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WO1999033772A1 - Procede de preparation d'alkyleneglycol - Google Patents

Procede de preparation d'alkyleneglycol Download PDF

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Publication number
WO1999033772A1
WO1999033772A1 PCT/EP1998/008347 EP9808347W WO9933772A1 WO 1999033772 A1 WO1999033772 A1 WO 1999033772A1 EP 9808347 W EP9808347 W EP 9808347W WO 9933772 A1 WO9933772 A1 WO 9933772A1
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WO
WIPO (PCT)
Prior art keywords
catalyst
oxide
groups
acidic
functional groups
Prior art date
Application number
PCT/EP1998/008347
Other languages
German (de)
English (en)
Inventor
Georg Heinrich Grosch
Bernd Stein
Eugen Gehrer
Original Assignee
Basf Aktiengesellschaft
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Basf Aktiengesellschaft filed Critical Basf Aktiengesellschaft
Priority to EP98966839A priority Critical patent/EP1042258A1/fr
Priority to KR1020007006990A priority patent/KR20010033489A/ko
Priority to JP2000526459A priority patent/JP2001527055A/ja
Priority to CA002310835A priority patent/CA2310835A1/fr
Publication of WO1999033772A1 publication Critical patent/WO1999033772A1/fr

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Classifications

    • 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
    • C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
    • C07C29/10—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of ethers, including cyclic ethers, e.g. oxiranes
    • 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
    • C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
    • C07C29/10—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of ethers, including cyclic ethers, e.g. oxiranes
    • C07C29/103—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of ethers, including cyclic ethers, e.g. oxiranes of cyclic ethers
    • C07C29/106—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of ethers, including cyclic ethers, e.g. oxiranes of cyclic ethers of oxiranes
    • 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 invention relates to a process for the preparation of alkylene glycol by reacting a reaction mixture containing alkylene oxide and water in the presence of a solid catalyst which is not soluble in the reaction mixture.
  • Alkylene glycols are used in a wide range of applications. These include, for example, use as a polyol component in the synthesis of polymers, in particular polyesters, polyethers and polyurethanes, use as an antifreeze in cooling systems or as a deicing agent in aviation. Furthermore, glycols can be used as difunctional alcohols, in particular in the production of hydroxy esters of mono- or polycarboxylic acids, the synthesis of hydroxy esters of (meth) acrylic acid being particularly noteworthy.
  • alkylene glycols e.g. Ethylene glycol or propylene glycol are generally based on liquid phase hydrolysis of the corresponding alkylene oxide in the presence of an excess of water. Furthermore, processes for the production of alkylene glycols by hydrolysis in a heterogeneous system already exist.
  • ion exchange materials have proven to be suitable, for example, for replacing soluble mineral acids as catalysts.
  • the documents US-A 4, 165,440 and US-A 4,504,685 describe thermally stable, fluorinated alkyl sulfonic acid ion exchange resins which have sufficient activities in the hydrolysis of alkylene oxides.
  • WO 87/06244 describes a material with sulfonic acid groups covalently bonded to polymer chains, in which the polymer chain is a generally defined, polar material. This material has a higher activity and is much more stable than commercially available organic polystyrene sulfonic acids.
  • US Pat. No. 4,620,044 describes silicates and zeolites with acidic hydrogen atoms, which likewise have high activities and thus enable hydrolysis of alkylene oxides to alkylene glycols under mild conditions (25 ° C., 1 bar).
  • US Pat. No. 4,393,254 describes a catalyst which consists of amine-neutralized sulfonic acid groups and shows satisfactory selectivities at low water / alkylene oxide ratios.
  • the activity and the improved selectivity of the described method are believed to be due to the action of the sulfonic acid anion as an attacking nucleophile.
  • a disadvantage of this process is that the product stream generally always has a proportion of cations which are derived from the th catalyst material originate. This can lead to a reduction in product quality and a limited service life for the catalyst material.
  • EP-A 0 156 449 describes a process for the preparation of alkylene glycol in the presence of organometallates.
  • the hydrolysis of an alkylene oxide takes place in the presence of a solid with cationic centers that are coordinated with metalate anions.
  • Molybdates, tungstates, metavanadates, hydrogen pyrovanadates and pyrovanadates are mentioned in particular as metalate anions.
  • WO 95/20559 describes a process for the preparation of alkylene glycols with water in the presence of a solid material with one or more cationic centers. These electropositive centers are coordinated with one or more anions (no metallates, halides) via ionic bonds.
  • WO 97/19043 describes a polymeric organosiloxane ammonium salt which has carboxylates, hydrogen sulfites, hydrogen phosphates, hydrogen carbonates, formates or metalates as counterions.
  • EP-A 0 156 447 therefore describes the use of an anion exchanger to purify the product stream, as a result of which the concentration of nucleophiles (for example metallates) in the product is to be reduced. This also applies correspondingly to the method known from US Pat. No. 4,393,254.
  • EP-A 0 160 330 relates to a process for the production of alkylene glycol, in which an inorganic or organic carrier coated with metalate anions and capable of exchanging anions is used as the catalyst.
  • the metalate anions are ionically bound to amino groups of the support.
  • the object of the present invention is then to provide a process for the selective production of monoalkylene glycol from alkylene oxide with the aid of a solid, insoluble catalyst, which with a low water / alkylene oxide ratio high selectivity leads to monoalkylene glycol. Furthermore, it was an object of the present invention to provide a process for the preparation of monoalkylene glycol from alkylene oxide with the aid of a solid, insoluble catalyst which does not lead to impurities in the product formed. It was also an object of the present invention to provide a process for the preparation of monoalkylene glycol from alkylene oxide with the aid of a solid, insoluble catalyst which enables the catalyst to have a long service life. Furthermore, it was an object of the present invention to provide a catalytically active shaped body (catalyst) that enables the above procedures to be carried out successfully.
  • the present invention thus relates to a process for the preparation of alkylene glycol. or a mixture of two or more different alkylene glycols, in which a reaction mixture containing at least one alkylene oxide or a mixture of two or more different alkylene oxides, a catalyst and water is reacted, characterized in that the catalyst in Reaction mixture is insoluble and has at least one covalently bonded acidic functional group and at least one covalently bonded basic functional group.
  • the alkylene oxide which can be converted by the process according to the invention or the mixture of two or more alkylene oxides is preferably an alkylene oxide or a number of different alkylene oxides of the general formula I
  • R 1 , R-, R J and R 4 are each the same or different and are independently hydrogen, C 0 alkyl, C 2 . 10 alkenyl, C 2-10 alkynyl, C 3 . 10 -cycloalkyl, C 3 . 10 -cycloalkenyl, C 6 . 12 aryl or heteroaryl, where the alkyl, alkenyl or alkynyl radicals can be linear or, if appropriate, branched and in turn can carry further functional groups, and the cycloalkyl, aryl and heteroaryl radicals can in turn carry further functional groups or can be substituted with C 0 alkyl, alkenyl, alkynyl or aryl radicals.
  • Alkylene oxides which are preferably used are, for example, ethylene oxide and propylene oxide.
  • the alkylene oxide which can be used in the context of the present process, or the mixture of two or more different alkylene oxides, can come from any source or from any number of sources, i. H. be made by any method.
  • ethylene oxide can be obtained by catalytic oxidation of ethylene, ethylene and a gas containing molecular oxygen, for example air, oxygen-enriched air or pure oxygen, being reacted in the gas phase on a silver-containing catalyst.
  • the alkylene oxide which can be used in the context of the present invention, or the mixture of two or more different alkylene oxides, is preferably used in pure form. This means that the alkylene oxide or alkylene oxides used are essentially free of impurities, and thus essentially 100% of the alkylene oxide or Mixture of two or more different alkylene oxides. However, it is also possible to use a technical grade of alkylene oxide which still contains impurities which are usually present before the alkylene oxide is purified after production.
  • the water used in the context of the present invention can come from a wide variety of sources and does not have to meet any particular conditions with regard to its purity. Suitable are, for example, fresh water, as is generally available from process water treatment plants or, for example, from waterworks, water which has been subjected to an ion exchange process, water vapor condensate, and water of reaction which is usually obtainable in the case of chemical reactions which proceed with the elimination of water.
  • a molar ratio of water to compounds carrying alkylene oxide groups of from about 1 to about 50 leads to advantageous results in the process according to the invention.
  • the molar ratio of alkylene oxide groups in the alkylene oxide, or in a mixture of two or more different alkylene oxides, to water is about 1: 1 to about 1:40.
  • Molar ratios of greater than about 2 to less than about 25, for example less than about 20, and in particular less than about 20 are preferred. It is particularly preferred if the molar ratio is about 5 to about 17.5.
  • a weight ratio of water to compounds carrying alkylene oxide groups of from about 1 to 20 is generally correspondingly advantageous if the weight ratio of water to compounds carrying alkylene oxide groups is greater than 1 and less than about 10, in particular less than about 8, and particularly preferably about 2 to about 7
  • the catalyst according to the invention contains a solid support which is insoluble in the reaction medium and to which at least one acidic and at least one basic functional group is covalently bound.
  • acidic functional groups which can form a strong nucleophile.
  • the acid residues can, for example, be directly covalently bound to the support.
  • the catalyst has, as an acidic functional group, one or more functional groups selected from the group of acidic residues consisting of sulfonic acid, sulfinic acid, phosphonic acid, phosphinic acid, carboxylic acid and metal oxide acid residues of tungsten, rhenium, molybdenum and vanadium. Metal oxide, carbon and sulfonic acid residues are particularly preferred.
  • the catalyst used in the context of the present invention also has at least one basic functional group.
  • the basic functional group can, for example, be directly covalently bound to the support. Also possible is a covalent bond to the support via linear or branched carbon chains, which optionally have one or more heteroatoms such as oxygen, nitrogen, phosphorus or sulfur, or two or more different ones Heteroatoms, can contain, or via one or more identical or different heteroatoms.
  • the catalyst has as basic functional group one or more functional groups selected from the group consisting of primary, secondary and tertiary amino and phosphine groups.
  • the acidic functional groups and the basic functional groups can each be individually covalently bound to the support. However, it is also possible for two or more acidic or basic functional groups to be linked together to the support via a covalent bond. It is also possible in the context of the present invention that one or more acidic functional groups together with one or more basic functional groups are connected together to the support via a covalent bond. The same conditions apply to the type of covalent bond as for individually bound acidic or basic functional groups.
  • the molar ratio of the acidic to the basic groups can be from about 1:99 to about 99: 1.
  • a molar ratio of the acidic functional groups to the basic functional groups of from about 1:20 to about 20: 1 is preferred.
  • the ratio of acidic functional groups to basic functional groups is greater than 1 is, for example about 2 1 to about 10: 1, for example about 3 1 to about 6 1 or in between, for example about 4 1 or about 5: 1
  • a catalyst has a particularly advantageous effect on the process according to the invention when acidic functional groups and basic functional groups are combined in the catalyst in such a way that the basic functional groups are capable of deprotonating the acidic functional groups under reaction conditions.
  • the resulting deprotonated acidic functional group now acts as a strong nucleophile and reacts with the alkylene oxide to open the ring and form an intermediate. This intermediate is then hydrolyzed to monoalkylene glycol by the water present in the reaction mixture under the prevailing reaction conditions.
  • Inorganic or organic solids or even composite materials made of inorganic and organic substances can be used as solid support materials for the catalysts according to the invention.
  • organic polymers which are inert and stable under the reaction conditions in the process according to the invention are suitable as organic support materials.
  • These can be polymers in which the required acidic and basic functional groups have already been introduced during the polymerization.
  • it can be a question of polymers in which the acidic and basic functional groups are converted into the desired acidic and basic functional groups by subsequent functionalization by means of polymer-analogous reactions, for example by chemical modification of introduced auxiliary functions.
  • polymeric compounds which each have only acidic or basic functional groups by means of a matrix, the matrix being an organic or a can act inorganic matrix.
  • oligomeric or polymeric compounds each having only acidic or basic functional groups
  • a suitable matrix of an inert, neutral polymer or, for example, oligomeric or polymeric compounds, which only have acidic functional groups, into a suitable matrix polymerize a polymer that has only basic functional groups, or vice versa.
  • Possible carriers can be, for example, phenol / - or melamine / formaldehyde resins or styrene copolymers crosslinked with divinylbenzene, as partially functionalized in the Lewatit ® (Bayer) and Amberlite ® (Rohm.) Product ranges and Haas) are commercially available.
  • Copolymers based on acrylic acid / formamide or acrylic acid / vinylformamide, which can be polymerized, for example, with suitable protective groups and then converted into the corresponding catalyst by removing the protective groups, can also be used as carriers.
  • inorganic solids are used as carriers, there are different types of production and functionalization.
  • All micro-, meso- and or macroporous metal oxides with BET surface areas of 1 to 1100 m 2 / g, preferably 10 to 900 m 2 / g, can be used as supports for catalysts which can be used in the process according to the invention.
  • These metal oxides should preferably have a high OH group density, which can be used for the corresponding functionalization with acidic and basic functional groups, and thus for the preparation of the catalyst.
  • the following metal oxides are suitable, for example: elements of groups IIA to VIIA, and IB to VIIIB, and mixtures of two or more thereof, preferably metal oxides of groups IIIA, IVA, IIB-IVB, and mixtures of two or more thereof.
  • silicon dioxide, aluminum oxide, gallium oxide, boron oxide, indium oxide, germanium oxide, titanium oxide are particularly preferred. Zirconium oxide, and mixtures of two or more of them.
  • derivatized functional groups can be introduced as precursors, for example, by saponification, oxidation, hydrogenation, nucleophilic substitution , electrophilic substitution, polymerization, depolymerization, CH functionalization or other reactions, or combinations of two or more of the reactions mentioned, can be converted into the desired acidic or basic functional groups.
  • the conversion of the introduced group into the desired group is preferably carried out on the solid.
  • supports are used which can be produced, for example, using a conventional sol-gel process.
  • porous gels can contain silicon, aluminum, boron, titanium, zirconium, vanadium, niobium or tantalum, or a mixture of two or more thereof.
  • preference is given to gels which contain silicon, aluminum, titanium or zirconium, or a mixture of two or more thereof.
  • organometallic compounds for example
  • Catalysts which can be used in the process according to the invention can be obtained, for example, by adding appropriately functionalized monomers already during the sol-gel process during the preparation of the support and thus incorporating them into the resulting gel during gel formation.
  • a catalyst which is suitable in the context of the present invention can be produced by a sol-gel process in which a tetraalkoxysilane is hydrolyzed together with 3-cyanopropyltrimethoxysilane and 3-aminopropyltriethoxysilane. Subsequent saponification of the cyano group leads to a catalyst which has the acidic and basic functional groups required for successfully carrying out the process according to the invention.
  • the present invention thus also relates to a shaped body comprising an inorganic carrier which has at least one acidic and at least one basic functional group, characterized in that the functional groups are covalently linked to the carrier.
  • the carrier has, as at least one acidic functional group, one or more functional groups selected from the group consisting of sulfonic acids, sulfinic acids, phosphonic acids, phosphinic acids, carboxylic acids and metal oxide acids of tungsten, rhenium. Molybdenum and vanadium.
  • the carrier has at least one basic functional group one or more functional groups selected from the group consisting of primary, secondary and tertiary amino and phosphine groups.
  • the carrier predominantly contains silicon dioxide.
  • a finely divided particulate material which is insoluble during gel production and which can be completely or at least largely removed from the catalyst again after the gel has been prepared in the preparation of the support or the catalyst. If the diameter of the individual particles of the finely divided material is small compared to the diameter of the carrier particles, the removal of the finely divided material leads to voids in the carrier and thus generally to an increased porosity and increased activity of the corresponding catalyst.
  • the gels produced can optionally be functionalized subsequently.
  • a composite of organic and inorganic carriers can also be used as the carrier.
  • the carrier for example, it is possible to add acidic or basic functional groups or acidic and basic functional groups that are supported on an organic carrier. material bound to be incorporated into a matrix of a solid, inorganic carrier.
  • a particular embodiment of the invention accordingly consists in introducing a polymer doped with the corresponding functional groups into a matrix of a solid inorganic or organic material and thus heterogenizing it.
  • the polymer is then surrounded by the carrier matrix and is tightly enclosed by it so that rinsing out under reaction conditions is impossible.
  • the functional groups covalently bonded to the polymer are nevertheless accessible for the reaction with the alkylene oxide and are therefore catalytically active.
  • the inclusion of the correspondingly functionalized polymer can be carried out using a sol-gel process using an inorganic carrier.
  • the functionalized polymer can be present in the mixture to be polymerized, for example, during the polymerization of the carrier. Subsequent functionalization by chemical reactions on the catalyst is also possible in these embodiments.
  • the process according to the invention for the production of alkylene glycol can be operated both in a batch process and continuously, for example in a tubular reactor.
  • the catalyst can be present in a fixed bed or in suspended form, for example in a fluidized bed. Accordingly, the individual catalyst particles (shaped bodies) should have a shape adapted to the desired procedure.
  • the catalysts are used in the form of strands, grit, granules, tablets, and applied to packs, nets, fabrics, etc.
  • Other suitable shapes are, for example, spheres, grains, pellets, rods, platelets or similar suitable three-dimensional shapes.
  • the shaping will be carried out either before or after the functionalization.
  • the order of shaping and functionalization is arbitrary.
  • attempts will preferably be made to control the gel formation in such a way that the gel obtained already has one of the desired three-dimensional shapes.
  • organic and inorganic carrier materials those with polar and hydrophilic properties are preferred.
  • the method described in the invention can be operated in a continuous and discontinuous (batch) manner.
  • a continuous process is preferred.
  • a fixed bed process is preferred for the continuously operated processes, but suspension processes are also possible.
  • a liquid hourly space velocity (LHSV ml reac. Onsgem t i i sc i / ⁇ i Kata ysator * 11]) of at least about 0.3 h -1 with a selectivity to Achieve monoalkylene glycol of at least about 90%.
  • LHSV is preferably higher, for example at about 0.5 h "1 or 1.0 h " 1 or above.
  • the process according to the invention is preferably carried out at a temperature in the range from about 40 to about 200 ° C., a temperature of 80 to 150 ° C. is preferred.
  • the pressure at which the reaction is carried out is in the range from 200 to 10,000 kPa, preferably in the range from 200 to 6000 kPa.
  • the pressure can be adjusted, for example, with the Nitrogen, helium, neon or argon can be set in the reaction vessel.
  • Catalyst A (comparative product: acidic functional groups only):
  • Catalyst 2 (according to the invention):
  • the dried solid (355 g) was reacted with 1000 ml of 2-normal hydrochloric acid for 4 hours at 120 ° C. to remove the calcium carbonate, then washed neutral and neutral with water and dried at 120 ° C.
  • the solid obtained in this way was reacted to saponify the nitrile groups with 700 g of 85% strength H 3 PO 4 for 6 hours at 120 ° C. and then washed neutral with water and dried at 120 ° C.
  • the so obtained Solid was then classified and the fraction 1.5 mm to 0.5 mm was used for the fixed bed catalytic test.
  • silica gel (Fluka, silica gel 60) was dried in an oven at 200 ° C. for 20 hours. The silica gel was then stirred in a 1000 ml beaker for 4 hours at room temperature in a solution of 40 ml of 3-cyanopropyltriethoxysilane, 40 ml of 3-aminopropyltrimethoxysilane and 500 ml of anhydrous toluene. The solid was filtered off and dried in a drying cabinet at 120 ° C. The dried solid was then reacted with 1375 ml of 85% strength H 3 PO 4 at 120 ° C. for 6 hours to saponify the nitrile group. The solid was then washed neutral with water and dried at 120 ° C. The material thus obtained was classified and the fraction 1.0 mm to 0.5 mm was used for the catalytic test.
  • Catalyst 5 (according to the invention):
  • the test examples described below were carried out in a continuously operated flow tube (diameter 1 cm, length 40 cm).
  • the liquid starting materials in this case ethylene oxide (EO) and water, were mixed at a pressure of 45 bar at the reactor inlet.
  • the reactor consisted of a jacketed tube and was overlaid with oil heated a thermostat. The temperature was measured and controlled in the middle of the catalyst bed using an inserted thermocouple.
  • the selectivities S given below are molar selectivities, calculated from the quotient of converted ethylene oxide and monoethylene glycol formed.
  • Table 3 shows various experiments with catalysts 1 to 3 at different EO / water mass ratios. There is a significant increase in selectivity compared to the uncatalyzed hydration.
  • the catalysts 1 to 5 showed no signs of deactivation or changes in the selectivity over a period of 300 h.
  • Analyzes (GC, IR) of the reactor output stream were unable to detect any functional carboxyl or amino groups discharged and possible derivatives, and titration with sodium hydroxide solution of samples of catalysts 1 and 2 which had been treated with acid and rinsed again with water after their operation showed no change compared to the original loading with carboxylic acid groups
  • the catalyst material is stable due to the covalently bonded, acidic and basic functional groups under reaction conditions.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

L'invention concerne un procédé de préparation d'alkylèneglycol ou d'un mélange de deux différents alkylèneglycols ou plus, selon lequel un mélange réactionnel contenant au moins un oxyde d'alkylène ou un mélange de deux différents oxydes d'alkylène ou plus, un catalyseur et de l'eau sont mis à réagir. Le catalyseur est non soluble dans le mélange réactionnel et comprend au moins un groupe acide fonctionnel lié de manière covalente. L'invention concerne en outre un corps moulé contenant un support inorganique qui comporte au moins un groupe acide fonctionnel et au moins un groupe basique fonctionnel, lesdits groupes fonctionnels étant liés de manière covalente avec le support.
PCT/EP1998/008347 1997-12-23 1998-12-18 Procede de preparation d'alkyleneglycol WO1999033772A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP98966839A EP1042258A1 (fr) 1997-12-23 1998-12-18 Procede de preparation d'alkyleneglycol
KR1020007006990A KR20010033489A (ko) 1997-12-23 1998-12-18 알킬렌 글리콜을 제조하는 방법
JP2000526459A JP2001527055A (ja) 1997-12-23 1998-12-18 アルキレングリコールの製造方法
CA002310835A CA2310835A1 (fr) 1997-12-23 1998-12-18 Procede de preparation d'alkyleneglycol

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19757684.2 1997-12-23
DE19757684A DE19757684A1 (de) 1997-12-23 1997-12-23 Verfahren zur Herstellung von Alkylenglykol

Publications (1)

Publication Number Publication Date
WO1999033772A1 true WO1999033772A1 (fr) 1999-07-08

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EP (1) EP1042258A1 (fr)
JP (1) JP2001527055A (fr)
KR (1) KR20010033489A (fr)
CN (1) CN1283172A (fr)
CA (1) CA2310835A1 (fr)
DE (1) DE19757684A1 (fr)
ID (1) ID24736A (fr)
WO (1) WO1999033772A1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NZ515366A (en) * 2001-11-08 2004-07-30 Univ Waikato Method for producing vicinal diols of compounds (especially lanosterol and cyclohexane derivatives) by reacting compounds with acids with pKa of less than or equal to 2 in the presence of one or more reagents capable of supplying hydroxy groups
JP4592258B2 (ja) * 2003-05-07 2010-12-01 出光興産株式会社 ２−アルキルアルカン−１，２−ジオール類の製造方法
US7435858B2 (en) * 2004-12-23 2008-10-14 Shell Oil Company Process for the preparation of alkylene glycols

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3129956A1 (de) * 1981-07-29 1983-02-17 Vysoká škola chemicko-technologická Praha, Praha Verfahren zur herstellung von alkylenoxid-polyaddukten
US4620044A (en) * 1985-10-16 1986-10-28 Mobil Oil Corporation Hydrolysis of olefin oxides to glycols
JPS61271231A (ja) * 1985-05-28 1986-12-01 Mitsui Toatsu Chem Inc 多価アルコ−ルの製造法
WO1997019043A1 (fr) * 1995-11-23 1997-05-29 Shell Internationale Research Maatschappij B.V. Procede de preparation d'alkylene glycols

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3129956A1 (de) * 1981-07-29 1983-02-17 Vysoká škola chemicko-technologická Praha, Praha Verfahren zur herstellung von alkylenoxid-polyaddukten
JPS61271231A (ja) * 1985-05-28 1986-12-01 Mitsui Toatsu Chem Inc 多価アルコ−ルの製造法
US4620044A (en) * 1985-10-16 1986-10-28 Mobil Oil Corporation Hydrolysis of olefin oxides to glycols
WO1997019043A1 (fr) * 1995-11-23 1997-05-29 Shell Internationale Research Maatschappij B.V. Procede de preparation d'alkylene glycols

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 011, no. 133 (C - 418) 25 April 1987 (1987-04-25) *

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EP1042258A1 (fr) 2000-10-11
CN1283172A (zh) 2001-02-07
KR20010033489A (ko) 2001-04-25
ID24736A (id) 2000-08-03
JP2001527055A (ja) 2001-12-25
DE19757684A1 (de) 1999-06-24
CA2310835A1 (fr) 1999-07-08

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