flow

Claims (10)

A method of producing at least one polyol from a feedstock, the method comprising: a) contacting hydrogen, water, and a feedstock comprising at least one sugar with a catalyst system to produce an effluent stream comprising at least one polyol, the catalyst system comprising : an unsupported component comprising a compound comprising an element selected from the group consisting of IUPAC Groups 4, 5 and 6 of the Periodic Table of the Elements and having an oxidation state greater than or equal to 2+, wherein the carrier-free component is The compound is in the form of a non-carbide, nitride or phosphide; and a carrier hydrogenation component on a solid catalyst support selected from the group consisting of IUPAC Groups 8, 9 and 10 of the Periodic Table of the Elements; And b) recovering the polyol from the effluent stream. The method of claim 1, wherein the method operates in a mode selected from the group consisting of batch mode operation and continuous mode operation. The method of claim 1, wherein the contacting occurs in a reaction zone comprising at least a first input stream comprising at least a flowing feedstock and the second input stream comprising flowing hydrogen, wherein the second input stream comprises flowing hydrogen The first input stream is pressurized and optionally heated to a temperature below the decomposition temperature of the sugar in the feedstock prior to the reaction zone, and the second input stream is pressurized and heated prior to the reaction zone. . The method of claim 1, wherein the saccharide-containing material is selected from the group consisting of short-term rotation forestry, industrial wood waste, forest residues, agricultural residues, energy crops, industrial wastewater, municipal wastewater, paper, Cardboard, fabric, biomass pulp, corn starch, sugar cane, grain, sugar beet, glycogen, molecules comprising the molecular unit structure C _m (H ₂ O) _n , and combinations thereof. The method of claim 1, wherein the effluent stream further comprises at least one by-product selected from the group consisting of alcohols, organic acids, aldehydes, monosaccharides, polysaccharides, phenolic compounds, hydrocarbons, glycerol, depolymerization Lignin and protein. The method of claim 1, wherein the hydrogen, water, and feedstock are contacted with the catalyst system in a slurry reactor system at a temperature between 100 ° C and 350 ° C and a hydrogen pressure greater than 150 psig operating. A catalyst system comprising: a) an unsupported component comprising a compound comprising an element selected from the group consisting of IUPAC Groups 4, 5, and 6 of the Periodic Table of the Elements, and having an oxidation state greater than or equal to 2+, Wherein the compound in the unsupported component is in the form of a non-carbide, nitride or phosphide; and b) a carrier hydrogenation component comprising on the solid catalyst support selected from IUPAC No. 8 of the Periodic Table of the Elements, Elements of the group consisting of 9 and 10 families. The catalyst system of claim 7, wherein the unsupported component is contained in at least one compound selected from the group consisting of tungstic acid, molybdic acid, ammonium tungstate, ammonium metatungstate, ammonium paratungstate, tungsten Heteropoly compound, heteropoly compound of molybdenum, tungsten oxide, molybdenum oxide, vanadium oxide, metavanadate, chromium oxide, chromium sulfate, titanium ethoxide, zirconium acetate, zirconium carbonate, zirconium hydroxide, cerium oxide , ethanol oxime, and combinations thereof. The catalyst system of claim 7, wherein the hydrogenation component is selected from the group consisting of Pt, Pd, Ru, Rh, Ni, Ir, and combinations thereof. The catalyst system of claim 7, wherein the solid catalyst carrier is selected from the group consisting of carbon, Al ₂ O ₃ , ZrO ₂ , SiO ₂ , MgO, Ce _x ZrO _y , TiO ₂ , SiC, vermiculite, alumina, lanthanum A group of stone alumina, zeolite, clay, and combinations thereof.