USRE37329E1 - Ruthenium-based catalyst for producing lower polyhydric alcohols - Google Patents
Ruthenium-based catalyst for producing lower polyhydric alcohols Download PDFInfo
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- USRE37329E1 USRE37329E1 US08/832,763 US83276397A USRE37329E US RE37329 E1 USRE37329 E1 US RE37329E1 US 83276397 A US83276397 A US 83276397A US RE37329 E USRE37329 E US RE37329E
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- suspension
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- activated carbon
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- 239000003054 catalyst Substances 0.000 title claims abstract description 42
- 150000005846 sugar alcohols Polymers 0.000 title claims abstract description 21
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 229910052707 ruthenium Inorganic materials 0.000 title claims abstract description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 47
- 238000000034 method Methods 0.000 claims abstract description 15
- 238000007327 hydrogenolysis reaction Methods 0.000 claims abstract description 13
- 239000011148 porous material Substances 0.000 claims abstract description 9
- 239000000725 suspension Substances 0.000 claims description 40
- 239000007787 solid Substances 0.000 claims description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 5
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 5
- 230000005587 bubbling Effects 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 238000009826 distribution Methods 0.000 claims description 3
- 235000013311 vegetables Nutrition 0.000 claims description 2
- 239000008187 granular material Substances 0.000 claims 4
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 7
- 238000010924 continuous production Methods 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 39
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 29
- 239000000600 sorbitol Substances 0.000 description 29
- 235000010356 sorbitol Nutrition 0.000 description 29
- 238000006243 chemical reaction Methods 0.000 description 23
- 239000000243 solution Substances 0.000 description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 239000012530 fluid Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 150000001720 carbohydrates Chemical class 0.000 description 4
- 235000014633 carbohydrates Nutrition 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 2
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000008103 glucose Substances 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- -1 sulphide ion Chemical group 0.000 description 2
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- 239000004386 Erythritol Substances 0.000 description 1
- UNXHWFMMPAWVPI-UHFFFAOYSA-N Erythritol Natural products OCC(O)C(O)CO UNXHWFMMPAWVPI-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 229930091371 Fructose Natural products 0.000 description 1
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 1
- 239000005715 Fructose Substances 0.000 description 1
- 229930195725 Mannitol Natural products 0.000 description 1
- 229910019891 RuCl3 Inorganic materials 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 description 1
- PIKZHTNNKKFXSW-UHFFFAOYSA-N [N].[Hg] Chemical compound [N].[Hg] PIKZHTNNKKFXSW-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 150000002016 disaccharides Chemical class 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- UNXHWFMMPAWVPI-ZXZARUISSA-N erythritol Chemical compound OC[C@H](O)[C@H](O)CO UNXHWFMMPAWVPI-ZXZARUISSA-N 0.000 description 1
- 235000019414 erythritol Nutrition 0.000 description 1
- 229940009714 erythritol Drugs 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 150000002402 hexoses Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000000594 mannitol Substances 0.000 description 1
- 235000010355 mannitol Nutrition 0.000 description 1
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002772 monosaccharides Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical class CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 239000000811 xylitol Substances 0.000 description 1
- 235000010447 xylitol Nutrition 0.000 description 1
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 description 1
- 229960002675 xylitol Drugs 0.000 description 1
Classifications
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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
-
- 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
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/462—Ruthenium
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/31—Density
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/617—500-1000 m2/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/638—Pore volume more than 1.0 ml/g
-
- 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
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/31—Density
- B01J35/32—Bulk density
-
- 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 method for production in a fixed bed reactor of lower polyhydric alcohols and their mixtures, comprising hydrogenolysis under pressure of higher polyhydric alcohols in the presence of a supported metal catalyst.
- higher polyhydric alcohols means products such as sorbitol, mannitol and xylitol derived from catalytic hydrogenation of carbohydrates (and in particular of glucose, fructose and their mixtures).
- lower polyhydric alcohols means polyalcohols having a maximum of 6 carbon atoms and a maximum of 3 hydroxyl groups, in particular ethanediol, propylene glycol, butanediol and glycerol.
- the invention also relates to a new supported ruthenium-based catalyst and its use in the production of chemicals from renewable raw materials (carbohydrates and their derivatives); in particular for selective transformation of low molecular weight polyhydric alcohol hexoses.
- a first object of the present invention is to provide a method of the type specified initially in the description, which enables hydrogenolysis of higher polyhydric alcohols to take place in a continuous fixed bed reactor.
- a second aspect of the invention consists of use of a ruthenium-based catalyst supported on granulated activated carbon, having:
- the specific type of activated carbon used having the aforementioned features also has high mechanical resistance and a particle size which make it suitable for use in a fixed reactor of the trickle-bed type.
- the specific surface area of the granulated activated carbon support is preferably between 800 and 1000 m 2 /g, and the total volume of the pores is between 0.6 and 0.7 cm 3 /g.
- granulated activated carbon is meant a carbon which has a particle size of between 5.7 and 0.5 mm (3 and 32 mesh) and preferably a particle size of between 4.7 and 2.4 mm (4 and 8 mesh, Tiller series).
- the optimum particle size is selected on the basis of the process parameters, according to known criteria.
- Activated carbon of the aforementioned type is available commercially in the form of the activated carbons made by ACQUE NYMCO having the references GH12132 and CA12132.
- the reaction temperature is generally between 200° and 300° C., and preferably 220° -270° C.
- the spatial hourly velocity of the fluid is between 0.3 and 4, and preferably between 0.67 and 2.50 h ⁇ 1
- the reaction pressure is between 5 and 20 MPa and preferably between 7.5 and 15 MPa.
- the continuous reactor is preferably supplied with a reaction promoter selected from amongst alkaline and alkaline earth hydroxides, and preferably sodium hydroxide, or basic reaction salts; the molar ratio between the higher polyhydric alcohols and the promoter supplied is between 3 and 30.
- the reactor is preferably also supplied with sulphides as reaction moderators (in order to avoid the formation of undesirable final products such as methane), with a concentration in the solution supplied lower than 150 ppm calculated relative to the sulphide ion.
- the concentration of the ruthenium on the activated carbon is between 0.5 and 5 weight %, and preferably between 1 and 3 weight %.
- the higher polyhydric alcohol or mixture of higher polyhydric alcohols is supplied to the hydrogenation reactor, preferably in an aqueous solution in a concentration of 20 to 40 weight %.
- the higher polyhydric alcohol or mixture of higher polyhydric alcohols is preferably obtained in a first stage of hydrogenation of carbohydrates, carried out at a low basic pH and preferably between 7.5 and 8 with a reaction temperature of between 120° and 150° C.
- This first stage is also preferably carried out in an aqueous solution in the presence of a basic promoter, such as those previously described, in a quantity sufficient to maintain the pH in the above-described field.
- the carbohydrate may consist of monosaccharides or disaccharides.
- the supply preferably consists of an aqueous solution of glucose which is converted with virtually maximum theoretical yield into sorbitol.
- this hydrogenation stage also, which is carried out continuously on a fixed bed, the ruthenium catalyst supported on granulated activated carbon, as previously described, is advantageously used.
- the method of preparing the catalyst according to the invention comprises the main stages of suspending the granulated activated carbon in water, adding a ruthenium chloride solution to the suspension, adjusting the pH of the suspension to a value of between 4.5 and 8 by adding an alkaline agent, heating the suspension to a temperature of between 70° and 100° C. and maintaining the suspension at this temperature for a time of between 30 minutes and 2 hours, separating the solid from the suspension by filtration, re-suspending the solid in a solution of alkaline agent, heating the suspension to a temperature of between 60° and 100° C., bubbling a hydrogen flow into the suspension for a time of between 1 and 3 hours, and separating the solid from the suspension.
- the catalyst thus obtained has the features of porosity, specific surface area and specific weight of the original activated carbon.
- an activated carbon CA 12132 of vegetable origin was used:
- a quantity of 303.3 g of this granulated activated carbon with 6% humidity is suspended in a liter of distilled water and is mechanically agitated. After approximately 30 minutes the pH of the suspension is 10.5. 2 liters of solution of RuCl 3 containing 15 g of ruthenium is added slowly to this suspension (over a period of approximately 2 hours) with a constant flow. When this addition is completed, the pH of the suspension is 0.92. The suspension is adjusted to a pH value of 4.8 by means of a 1 molar solution of sodium carbonate and after approximately 20 minutes the pH is adjusted to 6 by adding another solution, or sodium carbonate. The suspension is then heated to a temperature of 90° C. and is maintained at that temperature for approximately 2 hours.
- the granulated solid is separated from the solution by means of filtering, and is preliminarily washed. It is then resuspended in 2 liters of 0.1 molar solution of sodium carbonate. An argon flow is bubbled through the suspension, which is contained in a three-necked flask and is gently mechanically agitated, until the air is completely removed. The argon flow is then replaced by a hydrogen flow, and the suspension is heated to a temperature of 80° C. The suspension is maintained for 2 hours in the hydrogen flow, preferably at 80° C. The hydrogen flow is then replaced by an argon flow and the catalyst is filtered and washed until there are no chlorides in the washing waters. The wet ruthenium-based catalyst is stored in a closed container.
- the catalyst prepared according to example 1 is loaded (100 cm 3 ) into a tubular, fixed, regular-flow, trickle-bed reactor provided with a gas—fluid separator disposed at the reactor outlet, a tank for supplying the reagents and a hydrogen gas tank.
- the reactor has a diameter of 20.5 mm (height of the catalytic bed approximately 30 cm), and is provided with a coaxial thermocouple which has 3 temperature-measuring areas disposed at 2.5, 15 and 28 cm below the upper edge of the catalytic bed.
- the reactor is closed and is connected to the system for supplying the reagents and discharging the products, and is pressurised with nitrogen in order to ensure that it is airtight.
- the reactor is then supplied at the test pressure with 2 flows: a mixed hydrogen—water flow, obtained by injecting water into the hydrogen current in order to saturate it, and a second flow of deionised water. Before reaching the catalytic bed, the two flows are thoroughly mixed through the layer of inert material. Heating of the reactor is then started and the test temperature is reached in approximately 2 hours. In these conditions the water flow is replaced by a flow of aqueous solution of sorbitol containing sodium hydroxide and sodium sulphide. After approximately 8 hours the temperature and spatial velocity (LHSV) of the system are steady.
- LHSV spatial velocity
- the fluid samples of the reaction products are analysed by means of high pressure liquid chromatography (HPLC).
- HPLC high pressure liquid chromatography
- the gas output by the gas—fluid separator is measured and analysed by means of gas chromatography, in order to reveal any hydrocarbons present (methane, ethane etc.) and the carbon dioxide.
- the fluid product contains mainly 1.2-propylene glycol, ethanediol, butanediol, and smaller amounts of glycerol, lactic acid and monovalent alcohols, as well as products such as erythritol, pentanediols, and possibly non-converted sorbitol.
- the results of examples 2-3 for two different reaction temperatures are given in tables 1 and 2 hereinafter, relative respectively to the operative conditions and distribution of the reaction products.
- the catalyst prepared according to example 1 is used in a reactor according to examples 2 and 3 in a sorbitol hydrogenolysis process which varies the molar ratio between the sorbitol and promoter (NaOH) in the supply flow.
- the catalyst prepared according to example 1 is used in a reactor according to examples 2 and 3 for hydrogenation of sorbitol, varying the sulphur ion content, the sorbitol/promoter molar ratio in the supply, and the reaction temperature.
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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)
Abstract
A ruthenium-based hydrogenation catalyst, particularly but not exclusively for hydrogenolysis under pressure of higher polyhydric alcohols, comprises ruthenium supported on granular activated carbon, and has:
a specific surface area of from 600 to 1000 m2/g;
a total pore volume of from 0.5 to 1.2 cm3/g;
an apparent specific weight (bulk density) of from 0.45 to 0.55 g/cm3;
an actual specific weight of from 1.9 to 2.3 g/cm3;
a total volume of micropores having a radius smaller than 75 A of from 0.4 to 0.55 cm3/g; and
an ash content of from 2 to 5% by weight.
The catalyst is used in a method for the continuous production of lower polyhydric alcohols in a fixed bed reactor, by means of hydrogenolysis under pressure of higher polyhydric alcohols.
Description
The present invention relates to a method for production in a fixed bed reactor of lower polyhydric alcohols and their mixtures, comprising hydrogenolysis under pressure of higher polyhydric alcohols in the presence of a supported metal catalyst.
In the present description, the term higher polyhydric alcohols means products such as sorbitol, mannitol and xylitol derived from catalytic hydrogenation of carbohydrates (and in particular of glucose, fructose and their mixtures). The term lower polyhydric alcohols means polyalcohols having a maximum of 6 carbon atoms and a maximum of 3 hydroxyl groups, in particular ethanediol, propylene glycol, butanediol and glycerol.
The invention also relates to a new supported ruthenium-based catalyst and its use in the production of chemicals from renewable raw materials (carbohydrates and their derivatives); in particular for selective transformation of low molecular weight polyhydric alcohol hexoses.
U.S. Pat. Nos. 2,868,847 and 4,476,331 describe the use of a ruthenium-based catalyst on a powdered active carbon support. The methods of hydrogenation and catalytic hydrogenolysis described in these documents comprise batch reactions in which the powdered catalyst is supplied to the reactor together with the reagents.
A first object of the present invention is to provide a method of the type specified initially in the description, which enables hydrogenolysis of higher polyhydric alcohols to take place in a continuous fixed bed reactor.
For this purpose, a second aspect of the invention consists of use of a ruthenium-based catalyst supported on granulated activated carbon, having:
a specific surface area of 600 to 1000 m2/g (B.E.T. method);
a total pore volume of 0.5 to 1.2 cm3/g (combined nitrogen-mercury method);
an apparent specific weight (bulk density) of 0.45 to 0.55 g/cm3;
an actual specific weight of 1.9 to 2.3 g/cm3;
a total volume of micropores having a radius smaller than 75 A of 0.4 to 0.55 cm3/g; and
an ash content of 2 to 5 weight %.
The specific type of activated carbon used having the aforementioned features also has high mechanical resistance and a particle size which make it suitable for use in a fixed reactor of the trickle-bed type.
The possibility of being able to carry out fixed bed hydrogenation/hydrogenolysis enables increased productivity of the plant to be obtained. It has also been found unexpectedly that fixed bed hydrogenolysis enables increased selectivity of lower polyhydric alcohols to be obtained in comparison with a reaction in batch form.
The specific surface area of the granulated activated carbon support is preferably between 800 and 1000 m2/g, and the total volume of the pores is between 0.6 and 0.7 cm3/g.
By granulated activated carbon is meant a carbon which has a particle size of between 5.7 and 0.5 mm (3 and 32 mesh) and preferably a particle size of between 4.7 and 2.4 mm (4 and 8 mesh, Tiller series). The optimum particle size is selected on the basis of the process parameters, according to known criteria.
Use of activated carbon which has the above-described characteristics is critical for the purposes of the activity of the catalyst and the possibility of using it on a fixed bed.
Activated carbon of the aforementioned type is available commercially in the form of the activated carbons made by ACQUE NYMCO having the references GH12132 and CA12132.
In the hydrogenolysis method according to the invention, the reaction temperature is generally between 200° and 300° C., and preferably 220° -270° C., the spatial hourly velocity of the fluid is between 0.3 and 4, and preferably between 0.67 and 2.50 h−1, and the reaction pressure is between 5 and 20 MPa and preferably between 7.5 and 15 MPa. The continuous reactor is preferably supplied with a reaction promoter selected from amongst alkaline and alkaline earth hydroxides, and preferably sodium hydroxide, or basic reaction salts; the molar ratio between the higher polyhydric alcohols and the promoter supplied is between 3 and 30. The reactor is preferably also supplied with sulphides as reaction moderators (in order to avoid the formation of undesirable final products such as methane), with a concentration in the solution supplied lower than 150 ppm calculated relative to the sulphide ion.
The concentration of the ruthenium on the activated carbon is between 0.5 and 5 weight %, and preferably between 1 and 3 weight %.
The higher polyhydric alcohol or mixture of higher polyhydric alcohols is supplied to the hydrogenation reactor, preferably in an aqueous solution in a concentration of 20 to 40 weight %.
The higher polyhydric alcohol or mixture of higher polyhydric alcohols is preferably obtained in a first stage of hydrogenation of carbohydrates, carried out at a low basic pH and preferably between 7.5 and 8 with a reaction temperature of between 120° and 150° C. This first stage is also preferably carried out in an aqueous solution in the presence of a basic promoter, such as those previously described, in a quantity sufficient to maintain the pH in the above-described field. In this first stage the carbohydrate may consist of monosaccharides or disaccharides. However the supply preferably consists of an aqueous solution of glucose which is converted with virtually maximum theoretical yield into sorbitol. In this hydrogenation stage also, which is carried out continuously on a fixed bed, the ruthenium catalyst supported on granulated activated carbon, as previously described, is advantageously used.
The method of preparing the catalyst according to the invention comprises the main stages of suspending the granulated activated carbon in water, adding a ruthenium chloride solution to the suspension, adjusting the pH of the suspension to a value of between 4.5 and 8 by adding an alkaline agent, heating the suspension to a temperature of between 70° and 100° C. and maintaining the suspension at this temperature for a time of between 30 minutes and 2 hours, separating the solid from the suspension by filtration, re-suspending the solid in a solution of alkaline agent, heating the suspension to a temperature of between 60° and 100° C., bubbling a hydrogen flow into the suspension for a time of between 1 and 3 hours, and separating the solid from the suspension.
The catalyst thus obtained has the features of porosity, specific surface area and specific weight of the original activated carbon.
Further advantages and features of the method of producing the catalyst and of the method according to the invention which uses this catalyst will become apparent from the attached examples, which should not be understood as limitations of the scope of the present invention.
For preparation of the catalyst according to the present invention, an activated carbon CA 12132 of vegetable origin, and having the following characteristics, was used:
specific surface area: 800 m2/g;
actual specific weight: 2.1 g/cm3;
total volume of the pores: 0.6 cm3/g;
micropore volume (R<75 A): 0.5 cm3/g;
apparent specific weight (bulk density): 0 52 g/cm3;
ash content: 3 weight %;
particle size: 10-18 mesh: (series 2—1 mm): 20-30 weight % 18-35 mesh: (series 1—0.5 mm): 80-70 weight %.
A quantity of 303.3 g of this granulated activated carbon with 6% humidity is suspended in a liter of distilled water and is mechanically agitated. After approximately 30 minutes the pH of the suspension is 10.5. 2 liters of solution of RuCl3 containing 15 g of ruthenium is added slowly to this suspension (over a period of approximately 2 hours) with a constant flow. When this addition is completed, the pH of the suspension is 0.92. The suspension is adjusted to a pH value of 4.8 by means of a 1 molar solution of sodium carbonate and after approximately 20 minutes the pH is adjusted to 6 by adding another solution, or sodium carbonate. The suspension is then heated to a temperature of 90° C. and is maintained at that temperature for approximately 2 hours. The granulated solid is separated from the solution by means of filtering, and is preliminarily washed. It is then resuspended in 2 liters of 0.1 molar solution of sodium carbonate. An argon flow is bubbled through the suspension, which is contained in a three-necked flask and is gently mechanically agitated, until the air is completely removed. The argon flow is then replaced by a hydrogen flow, and the suspension is heated to a temperature of 80° C. The suspension is maintained for 2 hours in the hydrogen flow, preferably at 80° C. The hydrogen flow is then replaced by an argon flow and the catalyst is filtered and washed until there are no chlorides in the washing waters. The wet ruthenium-based catalyst is stored in a closed container.
The catalyst prepared according to example 1 is loaded (100 cm3) into a tubular, fixed, regular-flow, trickle-bed reactor provided with a gas—fluid separator disposed at the reactor outlet, a tank for supplying the reagents and a hydrogen gas tank. The reactor has a diameter of 20.5 mm (height of the catalytic bed approximately 30 cm), and is provided with a coaxial thermocouple which has 3 temperature-measuring areas disposed at 2.5, 15 and 28 cm below the upper edge of the catalytic bed. On top of the catalytic bed there is a layer of inert material (Berl Saddles) 7.5 cm deep, in order to ensure that the reagents are well-mixed before coming into contact with the catalytic bed.
The reactor is closed and is connected to the system for supplying the reagents and discharging the products, and is pressurised with nitrogen in order to ensure that it is airtight. The reactor is then supplied at the test pressure with 2 flows: a mixed hydrogen—water flow, obtained by injecting water into the hydrogen current in order to saturate it, and a second flow of deionised water. Before reaching the catalytic bed, the two flows are thoroughly mixed through the layer of inert material. Heating of the reactor is then started and the test temperature is reached in approximately 2 hours. In these conditions the water flow is replaced by a flow of aqueous solution of sorbitol containing sodium hydroxide and sodium sulphide. After approximately 8 hours the temperature and spatial velocity (LHSV) of the system are steady. After this period of stabilisation two-hourly collection of the reaction products is begun. The fluid samples of the reaction products are analysed by means of high pressure liquid chromatography (HPLC). The gas output by the gas—fluid separator is measured and analysed by means of gas chromatography, in order to reveal any hydrocarbons present (methane, ethane etc.) and the carbon dioxide. The fluid product contains mainly 1.2-propylene glycol, ethanediol, butanediol, and smaller amounts of glycerol, lactic acid and monovalent alcohols, as well as products such as erythritol, pentanediols, and possibly non-converted sorbitol. The results of examples 2-3 for two different reaction temperatures are given in tables 1 and 2 hereinafter, relative respectively to the operative conditions and distribution of the reaction products.
TABLE 1 | |||||||
Total pres- | Temp. | S= | Sorbitol/NaOH | H2/Sorb. | LHSV | Conversion | |
Example | sure (bar) | (° C.) | supply (ppm) | (molar ratio) | (molar ratio) | (h−1) | (% sorbitol) |
2 | 150 | 250 | 600 | 3 | 6 | 1 | 100 |
3 | 150 | 225 | 600 | 3 | 6 | 1 | 100 |
TABLE 1 | |||||||
Total pres- | Temp. | S= | Sorbitol/NaOH | H2/Sorb. | LHSV | Conversion | |
Example | sure (bar) | (° C.) | supply (ppm) | (molar ratio) | (molar ratio) | (h−1) | (% sorbitol) |
2 | 150 | 250 | 600 | 3 | 6 | 1 | 100 |
3 | 150 | 225 | 600 | 3 | 6 | 1 | 100 |
It can be seen that a decrease in the reaction temperature gives rise to an increase in selectiveness as far as the required reaction products are concerned.
In these examples the catalyst obtained according to example 1 and the fixed bed reactor described in examples 2-3 are used, at different spatial velocities (LHSV). The results of these tests are given in tables 3 and 4 hereinafter.
TABLE 3 | |||||||
Total pres- | Temp. | S= | Sorbitol/NaOH | H2/Sorb. | LHSV | Conversion | |
Example | sure (bar) | (° C.) | supply (ppm) | (molar ratio) | (molar ratio) | (h−1) | (% sorbitol) |
4 | 150 | 225 | 600 | 3 | 9 | 0.67 | 100 |
5 | 150 | 225 | 600 | 3 | 9 | 1.00 | 100 |
6 | 150 | 225 | 600 | 3 | 9 | 1.25 | 99.8 |
7 | 150 | 225 | 600 | 3 | 9 | 1.60 | 99.8 |
8 | 150 | 225 | 600 | 3 | 9 | 2.50 | 99.0 |
TABLE 3 | |||||||
Total pres- | Temp. | S= | Sorbitol/NaOH | H2/Sorb. | LHSV | Conversion | |
Example | sure (bar) | (° C.) | supply (ppm) | (molar ratio) | (molar ratio) | (h−1) | (% sorbitol) |
4 | 150 | 225 | 600 | 3 | 9 | 0.67 | 100 |
5 | 150 | 225 | 600 | 3 | 9 | 1.00 | 100 |
6 | 150 | 225 | 600 | 3 | 9 | 1.25 | 99.8 |
7 | 150 | 225 | 600 | 3 | 9 | 1.60 | 99.8 |
8 | 150 | 225 | 600 | 3 | 9 | 2.50 | 99.0 |
These examples show the effect of the overall reaction pressure on the output of diols in the continuous fixed bed process for conversion of the sorbitol on a catalyst prepared according to example 1 and used in a reactor according to examples 2 and 3. The results of the tests are given in tables 5 and 6 hereinafter.
TABLE 5 | |||||||
Total pres- | Temp. | S= | Sorbitol/NaOH | H2/Sorb. | LHSV | Conversion | |
Example | sure (bar) | (° C.) | supply (ppm) | (molar ratio) | (molar ratio) | (h−1) | (% sorbitol) |
9 | 150 | 225 | 600 | 3 | 6 | 1.25 | 99.8 |
10 | 105 | 225 | 600 | 3 | 6 | 1.25 | 99.8 |
11 | 75 | 225 | 600 | 3 | 6 | 1.25 | 99.2 |
TABLE 5 | |||||||
Total pres- | Temp. | S= | Sorbitol/NaOH | H2/Sorb. | LHSV | Conversion | |
Example | sure (bar) | (° C.) | supply (ppm) | (molar ratio) | (molar ratio) | (h−1) | (% sorbitol) |
9 | 150 | 225 | 600 | 3 | 6 | 1.25 | 99.8 |
10 | 105 | 225 | 600 | 3 | 6 | 1.25 | 99.8 |
11 | 75 | 225 | 600 | 3 | 6 | 1.25 | 99.2 |
In these examples the catalyst prepared according to example 1 is used in a reactor according to examples 2 and 3 in a sorbitol hydrogenolysis process which varies the molar ratio between the sorbitol and promoter (NaOH) in the supply flow.
The results are given in tables 7 and 8 hereinafter.
TABLE 7 | |||||||
Total pres- | Temp. | S= | Sorbitol/NaOH | H2/Sorb. | LHSV | Conversion | |
Example | sure (bar) | (° C.) | supply (ppm) | (molar ratio) | (molar ratio) | (h−1) | (% sorbitol) |
12 | 150 | 235 | 600 | 4 | 6 | 1.25 | 100 |
13 | 150 | 235 | 600 | 6 | 6 | 1.25 | 99.7 |
14 | 150 | 235 | 600 | 12 | 6 | 1.25 | 74.0 |
15 | 150 | 235 | 600 | 30 | 6 | 1.25 | 43.0 |
TABLE 7 | |||||||
Total pres- | Temp. | S= | Sorbitol/NaOH | H2/Sorb. | LHSV | Conversion | |
Example | sure (bar) | (° C.) | supply (ppm) | (molar ratio) | (molar ratio) | (h−1) | (% sorbitol) |
12 | 150 | 235 | 600 | 4 | 6 | 1.25 | 100 |
13 | 150 | 235 | 600 | 6 | 6 | 1.25 | 99.7 |
14 | 150 | 235 | 600 | 12 | 6 | 1.25 | 74.0 |
15 | 150 | 235 | 600 | 30 | 6 | 1.25 | 43.0 |
In these examples the catalyst prepared according to example 1 is used in a reactor according to examples 2 and 3 for hydrogenation of sorbitol, varying the sulphur ion content, the sorbitol/promoter molar ratio in the supply, and the reaction temperature.
The results are given in tables 9 and 10 hereinafter.
TABLE 9 | |||||||
Total pres- | Temp. | S= | Sorbitol/NaOH | H2/Sorb. | LHSV | Conversion | |
Example | sure (bar) | (° C.) | supply (ppm) | (molar ratio) | (molar ratio) | (h−1) | (% sorbitol) |
16 | 100 | 225 | 115 | 6 | 6 | 1.25 | 78 |
17 | 100 | 225 | 115 | 6 | 6 | 1.25 | 76 |
18 | 100 | 225 | 0 | 3 | 6 | 1.25 | 98.5 |
TABLE 9 | |||||||
Total pres- | Temp. | S= | Sorbitol/NaOH | H2/Sorb. | LHSV | Conversion | |
Example | sure (bar) | (° C.) | supply (ppm) | (molar ratio) | (molar ratio) | (h−1) | (% sorbitol) |
16 | 100 | 225 | 115 | 6 | 6 | 1.25 | 78 |
17 | 100 | 225 | 115 | 6 | 6 | 1.25 | 76 |
18 | 100 | 225 | 0 | 3 | 6 | 1.25 | 98.5 |
Claims (11)
1. A method of producing a catalyst comprising from 0.5 to 5% by weight of ruthenium supported on granulated activated carbon useful for hydrogenolysis under pressure of higher polyhydric alcohols, wherein it comprises the steps of:
suspending granular activated carbon in water, the granular activated carbon having:
a specific surface area of from 600 to 1000 m2/g;
a total pore volume of from 0.5 to 1.2 cm3/g;
an apparent specific weight (bulk density) of from 0.45 to 0.55 g/cm3;
an actual specific weight of from 1.9 to 2.3 g/cm3;
a total volume of micropores having a radius smaller than 75 A of from 0.4 to 0.55 cm3/g; and
an ash content of from 2 to 5% by weight;
adding an aqueous ruthenium chloride solution to the suspension;
adjusting the pH of the suspension to a value of between 4.5 and 8 by adding an alkaline agent;
heating the suspension to a temperature of between 70° and 100° C. and maintaining the suspension at this temperature for a time of between 30 minutes and 2 hours;
separating the solid from the suspension by filtration;
re-suspending the solid in a solution of alkaline agent by heating the suspension to a temperature of between 60° and 100° C.;
reducing the catalyst obtained by bubbling a hydrogen flow into the suspension for a time of between 1 and 3 hours; and
separating the solid from the suspension.
2. A catalyst according to claim 1, wherein it has a specific surface area of from 800 to 1000 m2/g and a total pore volume of from 0.6 to 0.7 cm3/g.
3. A catalyst produced according to claim 1, wherein the catalyst has a particle-size distribution of 20-30% by weight of granules between 10 and 18 mesh (2.0-1.0 mm) and 80-70% by weight of granules between 18 and 35 mesh (1.0-0.5 mm).
4. A catalyst produced according to claim 1.
5. A method of producing a catalyst comprising from 0.5 to 5% by weight of ruthenium supported on granulated activated carbon useful for hydrogenolysis under pressure of higher polyhydric alcohols, wherein it comprises the steps of:
(a) suspending granular activated carbon in water, the granular activated carbon having:
a specific surface area of from 600 to 1000 m2/g;
a total pore volume of from 0.5 to 1.2 cm3/g;
an apparent specific weight (bulk density) of from 0.45 to 0.55 g/cm3;
an actual specific weight of from 1.9 to 2.3 g/cm3;
a total volume of micropores having a radius smaller than 75 A of from 0.4 to 0.55 cm3/g; and
an ash content of from 2 to 5% by weight;
(b) adding an aqueous ruthenium chloride solution to the suspension;
(c) adjusting the pH of the suspension to a value of between 4.5 and 8 by adding an alkaline agent;
(d) heating the suspension to a temperature of between 70° and 100° C. and maintaining the suspension at this temperature for a time of between 30 minutes and 2 hours;
(e) separating the solid from the suspension by filtration;
(f) re-suspending the solid in a solution of alkaline agent by heating the suspension to a temperature of between 60° and 100° C.;
(g) reducing the catalyst obtained by bubbling a hydrogen flow into the suspension for a time of between 1 and 3 hours; and
(h) separating the solid from the suspension.
6. A catalyst produced according to claim 5.
7. A method of producing a catalyst comprising from 1 to 3% by weight of ruthenium supported on granulated activated carbon, useful for hydrogenolysis under pressure of higher polyhydric alcohols, wherein it comprises the steps of:
(a) suspending granular activated carbon in water, the granular activated carbon having:
a specific surface area of from 600 to 1000 m2/g;
a total pore volume of from 0.5 to 1.2 cm3/g;
an apparent specific weight (bulk density) of from 0.45 to 0.55 g/cm3;
an actual specific weight of from 1.9 to 2.3 g/cm3;
a total volume of micropores having a radius smaller than 75 A of from 0.4 to 0.55 cm3/g; and
an ash content of from 2 to 5% by weight;
(b) adding an aqueous ruthenium chloride solution to the suspension;
(c) adjusting the pH of the suspension to a value of between 4.5 and 8 by adding an alkaline agent;
(d) heating the suspension to a temperature of between 70° and 100° C. and maintaining the suspension at this temperature for a time of between 30 minutes and 2 hours;
(e) separating the solid from the suspension by filtration;
(f) re-suspending the solid in a solution of alkaline agent by heating the suspension to a temperature of between 60° and 100° C.;
(g) reducing the catalyst obtained by bubbling a hydrogen flow into the suspension for a time of between 1 and 3 hours; and
(h) separating the solid from the suspension.
8. A catalyst produced according to claim 7.
9. A catalyst comprising ruthenium in an amount from 0.5 to 5% by weight supported on active granulated carbon of vegetable origin, the catalyst being capable of catalyzing hydrogenolysis of higher polyhydric alcohols under pressure, the catalyst having:
(a) a specific surface area of from 600 to 1000 m 2 /g;
(b) a total pore volume of from 0.5 to 1.2 cm 3 /g;
(c) a total volume of micropores having a radius smaller than 75 Å of from 0.4 to 0.55 cm 3 /g; and
(d) an ash content of from 2 to 5 % by weight.
10. A catalyst according to claim 9, wherein:
(a) the specific surface area is between 800 and 1000 m 2 /g;
(b) the catalyst has an apparent specific weight (bulk density) of from 0.45 to 0.55 g/cm 3;
(c) the catalyst has an actual specific weight of from 1.9 to 2.3 g/cm 3.
11. A catalyst according to claim 9, wherein the catalyst has a particle size distribution of 20-30% by weight of granules between 10 and 18 mesh ( 2.0 mm-1.0 mm) and 80 %-70 % by weight of granules between 18 and 35 mesh ( 1.0 mm and 0.5 mm).
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ITTO920079A IT1256800B (en) | 1992-01-31 | 1992-01-31 | PROCEDURE FOR THE PRODUCTION OF LOWER POLYOLS AND A NEW RUTHENIUM-BASED CATALYST USED IN THIS PROCEDURE. |
ITTO92A0079 | 1992-01-31 | ||
US08/010,564 US5403805A (en) | 1992-01-31 | 1993-01-28 | Ruthenium-based catalyst for producing lower polyhydric alcohols |
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US08/376,802 Expired - Lifetime US5600028A (en) | 1992-01-31 | 1995-01-23 | Method for producing lower polyhydric alcohols and a new ruthenium-based catalyst used in this method |
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IT1256800B (en) * | 1992-01-31 | 1995-12-15 | Novamont Spa | PROCEDURE FOR THE PRODUCTION OF LOWER POLYOLS AND A NEW RUTHENIUM-BASED CATALYST USED IN THIS PROCEDURE. |
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1992
- 1992-01-31 IT ITTO920079A patent/IT1256800B/en active IP Right Grant
-
1993
- 1993-01-28 US US08/010,564 patent/US5403805A/en not_active Ceased
- 1993-01-28 DK DK93101313.0T patent/DK0553815T3/en active
- 1993-01-28 ES ES93101313T patent/ES2109379T3/en not_active Expired - Lifetime
- 1993-01-28 EP EP93101313A patent/EP0553815B1/en not_active Expired - Lifetime
- 1993-01-28 DE DE69314506T patent/DE69314506T2/en not_active Expired - Fee Related
- 1993-01-28 AT AT93101313T patent/ATE159187T1/en not_active IP Right Cessation
-
1995
- 1995-01-23 US US08/376,802 patent/US5600028A/en not_active Expired - Lifetime
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1997
- 1997-04-04 US US08/832,763 patent/USRE37329E1/en not_active Expired - Lifetime
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1998
- 1998-01-07 GR GR980400004T patent/GR3025830T3/en unknown
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US20090211942A1 (en) * | 2005-12-21 | 2009-08-27 | Cortright Randy D | Catalysts and methods for reforming oxygenated compounds |
US8231857B2 (en) | 2005-12-21 | 2012-07-31 | Virent, Inc. | Catalysts and methods for reforming oxygenated compounds |
US7989664B2 (en) | 2006-05-08 | 2011-08-02 | Virent Energy Systems, Inc. | Methods and systems for generating polyols |
US8754263B2 (en) | 2006-05-08 | 2014-06-17 | Virent, Inc. | Methods and systems for generating polyols |
US20080025903A1 (en) * | 2006-05-08 | 2008-01-31 | Cortright Randy D | Methods and systems for generating polyols |
US7767867B2 (en) | 2006-05-08 | 2010-08-03 | Virent Energy Systems, Inc. | Methods and systems for generating polyols |
US20100280275A1 (en) * | 2006-05-08 | 2010-11-04 | Cortright Randy D | Methods and systems for generating polyols |
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US8362307B2 (en) | 2007-03-08 | 2013-01-29 | Virent, Inc. | Synthesis of liquid fuels and chemicals from oxygenated hydrocarbons |
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US8053615B2 (en) | 2007-03-08 | 2011-11-08 | Virent Energy Systems, Inc. | Synthesis of liquid fuels and chemicals from oxygenated hydrocarbons |
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US8933281B2 (en) | 2007-03-08 | 2015-01-13 | Virent, Inc. | Synthesis of liquid fuels and chemicals from oxygenated hydrocarbons |
US20080216391A1 (en) * | 2007-03-08 | 2008-09-11 | Cortright Randy D | Synthesis of liquid fuels and chemicals from oxygenated hydrocarbons |
US8367882B2 (en) | 2007-03-08 | 2013-02-05 | Virent, Inc. | Synthesis of liquid fuels and chemicals from oxygenated hydrocarbons |
US8455705B2 (en) | 2007-03-08 | 2013-06-04 | Virent, Inc. | Synthesis of liquid fuels and chemicals from oxygenated hydrocarbons |
US20080300434A1 (en) * | 2007-03-08 | 2008-12-04 | Cortright Randy D | Synthesis of liqiud fuels and chemicals from oxygenated hydrocarbons |
US8017818B2 (en) | 2007-03-08 | 2011-09-13 | Virent Energy Systems, Inc. | Synthesis of liquid fuels and chemicals from oxygenated hydrocarbons |
US20100076233A1 (en) * | 2008-08-27 | 2010-03-25 | Cortright Randy D | Synthesis of liquid fuels from biomass |
US8350108B2 (en) | 2008-08-27 | 2013-01-08 | Virent, Inc. | Synthesis of liquid fuels from biomass |
US20110009614A1 (en) * | 2009-06-30 | 2011-01-13 | Paul George Blommel | Processes and reactor systems for converting sugars and sugar alcohols |
Also Published As
Publication number | Publication date |
---|---|
DE69314506T2 (en) | 1998-03-12 |
ITTO920079A1 (en) | 1993-07-31 |
US5403805A (en) | 1995-04-04 |
DK0553815T3 (en) | 1998-01-26 |
EP0553815B1 (en) | 1997-10-15 |
EP0553815A1 (en) | 1993-08-04 |
IT1256800B (en) | 1995-12-15 |
ATE159187T1 (en) | 1997-11-15 |
ES2109379T3 (en) | 1998-01-16 |
GR3025830T3 (en) | 1998-04-30 |
DE69314506D1 (en) | 1997-11-20 |
US5600028A (en) | 1997-02-04 |
ITTO920079A0 (en) | 1992-01-31 |
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