GB2362157A - Preparation of Propane-1,3-Diol - Google Patents
Preparation of Propane-1,3-Diol Download PDFInfo
- Publication number
- GB2362157A GB2362157A GB0006722A GB0006722A GB2362157A GB 2362157 A GB2362157 A GB 2362157A GB 0006722 A GB0006722 A GB 0006722A GB 0006722 A GB0006722 A GB 0006722A GB 2362157 A GB2362157 A GB 2362157A
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- United Kingdom
- Prior art keywords
- hydrogenation
- catalyst
- process according
- propane
- diol
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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
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
- C07C29/149—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof with hydrogen or hydrogen-containing gases
-
- 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
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
- C07C29/141—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group with hydrogen or hydrogen-containing gases
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
A process for the production of propane-1,3-diol comprises subjecting a vaporous feed mixture comprising a hydrogen-containing gas and a feedstock selected from 3-hydroxypropanal, b -propiolactone, oligomers of b -propiolactone, esters of 3-hydroxypropanoic acid, and mixtures of two or more thereof to hydrogenation conditions in a hydrogenation zone in the presence of a heterogeneous hydrogenation catalyst, and recovering a reaction product comprising propane-1,3-diol. A preferred catalyst is a reduced manganese-promoted copper catalyst.
Description
2362157 PROCESS This invention relates to the production of
propane-1,3diol.
Propane-1,3-diol is used as an intermediate in the production of polyesters for production of fibres or films. It can be prepared by a two-step process in which ethylene oxide is subjected to an oxonation reaction followed by hydrogenation:
0 + H2 + CO HOCH2CH2CHO CH2-CH2 HOCH2CH2CHO + H2 HOCH2CH2CH20H United States Patent Specification No. 5,981,808 describes the use of a non-phosphine-ligated cobalt compound as oxonation catalyst in an essentially non-water-miscible solvent followed by water extraction to separate the catalyst from the 3-hydroxypropanal produced as oxonation product. The aqueous mixture containing the 3-hydroxypropanal is then subjected to hydrogenation. United States Patent Specification No. 5,585,528 proposes addition of a lipophilic tertiary amine as a promoter in such a process. Use of methyl t-butyl ether for extraction of the aqueous mixture to recover cobalt catalyst for re-use is described in United States Patent Specification No. 5,770,776. United States Patent Specification No. 5,786, 524 teaches a similar process and proposes the use of a rhodium catalyst as an alternative catalyst in the oxonation step.
It is, however, a drawback of such a process that high levels of byproducts are produced during liquid phase hydrogenation of the intermediate 3-hydroxypropanal under the recommended hydrogenation conditions, namely liquid phase hydrogenation at 22CC and 100 bar (1000 kPa).Under such 2 conditions the conversion of 3-hydroxypropanal is only about 90% while up to 10% is converted to byproducts.
It has also been proposed to combine the oxonation and hydrogenation steps into a one-step process with, it is claimed, minimal production of 3-hydroxypropanal as byproduct. Such a one- step process can be effected using a phosphine complex of cobalt carbonyl as the major catalyst ingredient. However, the use of a ruthenium compound as catalyst has also been proposed. An organic solvent is used in the reaction enabling a water extraction to be used in order to separate propane-1,3-diol from the oxonation mixture. Ethylene oxide conversions of 55% with a selectivity towards propane-1,3-diol of 87% are reported.
United States Patents Nos. 5,310,948 and 5,359,081 teach formation of -propiolactone or polymers thereof by reaction of carbon monoxide and ethylene oxide in the presence of a cobalt-containing catalyst system comprising a source of cobalt and a hydroxyl-substituted pyridine.
Propane-1,3-diol can alternatively be produced from glycerol using recombinant bacteria expressing recombinant diol dehydratase. Such a process is taught in United States Patent Specification No. 5,821,092.
It has also been proposed to subject acrolein to hydration so as to form 3-hydroxypropanal which is then hydrogenated. In this connection reference may be made to United States Patent Specification No. 5,364,987.
In United States Patent Specification No. 5,334,778 it is proposed to produce propan-1,3-diol having a residual carbonyl content below 500 ppm by catalytically hydrogenating
3-hydroxypropanal in aqueous solution in the presence of a hydrogenation catalyst at 30'C to 80'C to a 3-hydroxypropanal conversion of 50% to 95% and then continuing the hydrogenation at 120'C to 140'C to achieve a 3hydroxypropanal 3 conversion of substantially 100%.
Both glycerol and acrolein are, however, generally more expensive and less available than ethylene oxide. Hence it is not currently an economic proposition to manufacture propane-1,3-diol by either of these last two mentioned processes.
It would be desirable to provide an improved process for the production of propane-1,3-diol. It would further be desirable to provide a process for producing propane-1,3-diol by hydrogenation of an appropriate carbonyl compound which exhibits increased selectivity towards propane-1,3-diol and reduced amounts of undesirable byproducts, such as propan-lol, which cannot readily be converted to propane-1,3-diol. It would further be desirable to provide a process for the production of propane-1,3-diol by hydrogenation of an intermediate compound which can be made from ethylene oxide and which contains at least one carbon-oxygen double bond, such as 3-hydroxypropanal, P- propiolactone, oligomers of Ppropiolactone, or an ester of 3- hydroxypropionic acid, with minimal formation of undesirable byproducts.
It is accordingly an objective of the present invention to provide an improved process for the production of propane1,3-diol. In addition the present invention seeks to provide a hydrogenation process for producing propane-1,3-diol that uses in a hydrogenation step an optimised catalyst system. Yet a further objective of the present invention is to provide a process for the production of propane-1,3-diol by hydrogenation of an intermediate compound which can be made from ethylene oxide, such intermediate compound containing at least one carbon-oxygen double bond, and preferably being selected from 3- hydroxypropanal, P-propiolactone, oligomers of P-propiolactone, esters of 3-hydroxypropionic acid, and mixtures of two or more thereof, with reduced amounts being 4 formed of undesirable byproducts, such as propan-1-ol, which cannot readily be converted to the desired propane-1,3-diol.
According to the present invention there is provided process for the production of propane-1,3-diol which comprises forming a vaporous feed mixture comprising a hydrogen- containing gas and a substantially anhydrous feedstock selected from 3- hydroxypropanal, -propiolactone, oligomers of -propiolactone, esters of 3- hydroxypropanoic acid, and mixtures of two or more thereof, supplying the vaporous feed mixture to a hydrogenation zone containing a heterogeneous hydrogenation catalyst and maintained under hydrogenation conditions effective for hydrogenating feedstock to propane-1,3-diol, and recovering from the hydrogenation zone a reaction product comprising propane-1,3- diol.
The feedstock to the hydrogenation step is substantially anhydrous, that is to say it contains no more than about 5% (w/v), preferably no more than about 1% (w/v), and even more preferably less than about 0.1% (w/v) of water. It is selected f rom 3-hydroxypropanal, -propiolactone, oligomers of - propiolactone, and esters of 3-hydroxypropanoic acid, and mixtures of two or more thereof. P-propiolactone can self-polymerise to form oligomers of P-propiolactone. The presence of more than a minor amount of such oligomers in the feedstock to the hydrogenation zone is generally undesirable because of their relative lack of volatility. Hence it will normally be preferred to use a feedstock to the hydrogenation zone which contains less than about 10 molar % of oligomers of P-propiolactone. Accordingly it will usually be preferred to minimise the proportion of oligomers of P-propiolactone in the feedstock to the hydrogenation zone.
Hydrogenation is effected using a vaporous feed mixture to the hydrogenation zone, this mixture containing in addition to the feedstock also a hydrogen-containing gas. The hydrogen- containing gas is preferably substantially free from carbon oxides but may contain one or more inert gases, such as nitrogen, argon and helium, in amounts of up to 50% v/v, but which preferably do not exceed about 10% v/v and more preferably do not exceed about 5% v/v, e.g. about 1% v/v or less.
The hydrogenation conditions may be selected so that the reaction mixture exiting the hydrogenation zone is also in the vapour phase. However, it is alternatively possible, and indeed may be preferable, to utilise hydrogenation conditions such that the reaction mixture at the exit end of the hydrogenation zone is below its dew point so that at least some of the condensable components thereof are present in the liquid phase.
The hydrogenation zone conveniently contains a fixed bed of a granular hydrogenation catalyst. If desired, the hydrogenation zone can contain more than one catalyst bed and the hydrogenation catalyst of one bed can, if desired, differ from the hydrogenation catalyst of at least one other bed.
The hydrogenation catalyst is preferably selected from noble metal catalysts, such as palladium catalysts, and copper-containing catalysts. More preferably the hydrogenation catalyst is a copper-containing catalyst. The active catalytic species in the hydrogenation catalyst may be at least partially supported on a supporting material selected from chromia, zinc oxide, alumina, silica, silicaalumina, silicon carbide, zirconia, titania, carbon, or a mixture of two or more thereof, for example, a mixture of chromia and carbon.
As examples of suitable copper-containing catalysts which may be utilised in the process of the invention there may be mentioned reduced copper oxide/zinc oxide 6 hydrogenation catalysts, reduced manganese-promoted copper catalysts, reduced copper chromite catalysts, and reduced promoted copper chromite catalysts.
Preferably the hydrogenation catalyst is a reduced manganese-promoted copper catalyst. Such manganese-promoted copper catalysts preferably have a total surface area of at least about 15 ml/g, more preferably at least about 20 m2/g, and even more preferably at least about 25 m2/g, in the unreduced form.
A particularly preferred hydrogenation catalyst is a reduced manganese-promoted copper catalyst which is available as DRD92/89A catalyst from Kvaerner Process Technology Limited of The Technology Centre, Princeton Drive, Thornaby, Stockton-on-Tees, TS17 6PY, England. Alternatively there may be used a reduced manganese-promoted copper catalyst which is available as DRD92/89B catalyst from Kvaerner Process Technology Limited.
The hydrogenation step is conducted under vapour phase feed conditions so that the feed stream to the hydrogenation zone is above its dew point and is thus a vaporous feed stream. The reaction product mixture from the hydrogenation zone can also be recovered at a temperature above its dew point so that it too is in vaporous form or it can be recovered at a temperature below its dew point so that at least part of the condensable components thereof are in liquid form.
Although it is possible to conduct the hydrogenation process of the present invention in a tubular reactor under substantially isothermal conditions, it will normally be preferred to operate under substantially adiabatic hydrogenation conditions using a fixed catalyst bed or beds since adiabatic reactors are much cheaper to construct than tubular reactors. However, care should be taken in designing 7 the plant, in particular in selecting a suitable gas:feedstock ratio and in choosing a catalyst size, that the temperature rise across any catalyst bed is limited to a reasonable value, typically not more than about 200C, so as to keep the temperature to which the reaction mixture is exposed within desired limits. In this way the formation of 1-propanol as a byproduct can be limited.
It will normally be preferred that, in the vaporous feed stream to the hydrogenation zone, the hydrogen-containing gas:feedstock molar ratio shall be in the range of from about 50:1 to about 1000:1.
Typically the feed temperature to the hydrogenation zone is from about 130'C to about 18CC, more preferably from about 135'C to about 15CC, while the feed pressure to the hydrogenation zone is from about 50 psia (about 344.74 kPa) to about 2000 psia (about 13789.52 kPa), for example, from about 350 psia (about 2413.17 kPa) to about 1000 psia (about 6894.76 kPa). The feedstock is also preferably supplied to the first hydrogenation zone at a rate corresponding to a liquid hourly space velocity of from about 0.05 to about 5.0 h'. Preferably unreacted hydrogen-containing gas is recycled for further use.
If desired, the feedstock to the hydrogenation zone can be diluted with a solvent, such as methanol, which is stable under the hydrogenation conditions utilised.
The invention is further illustrated in the following Examples.
Example 1
This Example was intended to provide a simulation of conditions similar to those that might exist in a commercial hydrogenation reactor for hydrogenation of methyl 3 hydroxypropionate utilising recycled hydrogen which would be saturated with methanol co-product.
8 A solution of crude methyl 3-hydroxypropionate (approximately 90% pure) was diluted with an approximately equal weight of methanol to form a feed solution. This feed solution was subjected to vapour phase hydrogenation in a once-through adiabatic fixed-bed reactor. The reactor was constructed from a 95 cm length of 20.96 mm internal diameter tube which was oil-jacketed to reduce heat losses. The reactor contained a charge of 100 ml of DRD92/89A catalyst which is obtainable from Kvaerner Process Technology Limited of The Technology Centre, Princeton Drive, Thornaby, Stockton-on-Tees, TS17 6PY, England. The catalyst was reduced by a procedure analogous to that described in United States Patent Specification No. 5,030,609.
The feed solution was supplied at a feed rate of 12 ml/h to a heater and vaporised by a stream of pure hydrogen at a rate of 1000 N1/h (i.e. 1000 litres per hour measured at 760 mm Hg [101.33 kPa] and OOC). The vaporous mixture was passed over the catalyst at a pressure of 400 psig (2757.90 kPa gauge) and a temperature of 1380C. The reaction product mixture exiting the reactor was cooled and the condensed liquid collected. The feed and product were analysed by gas chromatography using a 60 metre CP SIL 19 capillary column of 0.32 mm internal diameter with a 1.3 pm film thickness.
Conversion of the methyl 3-hydroxypropionate was determined as 73.3% with a selectivity to propane-1,3-diol of 83.4% and to 1-propanol of 5.8%. It is believed that the byproducts comprise mainly materials which, upon hydrogenation, can be converted to propane-1,3-diol and hence can be recycled.
Examnle 2 The general procedure of Example 1 was repeated except that the temperature was 1480C. Conversion of the methyl 3-hydroxypropionate was determined as 84.9% with a 9 selectivity to propane-1,3-diol of 84.8% and to 1-propanol of 7.2%. Operation at this slightly higher temperature provides an expected increase in conversion with a minor increase in selectivity to 1-propanol.
Exam-ple 3 The general procedure of Example 1 was repeated except that the temperature was 17CC. Conversion of the methyl 3-hydroxypropionate was determined as 99.95% with a selectivity to propane-1,3-diol of 13.1% and to 1-propanol of 81.8%. This shows that operation at high temperature favours formation of the alcohol, 1-propanol, rather than propan-1,3 diol.
Exami)1e 4 The same feed solution as used in Example 1 was subjected to vapour phase hydrogenation in an adiabatic fixed-bed reactor system which incorporated recycle of excess gas following condensation of the reactor product stream.
Make-up pure hydrogen was supplied to the system to maintain constant system pressure. The reactor was constructed from a 200 cm length of 26.64 mm internal diameter tube which was insulated and provided with electric trace heating means to prevent net heat loss from the reactor. The reactor contained a charge of 250 ml of DRD92/89A catalyst. The catalyst was reduced following reduced by a procedure analogous to that described in United States Patent Specification No. 5,030,609.
The feed solution was fed at a rate of 80 ml/h to a heater and vaporised by a stream of mixed recycle gas and pure hydrogen at a rate of 10900 N1/h. The vaporous mixture was passed over the catalyst at a pressure of 885 psig (6101.86 kPa gauge) and an inlet temperature of 1490C. The outlet temperature was measured as 15CC. The reactor product mixture was cooled and the condensed liquid collected. The feed and product were analysed by gas chromatography using a 60 metre CP SIL 19 capillary column of 0.32 mm internal diameter with a 1.3 pm film thickness.
Conversion of the methyl 3-hydroxypropionate was determined as 77.8% with a selectivity to propane-1,3-diol of 78.9% and to 1-propanol of 14.8%.
ExaMple 5
The general procedure of Example 4 was repeated except that the inlet pressure was 735 psig (5067.65 kPa), and the mixed recycle and pure hydrogen make-up flow rate was 8116 N1/h. Conversion of the methyl 3-hydroxypropionate was determined as 61. 1% with a selectivity to propane-1, 3-diol of 79.0% and to 1-propanol of 14. 4%. Operation at this lower pressure and lower gas rate provides an expected reduced conversion but with similar selectivities to propane-1,3-diol and to 1- propanol.
1
Claims (1)
11 CLAIMS: 1. A process for the production of propane-1,3-diol which
comprises forming a vaporous feed mixture comprising a hydrogencontaining gas and a substantially anhydrous feedstock selected from 3-hydroxypropanal, P-propiolactone, oligomers of P-propiolactone, esters of 3-hydroxypropanoic acid, and mixtures of two or more thereof, supplying the vaporous feed mixture to a hydrogenation zone containing a heterogeneous hydrogenation catalyst and maintained under hydrogenation conditions effective for hydrogenating feedstock to propane- 1, 3-diol, and recovering from the hydrogenation zone a reaction product comprising propane-1,3diol. 2. A process according to claim 1, wherein the feedstock comprises an alkyl ester or a hydroxyalkyl ester of 3hydroxypropanoic acid. 3. A process according to claim 1 or claim 2, wherein hydrogenation is effected using a fixed bed of a granular hydrogenation catalyst.
4. A process according to any one of claims 1 to 3, wherein the hydrogenation catalyst is selected from noble metal catalysts and coppercontaining catalysts. S. A process according to claim 4, wherein the hydrogenation catalyst is a copper-containing catalyst.
6. A process according to claim 5, wherein the coppercontaining catalyst is selected from reduced copper oxide/zinc oxide hydrogenation catalysts, reduced manganesepromoted copper catalysts, reduced copper chromite catalysts, and reduced promoted copper chromite catalysts.
7. A process according to claim 5 or claim 6, wherein the coppercontaining catalyst is a reduced manganese-promoted copper catalyst. 8. A process according to any one of claims 1 to 7, wherein 1 12 the hydrogen-containing gas:feedstock molar ratio in the vaporous feed mixture is in the range of from about 50:1 to about 1000:1.
9. A process according to any one of claims 1 to 8, wherein the feed temperature to the hydrogenation zone is from about 130'C to about 180'C.
10. A process according to claim 9, wherein the feed temperature to the hydrogenation zone is from about 135'C to about 150'C.
11. A process according to any one of claims 1 to 10, wherein the feed pressure to the hydrogenation zone is from about 50 psia (about 344.74 kPa) to about 2000 psia (about 13789.S2 kPa).
12. A process according to claim 11, wherein the feed pressure to the hydrogenation zone is from about 350 psia (about 2413.17 kPa) to about 1000 psia (about 6894.76 kPa).
13. A process according to any one of claims 1 to 12, wherein the feedstock is supplied to the first hydrogenation zone at a rate corresponding to a liquid hourly space velocityof from about 0.05 to about 5.0 h-1.
Priority Applications (13)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB0006722A GB2362157A (en) | 2000-03-20 | 2000-03-20 | Preparation of Propane-1,3-Diol |
| GBGB0020738.1A GB0020738D0 (en) | 2000-03-20 | 2000-08-22 | Process |
| TW090104200A TWI266760B (en) | 2000-03-20 | 2001-02-23 | Process for the preparation of propane-1,3-diol |
| US10/221,839 US6982357B2 (en) | 2000-03-20 | 2001-03-14 | Process for the preparation of propane-1,3-diol by vapor phase hydrogenation of 3-hydroxypropanal, beta-propiolactone, oligomers of beta-propiolactone, esters of 3-hydroxypropanoic acid or mixtures thereof |
| ES01911918T ES2263596T3 (en) | 2000-03-20 | 2001-03-14 | PROCEDURE FOR THE PREPARATION OF PROPANE-1,3-DIOL BY HYDROGENATION IN THE VAPOR PHASE OF BETAPROPIOLACTONE, OLIGOMEROS DE BETA-PROPIOLACTONA, ESTERES DELACIDO 3-HIDROXIPROPANOICO OR MIXTURES OF THE SAME. |
| DE60120939T DE60120939T2 (en) | 2000-03-20 | 2001-03-14 | PROCESS FOR PREPARING PROPANE-1,3-DIOL BY GAS PHASE-HYDROGENATION OF .BETA.-PROPIOLACTONE, OLIGOMERS OF .BETA.-PROPIOLACTONE, 3-HYDROXYPROPIONIC ACID ESTERS, OR MIXTURES THEREOF |
| JP2001568872A JP4657560B2 (en) | 2000-03-20 | 2001-03-14 | Method for preparing propane-1,3-diol by gas phase hydrogenation of 3-hydroxypropanal, β-propiolactone, oligomer of β-propiolactone, ester of 3-hydroxypropanoic acid, or a mixture thereof |
| MXPA02009174A MXPA02009174A (en) | 2000-03-20 | 2001-03-14 | Process for the preparation of propane 1,3 diol by vapor phase hydrogenation of 3 hydroxypropanal, beta propiolactone, oligomers of beta propiolactone, esters of 3 hydroxypropanoic acid or mixtures thereof. |
| AT01911918T ATE330922T1 (en) | 2000-03-20 | 2001-03-14 | METHOD FOR PRODUCING PROPANE-1,3-DIOL BY GAS PHASE HYDROGENATION OF .BETA.-PROPIOLACTONE, OLIGOMERS OF .BETA.-PROPIOLACTONE, 3-HYDROXYPROPIONIC ACID ESTERS OR MIXTURES THEREOF |
| PCT/GB2001/001128 WO2001070659A1 (en) | 2000-03-20 | 2001-03-14 | Process for the preparation of propane-1,3-diol by vapor phase hydrogenation of 3-hydroxypropanal, beta-propiolactone, oligomers of beta-propiolactone, esters of 3-hydroxypropanoic acid or mixtures thereof |
| AU40840/01A AU4084001A (en) | 2000-03-20 | 2001-03-14 | Process for the preparation of propane-1,3-diol by vapor phase hydrogenation of 3-hydroxypropanal, beta-propiolactone, oligomers of beta-propiolactone, esters of 3-hydroxypropanoic acid or mixtures thereof |
| EP01911918A EP1268376B1 (en) | 2000-03-20 | 2001-03-14 | Process for the preparation of propane-1,3-diol by vapor phase hydrogenation of .beta.-propiolactone, oligomers of .beta.-propiolactone, esters of 3-hydroxypropanoic acid or mixtures thereof |
| KR1020027011432A KR100580439B1 (en) | 2000-03-20 | 2001-03-14 | Process for the preparation of propane-1,3-diol by vapor phase hydrogenation of 3-hydroxypropanal, beta-propiolactone, oligomers of beta-propiolactone, esters of 3-hydroxypropanoic acid or mixtures thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB0006722A GB2362157A (en) | 2000-03-20 | 2000-03-20 | Preparation of Propane-1,3-Diol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB0006722D0 GB0006722D0 (en) | 2000-05-10 |
| GB2362157A true GB2362157A (en) | 2001-11-14 |
Family
ID=9888025
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB0006722A Withdrawn GB2362157A (en) | 2000-03-20 | 2000-03-20 | Preparation of Propane-1,3-Diol |
| GBGB0020738.1A Ceased GB0020738D0 (en) | 2000-03-20 | 2000-08-22 | Process |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GBGB0020738.1A Ceased GB0020738D0 (en) | 2000-03-20 | 2000-08-22 | Process |
Country Status (2)
| Country | Link |
|---|---|
| KR (1) | KR100580439B1 (en) |
| GB (2) | GB2362157A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004041421A2 (en) | 2002-11-01 | 2004-05-21 | Cargill, Incorporated | Process for preparation of 1,3-propanediol |
-
2000
- 2000-03-20 GB GB0006722A patent/GB2362157A/en not_active Withdrawn
- 2000-08-22 GB GBGB0020738.1A patent/GB0020738D0/en not_active Ceased
-
2001
- 2001-03-14 KR KR1020027011432A patent/KR100580439B1/en not_active IP Right Cessation
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004041421A2 (en) | 2002-11-01 | 2004-05-21 | Cargill, Incorporated | Process for preparation of 1,3-propanediol |
| WO2004041421A3 (en) * | 2002-11-01 | 2004-06-10 | Cargill Inc | Process for preparation of 1,3-propanediol |
| US7126034B2 (en) | 2002-11-01 | 2006-10-24 | Cargill, Incorporated | Process for preparation of 1,3-propanediol |
| CN100381411C (en) * | 2002-11-01 | 2008-04-16 | 嘉吉有限公司 | Process for preparation of 1,3-propanediol |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20020087062A (en) | 2002-11-21 |
| GB0006722D0 (en) | 2000-05-10 |
| KR100580439B1 (en) | 2006-05-15 |
| GB0020738D0 (en) | 2000-10-11 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| WAP | Application withdrawn, taken to be withdrawn or refused ** after publication under section 16(1) |