WO2010045766A1 - 一种纤维素制乙二醇的方法 - Google Patents
一种纤维素制乙二醇的方法 Download PDFInfo
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- WO2010045766A1 WO2010045766A1 PCT/CN2008/072894 CN2008072894W WO2010045766A1 WO 2010045766 A1 WO2010045766 A1 WO 2010045766A1 CN 2008072894 W CN2008072894 W CN 2008072894W WO 2010045766 A1 WO2010045766 A1 WO 2010045766A1
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- catalyst
- cellulose
- active component
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- tungsten
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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
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- 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
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
- B01J27/20—Carbon compounds
- B01J27/22—Carbides
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- 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
- B01J27/24—Nitrogen compounds
- B01J27/25—Nitrates
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
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- 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
Definitions
- the present invention relates to a process for the preparation of ethylene glycol from cellulose, in particular to a process in which cellulose is subjected to one-step catalytic hydrodegradation to ethylene glycol under hydrothermal conditions.
- Ethylene glycol is an important energy liquid fuel and is also a very important raw material for polyester synthesis.
- PET polyethylene terephthalate
- PEN polyethylene naphthalate
- ethylene glycol is mainly based on the petroleum raw material route, that is, ethylene epoxidation to obtain ethylene oxide, and then hydration to obtain ethylene glycol
- Document 1 Cui Huaweing, domestic and international ethylene glycol production development overview, chemistry Industrial, 2007, 25, (4), 15-21.
- Document 2 Pr ° C ess for preparing ethanediol by catalyzing epoxyethane hydration, Patent No. CN1463960-A; CN1204103-C].
- the synthesis method relies on non-renewable petroleum resources, and the production process includes selective oxidation or epoxidation steps, which are technically difficult, inefficient, have many by-products, high material consumption and serious pollution.
- cellulose glycols not only opens up new synthetic pathways, but also enables products of high economic value from inexpensive cellulose. Moreover, since cellulose is not consumed by humans, it does not affect human food security. Further, cellulose is formed by condensation of a glucose unit through a glycosidic bond and contains a large amount of a hydroxyl group. These hydroxyl groups are completely retained during the conversion of cellulose to ethylene glycol, making this conversion process extremely atomic. Thus, the conversion of cellulose to ethylene glycol has significant advantages that are unmatched by many other production routes.
- the cellulose is subjected to a one-step catalytic hydrogenation degradation process to produce ethylene glycol in high yield and high selectivity.
- the technical solution adopted by the present invention is as follows: cellulose is used as a reaction raw material, and the active component of the catalyst is composed of two parts.
- One part is a transition metal of Groups 8, 9, and 10, one or more of cobalt, nickel, ruthenium, rhodium, palladium, iridium, and platinum.
- the other part is a metallic molybdenum and/or tungsten, or a carbide with molybdenum, a nitride of molybdenum, a phosphide of molybdenum, and/or a carbide of tungsten, a nitride of tungsten, a phosphide of tungsten.
- the reaction was carried out by stirring in a closed autoclave.
- the initial pressure of hydrogen in the reactor at room temperature is l-12 MPa, the reaction temperature is 120-300 ° C, and the reaction time is not less than 5 minutes.
- the weight ratio of the second portion to the active component of the first portion is in the range of 0.02 to 1600 times.
- the active component is supported on a carrier, including activated carbon, alumina, silica, silicon carbide, zirconia, zinc oxide, titanium dioxide or one or more composites; the first part of the active component metal is on the catalyst at 0.05- 50 wt%, the second part of the active component metal is present on the catalyst in an amount of from 1 to 80% by weight.
- a framework metal catalyst having an active component as a catalyst skeleton such as Raney nickel or the like.
- the mass ratio of cellulose to water of the reaction raw material is 1:200-1:4, and the mass ratio of cellulose to catalyst is 1:1-30:1.
- the largest cellulose produced in natural biomass is used as a raw material, which has a wide range of sources, including wood, cotton, crop straw, etc., and has the advantages of low raw material cost.
- ethylene is used as a raw material, and the reaction process provided by the present invention does not consume fossil resources, and has the advantages of renewable raw material resources, and meets the requirements of sustainable development.
- the present invention utilizes cellulose which is inedible by humans as a raw material, thereby maximally eliminating raw materials.
- the process of material energy conversion may have adverse effects on human food security.
- the reaction process of the present invention is simple, and it is not necessary to carry out acid hydrolysis of cellulose in advance, and ethylene glycol made of cellulose can be realized only by one-step reaction process.
- the reaction system Hydrogenation and conversion of cellulose under hydrothermal conditions, the reaction system is environmentally friendly and non-polluting. Water is used as the reaction medium, and no inorganic acid or alkali is used in the reaction, which avoids the environmental pollution problems common in the cellulose degradation process. 6.
- the reaction process has high product yield and selectivity, and the yield of ethylene glycol can reach 70%, which has a good application prospect.
- the present invention achieves high efficiency, high selectivity, and high yield of ethylene glycol for the preparation of ethylene glycol.
- the reaction provided by the present invention has the remarkable advantages that the raw material is a renewable resource, the reaction process is green and environmentally friendly, and the atomic economy is obtained.
- metal tungsten catalyst Preparation of metal tungsten catalyst: The ammonium metatungstate solution (mass concentration 0.4 g/ml) was immersed on the activated carbon support, dried in an oven at 120 ° C for 12 h, and then placed in an H 2 atmosphere at 700 ° C for 1 h. W/AC with a tungsten loading of 30% was obtained.
- the tungsten catalyst prepared according to Example 1 was further impregnated with a nickel nitrate solution, dried at 120 ° C, and reduced at 400 ° C for 2 h to obtain MW /AC (15% Ni-25% W). ) Catalyst.
- tungsten carbide catalyst Preparation of tungsten carbide catalyst: The ammonium metatungstate solution (mass concentration 0.4 g/ml) was immersed on an activated carbon support (AC), and after drying in a 120 oven for 12 h, the catalyst precursor was placed in an H2 atmosphere at 800 °C. The carbothermal reaction was carried out for 1 hour to obtain a W2C/AC catalyst having a tungsten loading of 30%.
- AC activated carbon support
- tungsten nitride catalyst Preparation of tungsten nitride catalyst: Ammonium metatungstate solution (mass concentration 0.2 g / ml) was immersed in activated carbon support, dried in a 120 oven for 12 h, then placed in an NH3 atmosphere for 700 nitridation for 1 h to obtain tungsten The load is 15 ⁇ % of W2N/AC.
- Ni-W2N /AC catalyst 15 wt% Ni- 15 wt% W.
- Example 7 Preparation of a molybdenum nitride catalyst: An ammonium molybdate solution (mass concentration of 0.3 g/ml) was impregnated with an activated carbon support (AC). After drying in a 120 oven for 12 h, the catalyst precursor was placed in a H3 atmosphere at 700 ° C for 1 h to obtain a Mo2N /AC catalyst (15 wt% Mo).
- AC activated carbon support
- Ni-Mo 2 N /AC catalyst 15 wt% M-15 wt% Mo.
- molybdenum phosphide catalyst Preparation of molybdenum phosphide catalyst: Ammonium molybdate and diammonium phosphate were formulated into a solution according to a ratio of molybdenum to phosphorus atomic ratio of 1:1.2. The solution was immersed in a Ti02 support, dried over 120, and reduced with hydrogen at 650 ° C for 2 h to obtain a MoP/Ti02 catalyst (16 wt% Mo).
- ammonium molybdate, diammonium hydrogen phosphate and antimony trichloride are formulated into a solution according to a certain ratio, wherein the atomic ratio of molybdenum to phosphorus is 1:1.2, and the weight ratio of molybdenum and rhenium is 8:1.
- the solution was impregnated with a Ti02 support, dried over 120, and then reduced with hydrogen at 650 °C for 2 hours to obtain a Ru-MoP / Ti02 catalyst (2 wt% Ru-16 wt% Mo).
- the product yield is calculated only for the target product ethylene glycol and hexahydric alcohol (including sorbitol, mannitol).
- Other liquid products include propylene glycol, butyl glycol, ethanol, unknown components, and gaseous products (C02, CH4, C2H6). Etc.) The yield was not calculated.
- a catalyst composed of a nitrogen nitride, a phosphide of tungsten and molybdenum and a hydrogenation catalytically active component has a good ethylene glycol yield.
- Effect of catalyst usage A simple mechanical mixture of a catalyst containing a single active component of tungsten carbide, metal molybdenum and tungsten and a Group 8, 9, 10 metal catalyst in a weight ratio of 1:1 is added to the reaction system. Used in the middle, the cellulose reaction results are listed in the following table (Table 4). The reaction conditions were the same as in Example 11.
- the nickel-tungsten catalyst has excellent ethylene glycol yield in a certain reaction time.
- the preferred time is between 30 min and 3 h.
- the nickel-tungsten catalyst has excellent ethylene glycol yield in a certain temperature range.
- the preferred temperature is around 220-250 °C.
- the nickel-tungsten catalyst has excellent ethylene glycol yield under a certain reaction pressure.
- the preferred reaction pressure is 3-7 MPa.
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Claims
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP08877495.5A EP2338867B1 (en) | 2008-10-24 | 2008-10-31 | A process for preparing ethylene glycol using cellulose |
MX2010011284A MX2010011284A (es) | 2008-10-24 | 2008-10-31 | Un procedimiento para preparar etilenglicol con el uso de celulosa. |
ES08877495.5T ES2447367T3 (es) | 2008-10-24 | 2008-10-31 | Un proceso para preparar etilenglicol usando celulosa |
CA2725248A CA2725248C (en) | 2008-10-24 | 2008-10-31 | Method of preparing ethylene glycol from cellulose |
US12/734,601 US7960594B2 (en) | 2008-10-24 | 2008-10-31 | Method of preparing ethylene glycol from cellulose |
BRPI0822634A BRPI0822634B1 (pt) | 2008-10-24 | 2008-10-31 | método para a prepararação de etileno glicol a partir de celulose |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN2008102282577A CN101723802B (zh) | 2008-10-24 | 2008-10-24 | 一种纤维素制乙二醇的方法 |
CN200810228257.7 | 2008-10-24 |
Publications (1)
Publication Number | Publication Date |
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WO2010045766A1 true WO2010045766A1 (zh) | 2010-04-29 |
Family
ID=42118905
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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PCT/CN2008/072894 WO2010045766A1 (zh) | 2008-10-24 | 2008-10-31 | 一种纤维素制乙二醇的方法 |
Country Status (8)
Country | Link |
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US (1) | US7960594B2 (zh) |
EP (1) | EP2338867B1 (zh) |
CN (1) | CN101723802B (zh) |
BR (1) | BRPI0822634B1 (zh) |
CA (1) | CA2725248C (zh) |
ES (1) | ES2447367T3 (zh) |
MX (1) | MX2010011284A (zh) |
WO (1) | WO2010045766A1 (zh) |
Cited By (6)
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US8222465B2 (en) | 2011-07-28 | 2012-07-17 | Uop Llc | Catalytic process for continuously generating polyols |
US8222462B2 (en) | 2011-07-28 | 2012-07-17 | Uop Llc | Process for generation of polyols from saccharides |
US8222464B2 (en) | 2011-07-28 | 2012-07-17 | Uop Llc | Catalytic process for continuously generating polyols |
US8222463B2 (en) | 2011-07-28 | 2012-07-17 | Uop Llc | Process for generation of polyols from saccharide containing feedstock |
US8323937B2 (en) | 2011-07-28 | 2012-12-04 | Uop Llc | Continuous catalytic generation of polyols from cellulose |
US8410319B2 (en) | 2011-07-28 | 2013-04-02 | Uop Llc | Continuous catalytic generation of polyols from cellulose with recycle |
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Publication number | Publication date |
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ES2447367T3 (es) | 2014-03-11 |
EP2338867A1 (en) | 2011-06-29 |
MX2010011284A (es) | 2010-11-10 |
BRPI0822634B1 (pt) | 2017-03-07 |
CN101723802A (zh) | 2010-06-09 |
CN101723802B (zh) | 2013-06-19 |
CA2725248C (en) | 2015-01-20 |
CA2725248A1 (en) | 2010-04-29 |
EP2338867B1 (en) | 2014-01-08 |
US7960594B2 (en) | 2011-06-14 |
BRPI0822634A2 (pt) | 2015-06-16 |
EP2338867A4 (en) | 2012-06-13 |
US20100256424A1 (en) | 2010-10-07 |
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