WO2000035842A1 - Carboxylates in catalytic hydrolysis of alkylene oxides - Google Patents
Carboxylates in catalytic hydrolysis of alkylene oxides Download PDFInfo
- Publication number
- WO2000035842A1 WO2000035842A1 PCT/EP1999/010049 EP9910049W WO0035842A1 WO 2000035842 A1 WO2000035842 A1 WO 2000035842A1 EP 9910049 W EP9910049 W EP 9910049W WO 0035842 A1 WO0035842 A1 WO 0035842A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- acid
- process according
- solid support
- acid derivative
- catalyst
- Prior art date
Links
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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/08—Ion-exchange resins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0239—Quaternary ammonium compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0255—Phosphorus containing compounds
- B01J31/0267—Phosphines or phosphonium compounds, i.e. phosphorus bonded to at least one carbon atom, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, the other atoms bonded to phosphorus being either carbon or hydrogen
- B01J31/0268—Phosphonium compounds, i.e. phosphine with an additional hydrogen or carbon atom bonded to phosphorous so as to result in a formal positive charge on phosphorous
-
- 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 alkylene glycols by reacting an alkylene oxide with water in the presence of a catalytic composi ⁇
- Alkylene glycols in particular monoalkylene glycols, are of established commercial interest.
- monoalkylene glycols are being used in anti-freeze compositions, as solvents and as base materials in the production of polyalkylene terephthalates e.g. for fibres or bottles.
- alkylene glycols by liquid phase hydrolysis of alkylene oxide is known.
- the hydrolysis s performed without a catalyst by adding a large excess of water, e.g. 20 to 25 moles of water per mole of alkylene oxide, or it is performed with a smaller excess of water in a catalytic system.
- the reaction is considered to be a nucleophilic substitution reaction, whereby opening of the alkylene oxide ring occurs, water acting as the nucleophile.
- the primarily formed monoalkylene glycol also acts as a nucleophile, as a rule a mixture of monoalkylene glycol, dialkylene glycol and higher alkylene glycols is formed.
- One effective means for suppressing the secondary reaction is to increase the relative amount of water present m the reaction mixture. Although this measure improves the selectivity towards the production of the monoalkylene glycol, it creates a problem in that large amounts of water have to be removed for recovering the product .
- the metalate anions are specified as molybdate, tungstate, metavanadate, hydrogen pyrovanadate and pyrovanadate anions.
- a complication of this process is that the alkylene glycol-containing product stream also comprises a substantial amount of metalate anions, displaced from the electropositive complexing sites of the solid metalate anion containing material.
- this stream is contacted with a solid having electropositive complexing sites associated with anions which are replaceable by the said metalate anions.
- WO 95/20559 there is disclosed a process for the preparation of alkylene glycols wherein an alkylene oxide is reacted with water in the presence of a catalyst composition comprising a solid material having one or more electropositive sites, which are coordinated with one or more anions other than metalate or halogen anions, e.g. bicarbonate, bisulphite and carboxylate, with the proviso that when the solid material is an anionic exchange resin of the quaternary ammonium type and the anion is bicarbonate the process is performed in the substantial absence of carbon dioxide.
- a catalyst composition comprising a solid material having one or more electropositive sites, which are coordinated with one or more anions other than metalate or halogen anions, e.g. bicarbonate, bisulphite and carboxylate, with the proviso that when the solid material is an anionic exchange resin of the quaternary ammonium type and the anion is bicarbonate the process is performed in the substantial absence of carbon dioxide.
- a drawback shared by the conventional anionic exchange resins is their limited tolerance to heat.
- catalyst compositions based on conventional organic quaternary ammonium ion exchangers it has been found, that under severe alkylene oxide hydrolysis reaction conditions (high temperature and/or long service) the catalytic activity (selectivity and/or conversion) of the conventional resin-based catalysts tends to deteriorate. Moreover, under these reaction conditions these catalysts were found to undergo swelling .
- EP-A 226 799 there is disclosed a method for preparing ethylene glycol or propylene glycol by hydration of the respective oxide, in the presence of a dual composition catalyst consisting of a monobasic or polybasic carboxylic acid and a metal or ammonium salt of such a carboxylic acid.
- the present invention relates to a process for the preparation of alkylene glycols by reacting an alkylene oxide with water in the presence of a catalytic composition including a polycarboxylic acid derivative, having in its chain molecule one or more carboxyl groups and one or more carboxylate groups, the individual carboxyl and/or carboxylate groups being separated from each other in the chain molecule by a separating group consisting of at least one atom.
- a catalytic composition including a polycarboxylic acid derivative, having in its chain molecule one or more carboxyl groups and one or more carboxylate groups, the individual carboxyl and/or carboxylate groups being separated from each other in the chain molecule by a separating group consisting of at least one atom.
- the number of carboxylic groups in the molecule is at least equal to the number of carboxylate groups.
- the polycarboxylic acid derivative as defined above is immobilised on a solid support.
- Solid catalysts including such immobilised polycarboxylic acid derivatives are novel.
- the carboxylate groups may be metal salts such as alkali metal and earth alkali metal salts or ammonium salts .
- the carboxylates are alkali metal salts, most preferably sodium salts.
- the separating group may comprise several atoms, which then may be arranged in a linear or branched chain or in a ring.
- the separating group consists of a single carbon atom.
- dicarboxylic acid derivatives are the monosodium salts of malonic acid, succinic acid, adipic acid, tartaric acid, maleic acid, terephthalic acid, malic acid, suberic acid, phthalic acid, isophthalic acid, quinolinic acid (2,3 pyridine dicarboxylic acid), isochinchomeronic acid (2,5 pyridine dicarboxylic acid), dipicolinic acid (2,6 pyridine dicarboxylic acid), chinchomeronic acid (3,4 pyridine dicarboxylic acid), dinicotinic acid (3,5 pyridine dicarboxylic acid), cyclohexene-1, 2-dicarboxylic acid (3 , 4 , 5, 6-tetrahydrophtalic acid) and isomers, cyclohexane-1 , 2-dicarboxylic acid (hexahydrophthalic acid) and isomers, cyclohexane-1, 1-dicarboxylic acid,
- Examples of tricarboxylic acid derivatives according to the invention are the monosodium salts of citric acid, trimellitic acid ( 1, 2 , 4-benzenetricarboxylic acid), and trimesic acid ( 1, 3, 5-benzenetricarboxylic acid) .
- Examples of tetracarboxylic acid derivatives according to the invention are the monosodium and disodium salt of pyromellitic acid (1,2,4,5- benzenetetracarboxylic acid) .
- the polycarboxylic acid derivative as herein defined are effective as alkylene oxide hydrolysis catalysts in a homogeneous liquid reaction system.
- a particular advantage of these polycarboxylic acid derivatives emerges when they are used in a heterogeneous reaction system, wherein they are immobilised on a solid support, especially but not exclusively a solid material having electropositive sites as defined m WO 95/20559.
- the solid support is a strongly basic anionic exchange resin the anion of which is exchanged with a polycarboxylic acid derivative according to the present invention, a catalytic composition is formed which is stable and which retains its selectivity and stability under severe reaction conditions as well as being more resistant to swelling .
- IER's ion exchange resins
- the solid support m particular the strongly basic (anionic) IER's wherein the basic groups are quaternary ammonium or quaternary phosphomum, IER' s based on vmylpyridme, polysiloxanes, as well as other solid supports having electropositive complexing sites of inorganic nature, such as carbon, silica, silica-alumina, zeolites, glass and clays such as hydrotalcite .
- immobilised complexing macrocycles such as crown ethers, etc. can be used as well as solid support.
- Anionic exchange resins which are suitable for use in the present process are known per se and many are commercially available, e.g. the ones sold under the trade names AMBERJET 4200, AMBERLITE 400, IRA 404, LEWATIT M 500WS, DOWEX 1 x 8, DOWEX MSA-1 (all of which are products based on polystyrene, cross-linked with divinylbenzene) and REILLEX HPQ (based on polyvinyl- py ⁇ dme, cross-linked with divinylbenzene) .
- the catalyst carboxylic acid derivative according to the invention can be immobilised on the solid support by adding it in aqueous solution to a suspension of the solid support, which may or may not be adapted in a foregoing preparatory step.
- the immobilisation can be performed in a single step by mixing the resin with the catalyst in aqueous medium, followed by washing with water - or alternatively in two steps by first converting the resin to its hydroxyl form with a hydroxide such as aqueous sodium hydroxide, and then adding the catalyst.
- the alkylene oxides used as starting material in the process of the invention have their conventional definition, i.e. they are compounds having a vicinal oxide (epoxy) group in their molecules.
- R ⁇ ' R3 and/or R 4 preferably has from 1 to 3 carbon atoms.
- substituents inactive moieties, such as hydroxy groups may be present.
- R ⁇ ' R-2 and R 3 represent hydrogen atoms and R ⁇ represents a non-substituted C]_-C3 ⁇ alkyl group and, more preferably, R 1 , R-2 ,
- R3 and R ⁇ all represent hydrogen atoms.
- suitable alkylene oxides therefore include ethylene oxide, propylene oxide, 1, 2-epoxybutane, 2 , 3-epoxybutane and glycidol. Ethylene oxide and propylene oxide are of particular commercial importance.
- the process of the invention may be carried out in batch operation. However, in particular for large scale embodiments it is preferred to operate the process continuously .
- Such continuous process can be carried out in a fixed bed reactor, operated in up-flow or down-flow. Down-flow operation is preferred.
- the reactor may be maintained under isothermal, adiabatic or hybrid conditions.
- Isothermal reactors are generally shell- and tube reactors, mostly of the multitubular type, wherein the tubes contain the catalyst and a coolant passes outside the tubes.
- Adiabatic reactors are not cooled, and the product stream leaving them may be cooled in a separate heat exchanger.
- the catalytic conversion of EO may be incomplete, in which situation rest EO can be thermally hydrolysed in the dead space of the reactor below the catalyst bed. Since this thermal hydrolysis is less specific towards MEG, it is recommended to minimise the liquid hold-up m the reactor. This can be achieved by filling the reactor outlet part with internals or inert packing material to reduce its volume, and/or by adding an inert gas, such as nitrogen, to the reactor feed mixture and operating the reactor under so-called trickle flow conditions. In order to obtain adequate time-yield values, it is recommended to perform the process under elevated temperature and pressure conditions.
- Suitable reaction temperatures are generally in the range from 80 to 200 °C, whereby temperatures in the range from 90 to 150 °C are preferred.
- the reaction pressure is usually selected in the range of 200 to 3000, preferably 200 to 2000 kPa .
- the selected reaction pressure is advantageously obtained by pressurising with an inert gas, such as nitrogen. If desired, mixtures of gases may be used, for example a mixture of carbon dioxide and nitrogen is in certain instances advantageous.
- the reactor volume can advantageously be greater than the volume occupied by of the catalyst therein, for example 10 to 70 vol% greater.
- the process of the present invention is not limited to its operation in the presence of the defined catalyst alone.
- at least part, such as about 30-60 wt%, of the alkylene oxide feed stream it has been found to be advantageous to subject at least part, such as about 30-60 wt%, of the alkylene oxide feed stream to partial thermal hydrolysis in the absence of catalyst, before completing the hydrolysis catalytically .
- partial hydrolysis even in the absence of a catalyst, is still sufficiently selective towards the monoalkylene glycol while on the other hand this measure is effective in saving the catalyst.
- a problem which may occasionally arise in any process wherein ethylene oxide is being hydrolysed is the presence of small amounts of amines and/or phosphines as impurities in the product stream.
- the basic groups thereof are quaternary ammonium or quaternary phosphonium groups . It has been found that during operation, small amounts of amines or phosphines tend to leach from the resin into the product stream. Besides, amines in the product stream may also originate from corrosion inhibitors which may be added to the water used in the process. Although the amounts of such amine or phosphine contaminants reaching the end- product are generally very small, they may affect the quality of the end-product such that it may be desirable to keep them below the detection level.
- trimethylamine (TMA) and/or dimethylamine (DMA) may reach the end-product in an amount of up to 10 ppm while the fishy odour of TMA may be detected in an amount as low as 1 ppb .
- Using a mixture of the strongly acidic ion exchange resin in its H + form and salt form has the advantage of the pH of the product stream remaining close to neutral.
- An added advantage of the strongly acidic guard bed is that any remaining alkylene oxide which may be still present in the product stream is hydrolysed to alkylene glycol, albeit with a lesser selectivity towards the monoalkylene glycol.
- Oxalic acid HOOC-COOH and its mono- and disodium salt Malonic acid HOOC-CH2-COOH and its monosodium salt - Succinic acid HOOC-CH2-CH2-COOH and its mono- and disodium salt
- Adipic acid (HOOC- (CH2 ) 4-COOH) and its monosodium salt
- the gascap was purged 3 times with nitrogen and an initial pressure of 1000 kPa was employed.
- the mixture was heated to 100 °C.
- Ethylene oxide 44 g; 1 mol
- the reaction mixture was maintained under continuous stirring for 6 hours at 100 °C.
- An end of run sample was taken for GLC analysis.
- the resin was treated as follows to immobilise the carboxylic acid derivative:
- a 250 ml autoclave was filled with the catalyst (30 mmol) and water (100 g; 5.55 mol). The gascap was purged 3 times with nitrogen and an initial pressure of 1000 kPa was employed. The mixture was heated to 100 °C. Ethylene oxide (44 g; 1 mol) was slowly added under stirring (500 rpm) . The reaction mixture was maintained under continuous stirring for 6 hours at 100 °C. An end of run sample was taken for GLC analysis.
- the thermal stability of an AMBERJET 4200/carboxylate catalysts was evaluated and compared with the thermal stability of AMBERJET 4200/bicarbonate .
- the thermal stability was tested by placing 20 ml of the catalyst in a 65 cm long, 0.5 inch wide Hoke tube, provided with a heating jacket using a hot oil system. Water was pumped with an HPLC pump with an LHSV of 1 1/1. h over the catalyst bed at 150 °C and a pressure of 1000 kPa during 48 hours. Then the catalyst sample was removed from the reactor.
- the strongly basic capacity (quaternary ammonium groups), the weakly basic capacity (tertiary amine groups) and the total anion capacity (the sum of the two previous capacities) in the fresh and used catalyst were determined by titration and the % difference (change during use) noted.
- AMBERJET 4200/citrate mono-anion catalyst was used in this test, wherein process parameters were varied (water :EO molar ratio between 5.0 and 18.9; LHSV between 0.81-0.95 and maximum bed temperature between 95-112 °C) . Samples were taken periodically.
- AMBERJET 4200/citrate mono-anion catalyst was used in a continuous fixed-bed experiment. The long-time performance was compared with that of AMBERJET 4200/bicarbonate under exactly identical process conditions .
- the 24 cm long reactor consisted of a 20 mm (inner diameter) wide glass tube in a 34 mm wide stainless steel metal pipe. Between the glass reactor tube and the SS outer tube a Teflon (PTFE) layer was used as an insulator.
- PTFE Teflon
- An electrical heating system was used at the outer SS tube to compensate for heat losses; the temperature set point for this heating device was set at the temperature of the water/EO reactor feed.
- the water feed was preheated to achieve the desired reactor inlet temperature prior to mixing with EO.
- the temperature of the feed was measured using a thermocouple placed on top of the reactor and the outlet temperature was measured using a thermocouple just below the catalyst bed in the reactor outlet.
Abstract
Description
Claims
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CA002354777A CA2354777A1 (en) | 1998-12-14 | 1999-12-13 | Carboxylates in catalytic hydrolysis of alkylene oxides |
BR9916242-3A BR9916242A (en) | 1998-12-14 | 1999-12-13 | Process for the preparation of alkylene glycols, and, catalyst composition |
EP99965483A EP1140750A1 (en) | 1998-12-14 | 1999-12-13 | Carboxylates in catalytic hydrolysis of alkylene oxides |
KR1020017007325A KR20010082339A (en) | 1998-12-14 | 1999-12-13 | Carboxylates in catalytic hydrolysis of alkylene oxides |
JP2000588106A JP2002532448A (en) | 1998-12-14 | 1999-12-13 | Carboxylates in the catalytic hydrolysis of alkylene oxides |
AU20981/00A AU759133B2 (en) | 1998-12-14 | 1999-12-13 | Carboxylates in catalytic hydrolysis of alkylene oxides |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP98204234.3 | 1998-12-14 | ||
EP98204234 | 1998-12-14 | ||
EP99201348 | 1999-04-29 | ||
EP99201348.2 | 1999-04-29 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2000035842A1 true WO2000035842A1 (en) | 2000-06-22 |
Family
ID=26150968
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP1999/010049 WO2000035842A1 (en) | 1998-12-14 | 1999-12-13 | Carboxylates in catalytic hydrolysis of alkylene oxides |
Country Status (9)
Country | Link |
---|---|
EP (1) | EP1140750A1 (en) |
JP (1) | JP2002532448A (en) |
KR (1) | KR20010082339A (en) |
CN (1) | CN1146532C (en) |
AU (1) | AU759133B2 (en) |
BR (1) | BR9916242A (en) |
CA (1) | CA2354777A1 (en) |
PE (1) | PE20001571A1 (en) |
WO (1) | WO2000035842A1 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6448456B1 (en) | 2001-05-31 | 2002-09-10 | The Dow Chemical Company | Process for the preparation of alkylene glycols |
EP1451132A1 (en) * | 2001-11-08 | 2004-09-01 | The University Of Waikato | Chemical synthesis |
US7435858B2 (en) | 2004-12-23 | 2008-10-14 | Shell Oil Company | Process for the preparation of alkylene glycols |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6562890B2 (en) * | 2001-03-29 | 2003-05-13 | Milliken & Company | Disodium hexahydrophthalate salt compositions and nucleated polymers comprising such compositions |
US7663005B2 (en) * | 2007-05-30 | 2010-02-16 | Sd Lizenzverwertungsgesellschaft Mbh & Co. Kg | Process for preparing an alkylene glycol |
US8053609B2 (en) * | 2007-10-15 | 2011-11-08 | Sd Lizenzverwertungsgesellschaft Mbh & Co. Kg | Solid catalyst useful for converting an alkylene oxide to an alkylene glycol |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3933923A (en) * | 1972-11-20 | 1976-01-20 | Henkel & Cie Gmbh | Process for the manufacture of vicinal glycols |
EP0226799A2 (en) * | 1985-11-18 | 1987-07-01 | MITSUI TOATSU CHEMICALS, Inc. | Method for preparing ethylene glycol and/or propylene glycol |
-
1999
- 1999-12-10 PE PE1999001220A patent/PE20001571A1/en not_active Application Discontinuation
- 1999-12-13 CA CA002354777A patent/CA2354777A1/en not_active Abandoned
- 1999-12-13 KR KR1020017007325A patent/KR20010082339A/en not_active Application Discontinuation
- 1999-12-13 AU AU20981/00A patent/AU759133B2/en not_active Ceased
- 1999-12-13 JP JP2000588106A patent/JP2002532448A/en not_active Withdrawn
- 1999-12-13 EP EP99965483A patent/EP1140750A1/en not_active Withdrawn
- 1999-12-13 CN CNB998156361A patent/CN1146532C/en not_active Expired - Fee Related
- 1999-12-13 WO PCT/EP1999/010049 patent/WO2000035842A1/en not_active Application Discontinuation
- 1999-12-13 BR BR9916242-3A patent/BR9916242A/en not_active IP Right Cessation
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3933923A (en) * | 1972-11-20 | 1976-01-20 | Henkel & Cie Gmbh | Process for the manufacture of vicinal glycols |
EP0226799A2 (en) * | 1985-11-18 | 1987-07-01 | MITSUI TOATSU CHEMICALS, Inc. | Method for preparing ethylene glycol and/or propylene glycol |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6448456B1 (en) | 2001-05-31 | 2002-09-10 | The Dow Chemical Company | Process for the preparation of alkylene glycols |
US6479715B1 (en) | 2001-05-31 | 2002-11-12 | Dow Global Technologies Inc. | Process for the preparation of alkylene glycols |
WO2002098828A1 (en) * | 2001-05-31 | 2002-12-12 | Dow Global Technologies Inc. | Process for the preparation of alkylene glycols |
EP1451132A1 (en) * | 2001-11-08 | 2004-09-01 | The University Of Waikato | Chemical synthesis |
EP1451132A4 (en) * | 2001-11-08 | 2006-02-08 | Univ Waikato | Chemical synthesis |
US7435858B2 (en) | 2004-12-23 | 2008-10-14 | Shell Oil Company | Process for the preparation of alkylene glycols |
Also Published As
Publication number | Publication date |
---|---|
CN1146532C (en) | 2004-04-21 |
CA2354777A1 (en) | 2000-06-22 |
PE20001571A1 (en) | 2001-01-26 |
CN1333738A (en) | 2002-01-30 |
AU2098100A (en) | 2000-07-03 |
JP2002532448A (en) | 2002-10-02 |
AU759133B2 (en) | 2003-04-03 |
BR9916242A (en) | 2001-10-02 |
KR20010082339A (en) | 2001-08-29 |
EP1140750A1 (en) | 2001-10-10 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US6153801A (en) | Carboxylates in catalytic hydrolysis of alkylene oxides | |
US6124508A (en) | Quaternary phosphonium salt catalysts in catalytic hydrolysis of alkylene oxides | |
JP5306200B2 (en) | Method for producing alkylene carbonate | |
US7462748B2 (en) | Process for the preparation of alkylene glycol | |
NZ278896A (en) | Process for preparation of alkylene glycols by reacting alkylene oxide and water in the presence of a catalyst | |
EP1140748B1 (en) | Quaternary phosphonium salt catalysts in catalytic hydrolysis of alkylene oxides | |
US20080097129A1 (en) | Process for the preparation of alkylene glycol | |
AU759133B2 (en) | Carboxylates in catalytic hydrolysis of alkylene oxides | |
EP1828086B1 (en) | Process for the preparation of alkylene glycols wherein a guard bed is used before the catalyst bed | |
EP1140749B1 (en) | Catalyst stabilising additive in the hydrolysis of alkylene oxides | |
US6156942A (en) | Catalyst stabilizing additive in the hydrolysis of alkylene oxides | |
JP2010533682A (en) | Process for preparing alkylene glycols | |
MXPA01006063A (en) | Carboxylates in catalytic hydrolysis of alkylene oxides | |
MXPA01006058A (en) | Catalyst stabilising additive in the hydrolysis of alkylene oxides | |
MXPA01006059A (en) | Quaternary phosphonium salt catalysts in catalytic hydrolysis of alkylene oxides |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 99815636.1 Country of ref document: CN |
|
AK | Designated states |
Kind code of ref document: A1 Designated state(s): AE AL AM AT AU AZ BA BB BG BR BY CA CH CN CR CU CZ DE DK DM EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT TZ UA UG UZ VN YU ZA ZW |
|
AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): GH GM KE LS MW SD SL SZ TZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN GW ML MR NE SN TD TG |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
DFPE | Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101) | ||
WWE | Wipo information: entry into national phase |
Ref document number: 1999965483 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 20981/00 Country of ref document: AU Ref document number: IN/PCT/2001/00491/DE Country of ref document: IN |
|
ENP | Entry into the national phase |
Ref document number: 2354777 Country of ref document: CA Ref document number: 2354777 Country of ref document: CA Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 1020017007325 Country of ref document: KR |
|
ENP | Entry into the national phase |
Ref document number: 2000 588106 Country of ref document: JP Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: PA/a/2001/006063 Country of ref document: MX |
|
WWP | Wipo information: published in national office |
Ref document number: 1020017007325 Country of ref document: KR |
|
WWP | Wipo information: published in national office |
Ref document number: 1999965483 Country of ref document: EP |
|
REG | Reference to national code |
Ref country code: DE Ref legal event code: 8642 |
|
WWG | Wipo information: grant in national office |
Ref document number: 20981/00 Country of ref document: AU |
|
WWW | Wipo information: withdrawn in national office |
Ref document number: 1999965483 Country of ref document: EP |
|
WWW | Wipo information: withdrawn in national office |
Ref document number: 1020017007325 Country of ref document: KR |