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WO2008071616A1 - Procédé de fabrication de 1,2-éthylène glycol et de 1,2 propylène glycol par hydrogénolyse à catalysation hétérogène d'un polyol - Google Patents

Procédé de fabrication de 1,2-éthylène glycol et de 1,2 propylène glycol par hydrogénolyse à catalysation hétérogène d'un polyol Download PDF

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Publication number
WO2008071616A1
WO2008071616A1 PCT/EP2007/063407 EP2007063407W WO2008071616A1 WO 2008071616 A1 WO2008071616 A1 WO 2008071616A1 EP 2007063407 W EP2007063407 W EP 2007063407W WO 2008071616 A1 WO2008071616 A1 WO 2008071616A1
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Prior art keywords
hydrogenolysis
catalyst
polyol
propylene glycol
ethylene glycol
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German (de)
English (en)
Inventor
Bram Willem Hoffer
Roman Prochazka
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BASF SE
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BASF SE
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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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/60—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by elimination of -OH groups, e.g. by dehydration
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • the present invention relates to a process for the preparation of 1, 2-ethylene glycol and 1, 2-propylene glycol by heterogeneously catalyzed hydrogenolysis of a polyol.
  • 1, 2-ethylene glycol (monoethylene glycol, MEG) and 1, 2-propylene glycol (propane-1, 2-diol) are used as solvents, mineral oil-free lubricants, disinfectants, in brake and hydraulic fluids, as an additive to antifreezes, in organic synthesis , for the production of solvents, polymers, washing raw materials, textile auxiliaries, gas drying agents.
  • 1, 2-ethylene glycol and 1, 2-propylene glycol are usually prepared from the corresponding epoxides (ethylene oxide (EO) and propylene oxide (PO)) (K. Weissermel and H.-J. Arpe, Industrial Organic Chemistry, fourth completely revised Version, 2000, WILEY-VCH, Weinheim).
  • EO ethylene oxide
  • PO propylene oxide
  • the hydrogenolysis reaction is carried out at high temperatures (180-260 0 C) and high pressures (> 200 bar).
  • high temperatures (180-260 0 C) and high pressures (> 200 bar).
  • highly selective processes for the preparation of certain glycols are not yet known.
  • No. 4,401,823 (UOP Inc.) describes the use of certain metal catalysts based on a "shaped carbonaceous pyropolymer.” The preparation of the support is very complicated and the selectivity in the hydrogenolysis is in need of improvement.
  • No. 4,404,411 (Du Pont) teaches the use of hydrogenation catalysts, such as Ni, Pd or Pt catalysts, in particular Ni supported on silica / alumina, in the hydrolysis of polyols in the presence of bases and nonaqueous solvents.
  • a disadvantage of organic solvents is that they react in the hydrogenolysis and thus expensive solvent is lost.
  • Another disadvantage is that organic solvents can form azeotropes with the water of reaction formed and thus can not be completely separated.
  • US 4,496,780 (UOP Inc.) relates to the hydrocracking of carbohydrates in the presence of supported noble metal catalysts, in particular specific Ru / Ti / AbCh catalysts.
  • EP-A1-510 238 (MENON S.r.l.) relates to the use of sulfide-modified Pt catalysts in the hydrogenolysis of polyols.
  • WO-A-06 092085 (Global Polyol Invest., Ltd.) relates to the preparation of C 2-4 dihydroxy alcohols and polyols by hydrocracking sorbitol in the presence of Ni / Ru catalysts.
  • US-A1 -2007 / 0135301 (Süd-Chemie Inc.) describes for the hydrogenolysis of carbohydrates a catalyst comprising nickel on an alumina-silica carrier.
  • the present invention has for its object to provide an improved economical process for the preparation of 1, 2-ethylene glycol and 1, 2-propylene glycol find.
  • 1, 2-glycols in particular 1, 2-ethylene glycol and 1, 2-propylene glycol, should be obtained with high selectivity, yield and space-time yield.
  • heterogeneous catalyst is a catalyst containing iridium (Ir) and a support material selected from the group Carbon, zirconia, titania and calcium carbonate.
  • sugars are:
  • Monosaccharides such as glucose, sorbose, tagatose, disaccharides such as maltose, sucrose, lactose, isomaltulose, cellobiose, palatinose®, oligosaccharides and polysaccharides;
  • Aldotrioses such as glyceraldehyde, aldotetroses, such as erythrose, threose, aldopentoses, such as arabinose, ribose, xylose, lyxose, aldohexoses, such as allose, altrose, glucose, mannose, gulose, idose, galactose, talose, ketopentoses, such as ribulose, ketohexose like fructose; in particular D - (+) - glucose.
  • sugar alcohols examples are:
  • the catalytically active mass of the catalyst is defined as the sum of the masses of the catalytically active constituents and the support materials and contains iridium (Ir) of the oxidation state 0 and / or its compounds, such as. As oxides or hydroxides, and carbon (C), zirconia (Zr ⁇ 2), titanium dioxide ( ⁇ O2) or calcium carbonate (CaCOs) or mixtures of these support materials.
  • the catalysts are preferably used in the form of catalysts which consist only of catalytically active material and optionally a molding aid (such as graphite or stearic acid), if the catalyst is used as a molding, ie no further catalytically inactive impurities contain.
  • the catalytically active composition can be introduced into the reaction vessel as a powder or as a grit or, after milling, mixing with shaping aids, shaping and heat treatment, as a shaped catalyst article, for example as tablets, spheres, rings, extrudates (eg strands) be introduced into the reactor.
  • the sum of the o.g. catalytically active ingredients and the o.g. Support materials in the catalytically active composition - wherein the component Ir is calculated as metal in the oxidation state 0 - is usually 80 to 100 wt .-%, preferably 90 to 100 wt .-%, particularly preferably 95 to 100 wt .-% , in particular greater than 99% by weight, for example 100% by weight.
  • the catalytically active composition of the catalysts used in the process according to the invention contains in particular 80 to 99.9 wt .-%, preferably 90 to 99.8 wt .-%, particularly preferably 92 to
  • the support material carbon, especially activated carbon, and / or ZrÜ2 and / or TiÜ2 and / or CaCOs
  • Preferred catalysts contain in their catalytically active composition 80 to 99.9 wt .-%, preferably 90 to 99.8 wt .-%, particularly preferably 92 to 99.7 wt.%, Carbon, especially activated carbon, and 0.1 to 20 wt .-%, preferably 0.2 to 10 wt .-%, particularly preferably 0.3 to 8 wt .-%, Ir, calculated as metal in the oxidation state 0.
  • Preferred catalysts contain no Ni, Co, Cu, Pd, Pt, Ru and / or Rh in their catalytically active composition, preferably no Pd, Pt, Ru and / or Rh.
  • the catalytically active composition of particularly preferred catalysts consists of 80 to 99.9 wt .-%, in particular 90 to 99.8 wt .-%, particularly preferably 92 to 99.7 wt .-%, carbon, especially activated carbon, and 0 , 1 to 20 wt .-%, in particular 0.2 to 10 wt .-%, particularly preferably 0.3 to 8 wt .-%, Ir, calculated as metal in the oxidation state 0.
  • Carbon black, graphite and, in particular, activated carbon are preferred for the carbon support material.
  • the catalysts used in the process according to the invention have a surface area (according to DIN 66131) of preferably 500 to 2000 m 2 / g, more preferably 500 to 1800 m 2 / g, and a pore volume (according to DIN 66134) of preferred 0.05 to 5.0 cm 3 / g, particularly preferably 0.10 to 3 cm 3 / g, on.
  • the catalysts used in the process according to the invention are preferably impregnated with carbon, in particular activated carbon, zirconium dioxide (ZrO.sub.2), titanium dioxide (TiO.sub.2), calcium carbonate (CaCO.sub.2) or mixtures of two or more of these support materials, for example in the form of powder, chippings or shaped bodies , like strands, tablets, balls or rings, are prepared.
  • carbon in particular activated carbon, zirconium dioxide (ZrO.sub.2), titanium dioxide (TiO.sub.2), calcium carbonate (CaCO.sub.2) or mixtures of two or more of these support materials, for example in the form of powder, chippings or shaped bodies , like strands, tablets, balls or rings, are prepared.
  • Zirconia is used for catalyst preparation, for example, in the monoclinic or tetragonal form, preferably in the monoclinic form, and titanium dioxide, for example, as anatase or rutile.
  • Activated carbon with a surface area (according to DIN 66131) of preferably 500 to 2000 m 2 / g, more preferably 500 to 1800 m 2 / g, and a pore volume (according to DIN 66134) of preferably 0.05 to 5.0 cm 3 / g, more preferably 0.10 to 3 cm 3 / g used.
  • Examples of such activated carbons are the commercially available Norit® SX types from Norit (Netherlands).
  • the carbon support material is used in pulverulent form or in the form of strands, spheres, chippings, etc.
  • the carbon support can be pretreated before its doping, for example by oxidation with nitric acid, oxygen, hydrogen peroxide, hydrochloric acid, etc.
  • the production of moldings of the above-mentioned support materials can be carried out by the usual methods.
  • the impregnation of these substrates is also carried out by the usual methods, such as.
  • EP-A-599,180, EP-A-673 918 or AB Stiles, Catalyst Manufacture - Laboratory and Commercial Preparations, Marcel Dekker, pages 89 to 91, New York (1983) by application of each corresponding metal salt solution in one or more impregnation stages, wherein as metal salts z.
  • B. corresponding nitrates, acetates or chlorides can be used.
  • the mass is dried after the impregnation and possibly calcined.
  • the impregnation can be carried out by the so-called "incipient wetness” method, in which the oxidic support material is moistened maximally to saturation with the impregnation solution in accordance with its water absorption capacity.
  • the impregnation can also be done in supernatant solution.
  • multi-stage impregnation processes it is expedient to dry between individual impregnation steps and optionally to calcine.
  • the multi-stage impregnation is advantageous to use especially when the carrier material is to be applied with a larger amount of metal.
  • the impregnation can take place simultaneously with all metal salts or in any order of the individual metal salts in succession.
  • a special form of impregnation is the spray-drying, in which the mentioned catalyst support is sprayed in a spray dryer with the or to be applied component ⁇ ) in a suitable solvent.
  • An advantage of this variant is the combination of application and drying of the active component (s) in one step.
  • the catalyst can also be prepared by precipitation of the metal salts on the support, e.g. in EP-A-1 317 959 (BASF AG).
  • the catalysts prepared in this manner contain the catalytically active metal (s), such as Ir, in the form of a mixture of its oxygenated compound (s), i. especially as oxides and mixed oxides.
  • the catalysts used in the process according to the invention can be reduced before they are used.
  • the reduction can be done without pressure or under pressure. If it is reduced without pressure, the procedure is to heat the catalyst under inert gas, for example nitrogen, to the reduction temperature and then slowly replace the inert gas with hydrogen. In the case of a reduction under pressure, the procedure is conveniently such that the reduction is also carried out at the pressures and temperatures used later in the process according to the invention.
  • the Duration of reduction selected ie the more drastic the conditions, the shorter the reduction time can be selected.
  • catalysts which can be used in the process according to the invention are supported catalysts according to WO-A-96/36589 (BASF AG) which contain iridium and, as support material, activated carbon, titanium dioxide and / or zirconium dioxide.
  • catalysts which can be used according to the invention are the following commercially available catalysts:
  • the polyol (starting material) in the liquid phase i. dissolved or suspended in a solvent or diluent, hydrogenated.
  • Suitable solvents or diluents are, in particular, those which are able to dissolve the starting material as completely as possible or completely mix with it and which are inert under the process conditions.
  • Suitable solvents and diluents are water and aliphatic alcohols, in particular C 1 -5-alcohols, especially C 1-4 -alcohols, such as methanol, ethanol, n- or isopropanol, n-, 2-, iso- or tert-butanol ,
  • the hydrogenolysis is carried out in the presence of water as a solvent or diluent.
  • the concentration of starting material (polyol) in the liquid, solvent or diluent-containing phase is preferably in the range from 10 to 80% by weight, particularly preferably 30 to 70% by weight, in each case based on the total weight the solution or suspension (without catalyst).
  • a further increase in the selectivity can be achieved by adding a basic compound (a base), as described, for example, in US Pat. No. 5,107,018 (BASF AG) or US Pat. No. 4,404,411 (see above).
  • advantageous bases are alkali metal hydroxides, alkaline earth metal hydroxides, alkali metal carbonates, alkaline earth metal carbonates, alkali metal oxides, alkaline earth metal oxides, alkali metal alcoholates, alkaline earth metal alcoholates and nitrogen bases, e.g. Tetraalkylammonium hydroxides or carbonates.
  • lithium hydroxide LiOH
  • calcium oxide CaO
  • sodium hydroxide NaOH
  • magnesium hydroxide Mg (OH) 2
  • sodium carbonate Na2CÜ3
  • the process can be carried out continuously, discontinuously or semi-continuously. Preferred is a continuous driving style.
  • Preferred reactors are tubular reactors with fixed catalyst bed for continuous operation, autoclaves or bubble columns for discontinuous operation and autoclaves for semi-continuous operation.
  • the hydrogenolysis is preferably carried out at a temperature in the range of 150 to 325 ° C, particularly preferably 175 to 300 0 C, especially 200 to 275 ° C, is carried out.
  • the hydrogenolysis is preferably carried out at an absolute pressure in the range from 50 to 325 bar, more preferably from 75 to 300 bar, in particular from 100 to 275 bar.
  • the educt (polyol) is introduced as a solution or suspension, preferably as a solution, in a suitable solvent or diluent (see above) in the reactor; the catalyst material is suspended in the educt and solvent or diluent (see above).
  • the solution or suspension, catalyst and hydrogen gas must be well mixed, eg by a turbine stirrer in an autoclave.
  • the suspended catalyst material can be introduced by means of conventional techniques and separated again (sedimentation, centrifugation, cake filtration, crossflow filtration). The catalyst can be used one or more times.
  • the catalyst concentration is advantageously 0.1 to 20 wt .-%, preferably 0.5 to 10 wt .-%, in particular 1 to 5 wt .-%, each based on the Total weight of the solution or suspension (total weight with catalyst).
  • the mean catalyst particle size is advantageously in the range of 0.001 to 1 mm, preferably in the range of 0.005 to 0.5 mm, in particular 0.01 to 0.25 mm.
  • the educt (polyol) is passed as a solution or suspension, preferably as a solution, in a suitable solvent or diluent (see above) in the liquid phase including hydrogen over the catalyst, which is preferably in a (preferably from the outside) heated fixed bed reactor is located. It is both a trickle way and a sumping possible.
  • the catalyst loading is generally in the range from 0.05 to 5, preferably 0.1 to 2, particularly preferably 0.2 to 1, kg of polyol per liter of catalyst (bulk volume) and hour. It is expedient to heat the educt solution or educt suspension before it is fed into the reaction vessel, preferably to the reaction temperature.
  • the pressure in the reaction vessel which results from the sum of the partial pressures of the educt, the reaction products formed and the solvent or diluent at the respective temperature is expediently increased by pressing hydrogen to the desired reaction pressure.
  • Propylene glycol are again separated from the solvent or diluent used. This is done by methods known to those skilled in the art, e.g. by distilling off the solvent or diluent, optionally at reduced pressure.
  • the invention thus also provides a process for preparing an antifreeze, which comprises preparing a mixture of 1, 2-ethylene glycol and 1, 2-propylene glycol by the hydrogenolysis process according to the invention as described above and admixing the mixture with water ,
  • a corrosion protection component may be added.
  • the glycol mixture is preferably added with 40 to 90 wt .-% water, based on the weight of the glycol mixture.
  • the amount of anticorrosive component e.g. from the group of carboxylic acids, molybdate or triazoles is, for example, in the range of 1 to 10 wt .-%, based on the total weight of the antifreeze.
  • the antifreeze is used particularly advantageously for coolant circuits of internal combustion engines. See, e.g. W0-A1 -06 / 092376 (BASF AG).
  • An Ir / C catalyst containing 5% by weight of Ir was used to convert sorbitol to lower polyhydric alcohols by the following method.
  • an autoclave with a volume of 270 cm 3 , 150 g of an aqueous solution with 15 g of sorbitol, 750 mg of calcium oxide and 7.5 g of catalyst are added.
  • the autoclave is closed, after which the air contained in it is expelled by purging with nitrogen.
  • the inert gas is replaced by hydrogen and the autoclave is charged with hydrogen at ambient temperature up to a pressure of 10.0 MPa. Then it is heated and stirred at 1000 rpm. After about 40 minutes, a temperature of 230 0 C is reached and maintained for 10 hours.
  • the pressure is increased by adding hydrogen to about 25.0 MPa.
  • the pressure is maintained at 25.0 MPa by continuously adding fresh hydrogen.
  • the autoclave is cooled to ambient temperature, after which a gas sample is taken for analysis prior to autoclaving.
  • the reaction liquid is separated by filtration from the catalyst.
  • the gas sample is analyzed by gas chromatography to detect the presence of hydrocarbons (methane, ethane, ethylene, etc.) and carbon dioxide.
  • the reaction liquid is analyzed by gas chromatography. It contains mainly ethanediol, 1,2-propylene glycol, ethanol and 1-propanol and minor amounts of glycerol and butanediol. Sorbitol sales were 100%.
  • a Pd / ⁇ -AbOs catalyst containing 4.7% by weight of Pd was used to convert sorbitol to lower polyhydric alcohols by the following method.
  • an autoclave with a volume of 300 cm 3 , 150 g of an aqueous solution with 15 g of sorbitol, 750 mg of calcium oxide and 8 g of catalyst are added.
  • the autoclave is closed, after which the air contained in it is expelled by purging with nitrogen.
  • the inert gas is replaced by hydrogen and the autoclave is exposed to hydrogen at ambient temperature to a pressure of 5.0 MPa. Then it is heated and stirred at 1000 rpm. After about 30 minutes, a temperature of 230 0 C is reached and maintained for 16 hours.
  • the pressure is increased by adding hydrogen to about 25.0 MPa.
  • the pressure is maintained at 25.0 MPa by continuously adding fresh hydrogen.
  • the autoclave is cooled to ambient temperature, after which a gas sample is taken for analysis before the autoclave is purged.
  • the reaction liquid is separated by filtration from the catalyst.
  • the Reaction liquid is analyzed by gas chromatography. It contains mainly ethanediol, 1,2-propylene glycol, ethanol and 1-propanol and minor amounts of glycerine and butanediol. Sorbitol sales were only 88%.
  • An Ru / C catalyst containing 5% by weight of Ru was used to convert sorbitol to lower polyhydric alcohols by the following method.
  • an autoclave with a volume of 300 cm 3 , 150 g of an aqueous solution with 15 g of sorbitol, 750 mg of calcium oxide and 7.5 g of catalyst are added.
  • the autoclave is closed, after which the air contained in it is expelled by purging with nitrogen.
  • the inert gas is replaced by hydrogen and the autoclave is charged with hydrogen at ambient temperature to a pressure of 5.0 MPa. Then it is heated and stirred at 1000 rpm. After about 30 minutes, a temperature of 230 0 C is reached and maintained for 10 hours.
  • the pressure is increased by adding hydrogen to about 25.0 MPa.
  • the pressure is maintained at 25.0 MPa by continuously adding fresh hydrogen.
  • the autoclave is cooled to ambient temperature, after which a gas sample is taken for analysis prior to autoclaving.
  • the reaction liquid is separated by filtration from the catalyst.
  • the gas sample is analyzed by gas chromatography to detect the presence of hydrocarbons (methane, ethane, ethylene, etc.) and carbon dioxide.
  • the reaction liquid is analyzed by gas chromatography. It contains mainly ethanediol, 1,2-propylene glycol, ethanol and 1-propanol and smaller amounts of glycerine and butanediol.
  • the sorbitol turnover was 100%
  • a catalyst described in US 5,210,335 (BASF AG) (72% Co, 21% Cu, 7% Mn) was used to convert sorbitol to lower polyhydric alcohols by the following method.
  • an autoclave with a volume of 270 cm 3 , 175 g of an aqueous solution with 37.5 g of sorbitol, 2.5 g of sodium hydroxide and 10 g of catalyst are added.
  • the autoclave is closed, after which the air contained in it is expelled by purging with nitrogen.
  • the inert gas is replaced by hydrogen and the autoclave is charged with hydrogen at ambient temperature up to a pressure of 15.0 MPa. Then it is heated and stirred at 1000 rpm.
  • a temperature of 230 0 C is reached and maintained for 3 hours.
  • the pressure is increased by adding hydrogen to about 25.0 MPa and the temperature is raised to 250 ° C.
  • the pressure is maintained at 25.0 MPa by continuously adding fresh hydrogen.
  • the autoclave is cooled to ambient temperature, after which a gas sample is taken for analysis before the autoclave is purged. is taken.
  • the reaction liquid is separated by filtration from the catalyst.
  • the gas sample is analyzed by gas chromatography to detect the presence of hydrocarbons (methane, ethane, ethylene, etc.) and carbon dioxide.
  • the reaction liquid is analyzed by gas chromatography. It contains mainly ethanediol, 1,2-propylene glycol, ethanol and 1-propanol and minor amounts of glycerol and butanediol. Sorbitol sales were 100%.
  • Example 2 For this purpose in contrast the catalysts from Examples 3 and 4. In Example 2, only 88% sorbitol conversion is achieved after 16 hours. The catalyst 1 used according to the invention already showed full conversion after 10 hours, ie it is much more active.

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Abstract

Procédé de fabrication de 1,2-éthylène glycol et de 1,2 propylène glycol par hydrogénolyse à catalysation hétérogène d'un polyol. Selon ce procédé, on utilise comme catalyseur hétérogène de l'iridium (Ir) contenant un catalyseur, et un substrat sélectionné parmi le groupe constitué du carbone, du dioxyde de zirconium, du dioxyde de titane et du carbonate de calcium.
PCT/EP2007/063407 2006-12-15 2007-12-06 Procédé de fabrication de 1,2-éthylène glycol et de 1,2 propylène glycol par hydrogénolyse à catalysation hétérogène d'un polyol Ceased WO2008071616A1 (fr)

Applications Claiming Priority (2)

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EP06126226 2006-12-15
EP06126226.7 2006-12-15

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WO2008071616A1 true WO2008071616A1 (fr) 2008-06-19

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014133775A1 (fr) 2013-03-01 2014-09-04 Clariant Corporation Catalyseur pour l'hydrogénolyse de polyol
US8895763B2 (en) 2009-08-24 2014-11-25 Thyssenkrupp Uhde Gmbh Method and device for producing alkylene oxides and alkylene glycols

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0344561A2 (fr) * 1988-05-28 1989-12-06 BASF Aktiengesellschaft Procédé de préparation d'alcools polyvalents inférieurs
US6479713B1 (en) * 2001-10-23 2002-11-12 Battelle Memorial Institute Hydrogenolysis of 5-carbon sugars, sugar alcohols, and other methods and compositions for reactions involving hydrogen
WO2006092376A1 (fr) * 2005-02-28 2006-09-08 Basf Aktiengesellschaft Concentres d'agents antigel et anticorrosion contenant de la glycerine

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0344561A2 (fr) * 1988-05-28 1989-12-06 BASF Aktiengesellschaft Procédé de préparation d'alcools polyvalents inférieurs
US6479713B1 (en) * 2001-10-23 2002-11-12 Battelle Memorial Institute Hydrogenolysis of 5-carbon sugars, sugar alcohols, and other methods and compositions for reactions involving hydrogen
WO2006092376A1 (fr) * 2005-02-28 2006-09-08 Basf Aktiengesellschaft Concentres d'agents antigel et anticorrosion contenant de la glycerine

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
MONTASSIER C ET AL: "POLYOL CONVERSION BY LIQUID PHASE HETEROGENEOUS CATALYSIS OVER METALS", HETEROGENEOUS CATALYSIS AND FINE CHEMICALS, XX, XX, 1988, pages 165 - 170, XP009053599 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8895763B2 (en) 2009-08-24 2014-11-25 Thyssenkrupp Uhde Gmbh Method and device for producing alkylene oxides and alkylene glycols
WO2014133775A1 (fr) 2013-03-01 2014-09-04 Clariant Corporation Catalyseur pour l'hydrogénolyse de polyol
US9205412B2 (en) 2013-03-01 2015-12-08 Clariant Corporation Catalyst for polyol hydrogenolysis

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