EP2102137A1 - Procede pour produire du 1,2-ethyleneglycol et du 1,2-propyleneglycol par hydrogenolyse par catalyse heterogene d'un polyol - Google Patents

Procede pour produire du 1,2-ethyleneglycol et du 1,2-propyleneglycol par hydrogenolyse par catalyse heterogene d'un polyol

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Publication number
EP2102137A1
EP2102137A1 EP07857305A EP07857305A EP2102137A1 EP 2102137 A1 EP2102137 A1 EP 2102137A1 EP 07857305 A EP07857305 A EP 07857305A EP 07857305 A EP07857305 A EP 07857305A EP 2102137 A1 EP2102137 A1 EP 2102137A1
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EP
European Patent Office
Prior art keywords
hydrogenolysis
catalyst
polyol
carries out
propylene glycol
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EP07857305A
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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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Application filed by BASF SE filed Critical BASF SE
Priority to EP07857305A priority Critical patent/EP2102137A1/fr
Publication of EP2102137A1 publication Critical patent/EP2102137A1/fr
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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.
  • a process for the preparation of 1, 2-ethylene glycol and 1, 2-propylene glycol by heterogeneously catalyzed hydrogenolysis of a polyol which is characterized in that as a heterogeneous catalyst, a catalyst containing palladium (Pd) and a support material selected from the group Carbon, zirconia, titania and calcium carbonate, wherein the catalyst does not contain ruthenium (Ru) and hydrogenolysis is carried out in the presence of water.
  • a heterogeneous catalyst a catalyst containing palladium (Pd) and a support material selected from the group Carbon, zirconia, titania and calcium carbonate, wherein the catalyst does not contain ruthenium (Ru) and hydrogenolysis is carried out in the presence of water.
  • 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 palladium (Pd) of the oxidation state 0 and / or its compounds, such as.
  • Pd palladium
  • oxides or hydroxides oxides or hydroxides.
  • 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.
  • a molding aid such as graphite or stearic acid
  • 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 (for example strands), into the reactor be introduced.
  • the sum of the o.g. catalytically active ingredients and the o.g. Support materials in the catalytically active composition - wherein the component Pd 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% by weight, preferably 90 to 99.8% by weight, particularly preferably 92 to 99.7% by weight, of the support material (carbon, especially activated carbon, and / or ZrO 2 and / or TiO 2 and / or CaCO 3),
  • the support material carbon, especially activated carbon, and / or ZrO 2 and / or TiO 2 and / or CaCO 3
  • 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 .-%, Pd, calculated as metal in the oxidation state 0.
  • preferred (Ru-free) catalysts contain no Ni, Co, Cu, Rh, Pt and / or Ir, preferably no Rh, Pt and / or Ir.
  • 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 .-%, Pd, 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, grit or shaped articles, such as 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, grit or shaped articles, such as 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. In 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 according to its water absorption capacity to a maximum saturation with the impregnation solution.
  • 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-step impregnation is advantageous to apply 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 Pd, 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 the reduction is selected, ie the more drastic the conditions, the shorter the reduction time can be selected.
  • catalysts which can be used according to the invention are the following commercially available catalysts: 5% by weight of Pd on calcium carbonate, 5% by weight of Pd on carbon powder, "The Catalyst Technical Handbook” (2005) Johnson Matthey PLC, page 69, and FIG Wt .-% Pd on carbon, "noble metal catalysts” Company publication WC Heraeus (2003), page 18.
  • the polyol (starting material) in the liquid phase i. dissolved or suspended in water and optionally another solvent or diluent, hydrogenolysed.
  • Suitable additional solvents or diluents in addition to the water are, in particular, those which are able to dissolve the starting material as completely as possible or completely mix with them and which are inert under the process conditions.
  • aliphatic alcohols especially 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 the sole solvent or diluent.
  • concentration of starting material (polyol) in the liquid phase is preferably in the range from 10 to 80 wt .-%, particularly preferably 30 to 70 wt .-%, each based on the total weight of the solution or suspension (without catalyst).
  • 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.
  • oxides, hydroxides and carbonates of alkaline earth metals especially alkali metals, and combinations thereof.
  • Particularly preferred are lithium hydroxide (LiOH), calcium oxide (CaO), sodium hydroxide (NaOH), magnesium hydroxide (Mg (OH) 2) and 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 initially introduced into the reactor as a solution or suspension, preferably as a solution, in water and, if appropriate, another suitable solvent or diluent (see above);
  • 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 using conventional techniques and separated again (sedimentation, centrifugation, cake filtration, cross-flow 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 water and optionally another 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 of 0.05 to 5, preferably 0.1 to 2, more 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 already 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 separated from the water and any solvent or diluent again used. This is done by methods known to those skilled in the art, e.g. by distilling off the solvent or diluent (s), 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).
  • Separation column RTX-5 amines (30 mx 0.32 mm) with He as carrier gas. Temperature program: 50 0 C (15 min. Hold) at 10 ° C / min. heat to 280 0 C, hold for 30 min. Injector temperature is 280 0 C, Fl D detector temperature is 300 ° C.
  • a Pd / C catalyst containing 5% 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 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 ° 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 Ethanidi
  • 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 with hydrogen at ambient temperature to a pressure of 5.0 MPa applied. 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 Increased pressure by introducing 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. Sorbitol sales were 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 Maintain for 3 hours.
  • the pressure is increased by adding hydrogen to about 25.0 MPa and the temperature is increased to 250 0 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.
  • 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 / C catalyst containing 5% by weight of Pd 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, Added 750 mg of calcium oxide and 7.5 g of catalyst.
  • 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. It is then heated and stirred at 1000 rpm. After about 1 hour, a temperature of 230 0 C is reached and maintained for 8 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.
  • samples of the reaction liquid are taken.
  • the reaction liquid is separated from the catalyst by filtration and analyzed by gas chromatography. It contains mainly ethanediol, 1, 2-propylene glycol, ethanol and 1-propanol and smaller amounts of glycerol and butanediol.
  • the time-resolved liquid phase compositions are listed in Table 3.

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Abstract

L'invention concerne un procédé pour produire du 1,2-éthylèneglycol et du 1,2-propylèneglycol par hydrogénolyse par catalyse hétérogène d'un polyol, caractérisé en ce que le catalyseur hétérogène utilisé est un catalyseur contenant du palladium (Pd), et en ce qu'un support sélectionné dans le groupe comprenant carbone, dioxyde de zirconium, dioxyde de titane, et carbonate de calcium est employé. Selon l'invention, ledit catalyseur ne comporte pas de ruthénium (Ru), et l'hydrogénolyse est réalisée en présence d'eau.
EP07857305A 2006-12-15 2007-12-10 Procede pour produire du 1,2-ethyleneglycol et du 1,2-propyleneglycol par hydrogenolyse par catalyse heterogene d'un polyol Withdrawn EP2102137A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP07857305A EP2102137A1 (fr) 2006-12-15 2007-12-10 Procede pour produire du 1,2-ethyleneglycol et du 1,2-propyleneglycol par hydrogenolyse par catalyse heterogene d'un polyol

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP06126235 2006-12-15
EP07857305A EP2102137A1 (fr) 2006-12-15 2007-12-10 Procede pour produire du 1,2-ethyleneglycol et du 1,2-propyleneglycol par hydrogenolyse par catalyse heterogene d'un polyol
PCT/EP2007/063569 WO2008071642A1 (fr) 2006-12-15 2007-12-10 Procédé pour produire du 1,2-éthylèneglycol et du 1,2-propylèneglycol par hydrogénolyse par catalyse hétérogène d'un polyol

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EP2102137A1 true EP2102137A1 (fr) 2009-09-23

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US (1) US20100019191A1 (fr)
EP (1) EP2102137A1 (fr)
CN (1) CN101583583A (fr)
BR (1) BRPI0720288A2 (fr)
WO (1) WO2008071642A1 (fr)

Families Citing this family (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010101636A2 (fr) 2009-03-02 2010-09-10 Sud-Chemie Inc. Support de catalyseur d'oxyde de zirconium activé
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CN103420795B (zh) * 2012-05-18 2015-11-04 中国科学院大连化学物理研究所 一种低沸点有机相中由碳水化合物生产二元醇的方法
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US9205412B2 (en) 2013-03-01 2015-12-08 Clariant Corporation Catalyst for polyol hydrogenolysis
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BR112016003939B1 (pt) * 2013-08-26 2021-02-23 Shell Internationale Research Maatschappij B.V. processo para a preparação de um composto
ITTO20130711A1 (it) * 2013-09-02 2015-03-03 Biochemtex Spa Composizioni di glicole etilenico bioderivato per bottiglie di poliestere
US10253009B2 (en) 2014-08-14 2019-04-09 Shell Oil Company One-step production of furfural from biomass
EP3180321A4 (fr) 2014-08-14 2018-04-11 Shell International Research Maatschappij B.V. Procédé de préparation de furfural à partir d'une biomasse
CA2954306C (fr) 2014-08-14 2022-08-30 Shell Internationale Research Maatschappij B.V. Procede permettant de preparer du furfural a partir d'une biomasse
WO2016025677A1 (fr) 2014-08-14 2016-02-18 Shell Oil Company Procédé de fabrication de furural et des dérivés de furfural
CN105669373B (zh) * 2014-11-17 2017-09-15 中国科学院大连化学物理研究所 一种多元醇氢解的方法
CN109071478A (zh) 2016-05-03 2018-12-21 国际壳牌研究有限公司 木质素基溶剂和其制备方法
CA3039790A1 (fr) 2016-11-01 2018-05-11 Shell Internationale Research Maatschappij B.V. Procede de recuperation de furfural
US10899725B2 (en) 2016-11-01 2021-01-26 Shell Oil Company Process for the recovery of furfural
WO2018085176A1 (fr) 2016-11-01 2018-05-11 Shell Oil Company Procédé de récupération de furfural
US10501430B2 (en) 2016-11-01 2019-12-10 Shell Oil Company Process for the recovery of furfural
CN108070075A (zh) 2016-11-09 2018-05-25 可口可乐公司 生物基meg和聚酯纤维组合物以及制造它们的方法
CN108070079A (zh) * 2016-11-09 2018-05-25 可口可乐公司 生物基meg和pet组合物以及制造它们的方法
DE102017204322A1 (de) * 2017-03-15 2018-09-20 Rheinisch-Westfälische Technische Hochschule (Rwth) Aachen Verfahren zur chemischen Umsetzung von Zuckern oder Zuckeralkoholen zu Glykolen
KR102079120B1 (ko) * 2018-06-18 2020-02-19 한국과학기술연구원 칼슘염에 담지된 금속 촉매, 이의 제조방법 및 이를 이용한 함산소 화합물의 수첨탈산소 반응방법
DE102018215394A1 (de) * 2018-09-11 2020-03-12 Rheinisch-Westfälische Technische Hochschule Aachen Verfahren zur chemischen Umsetzung von Zuckern oder Zuckeralkoholen zu Glykolen
DE102019113135A1 (de) * 2019-05-17 2020-11-19 Rheinisch-Westfälische Technische Hochschule (Rwth) Aachen Verfahren zur Herstellung von Glycolen aus Zuckern und Zuckeralkoholen
WO2020234303A1 (fr) 2019-05-22 2020-11-26 Shell Internationale Research Maatschappij B.V. Procédé de production de furfural
CN110483239B (zh) * 2019-08-26 2021-04-06 同济大学 一种丙二醇的制备方法
KR20220069988A (ko) * 2019-09-26 2022-05-27 옴야 인터내셔널 아게 금속 화학종을 위한 촉매 담체로서의 srcc

Family Cites Families (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3030429A (en) * 1962-04-17 Process for the direct hydrogenation splitting of
US3396199A (en) * 1967-01-03 1968-08-06 Atlas Chem Ind Hydrogenolysis of reducible sugars to obtain a high percentage of glycerol
US4380678A (en) * 1981-01-21 1983-04-19 Hydrocarbon Research, Inc. Multi-stage aldoses to polyols process
US4401823A (en) * 1981-05-18 1983-08-30 Uop Inc. Hydrogenolysis of polyhydroxylated compounds
US4404411A (en) * 1982-02-01 1983-09-13 E. I. Du Pont De Nemours And Company Hydrogenolysis of polyols to ethylene glycol in nonaqueous solvents
US4496780A (en) * 1983-06-22 1985-01-29 Uop Inc. Hydrocracking of polyols
US4561990A (en) * 1984-10-04 1985-12-31 Texaco Inc. High lead solder corrosion inhibitors
DE3818198A1 (de) * 1988-05-28 1989-12-21 Basf Ag Verfahren zur herstellung niederer mehrwertiger alkohole
DE3928285A1 (de) * 1989-08-26 1991-02-28 Basf Ag Verfahren zur herstellung niederer, mehrwertiger alkohole
US5026927A (en) * 1989-11-16 1991-06-25 The United States Of America As Represented By The United States Department Of Energy Hydrocracking of carbohydrates making glycerol, glycols and other polyols
IT1256801B (it) * 1992-01-31 1995-12-15 Novamont Spa Catalizzatore di idrogenazione, procedimento per la sua preparazione ed impiego, particolarmente per l'idrogenazione e/o idrogenolisi di carboidrati e polioli.
DE4239782A1 (de) * 1992-11-26 1994-06-01 Basf Ag Verfahren zur Herstellung von Diaminen
DE4407466A1 (de) * 1994-03-07 1995-09-14 Basf Ag Verfahren zur Herstellung von peralkylierten Aminen
AU5813496A (en) * 1995-05-17 1996-11-29 Basf Aktiengesellschaft Process for producing n-methyl-2-(3,4 dimethoxyphenyl)-ethyl amine
US6548681B1 (en) * 2001-06-26 2003-04-15 Board Of Trustees Of Michigan State University Process for the recovery of a polyol from an aqueous solution
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
DE50211196D1 (de) * 2001-12-07 2007-12-27 Basf Ag Verfahren zur Herstellung von Ruthenium/Eisen/Kohlenstoffträger-Katalysatoren
DE10160143A1 (de) * 2001-12-07 2003-06-18 Basf Ag Verfahren zur selektiven Hydrierung von olefinisch ungesättigten Carbonylverbindungen
US6982328B2 (en) * 2003-03-03 2006-01-03 Archer Daniels Midland Company Methods of producing compounds from plant material
EP1859002B1 (fr) * 2005-02-28 2011-04-27 Basf Se Concentrés d'antigel contenant de la glycérine protégeant contre la corrosion
US20070135301A1 (en) * 2005-12-08 2007-06-14 Sud-Chemie Inc. Catalyst for the production of polyols by hydrogenolysis of carbohydrates

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2008071642A1 *

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