EP1379327A1 - Procede d'activation thermique rapide d'une reaction chimique dans une solution fluide surcritique - Google Patents
Procede d'activation thermique rapide d'une reaction chimique dans une solution fluide surcritiqueInfo
- Publication number
- EP1379327A1 EP1379327A1 EP02730025A EP02730025A EP1379327A1 EP 1379327 A1 EP1379327 A1 EP 1379327A1 EP 02730025 A EP02730025 A EP 02730025A EP 02730025 A EP02730025 A EP 02730025A EP 1379327 A1 EP1379327 A1 EP 1379327A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- fluid
- reaction
- temperature
- solution
- tetralin
- Prior art date
- Legal status (The legal status 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 status listed.)
- Withdrawn
Links
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 103
- 239000012530 fluid Substances 0.000 title claims abstract description 99
- 238000000034 method Methods 0.000 title claims abstract description 38
- 238000007725 thermal activation Methods 0.000 title abstract 2
- 239000000376 reactant Substances 0.000 claims abstract description 19
- 239000000203 mixture Substances 0.000 claims abstract description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 56
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 28
- 239000001569 carbon dioxide Substances 0.000 claims description 28
- 238000002156 mixing Methods 0.000 claims description 11
- 239000000852 hydrogen donor Substances 0.000 claims description 8
- 239000011541 reaction mixture Substances 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 229910001868 water Inorganic materials 0.000 claims description 5
- LUJVUUWNAPIQQI-UHFFFAOYSA-N (+)-androsta-1,4-diene-3,17-dione Natural products O=C1C=CC2(C)C3CCC(C)(C(CC4)=O)C4C3CCC2=C1 LUJVUUWNAPIQQI-UHFFFAOYSA-N 0.000 claims description 4
- LUJVUUWNAPIQQI-QAGGRKNESA-N androsta-1,4-diene-3,17-dione Chemical compound O=C1C=C[C@]2(C)[C@H]3CC[C@](C)(C(CC4)=O)[C@@H]4[C@@H]3CCC2=C1 LUJVUUWNAPIQQI-QAGGRKNESA-N 0.000 claims description 4
- 230000005284 excitation Effects 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 115
- 239000000243 solution Substances 0.000 description 32
- DNXHEGUUPJUMQT-CBZIJGRNSA-N Estrone Chemical compound OC1=CC=C2[C@H]3CC[C@](C)(C(CC4)=O)[C@@H]4[C@@H]3CCC2=C1 DNXHEGUUPJUMQT-CBZIJGRNSA-N 0.000 description 14
- 229960003399 estrone Drugs 0.000 description 14
- DNXHEGUUPJUMQT-UHFFFAOYSA-N (+)-estrone Natural products OC1=CC=C2C3CCC(C)(C(CC4)=O)C4C3CCC2=C1 DNXHEGUUPJUMQT-UHFFFAOYSA-N 0.000 description 13
- 239000012071 phase Substances 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 7
- 239000000126 substance Substances 0.000 description 6
- 238000000354 decomposition reaction Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 4
- 239000004071 soot Substances 0.000 description 4
- 238000013021 overheating Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000000197 pyrolysis Methods 0.000 description 3
- 239000012266 salt solution Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 125000005329 tetralinyl group Chemical group C1(CCCC2=CC=CC=C12)* 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000012442 inert solvent Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- WCYWZMWISLQXQU-UHFFFAOYSA-N methyl Chemical compound [CH3] WCYWZMWISLQXQU-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- FLTNWMFPQFIBDA-UHFFFAOYSA-N 1,2,3,4-tetrahydronaphthalene Chemical compound C1=CC=C2CCCCC2=C1.C1=CC=C2CCCCC2=C1 FLTNWMFPQFIBDA-UHFFFAOYSA-N 0.000 description 1
- 229920013685 Estron Polymers 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000003541 multi-stage reaction Methods 0.000 description 1
- 229910052756 noble gas Inorganic materials 0.000 description 1
- 150000002835 noble gases Chemical class 0.000 description 1
- 238000010587 phase diagram Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000003254 radicals Chemical group 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 150000003431 steroids Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07J—STEROIDS
- C07J1/00—Normal steroids containing carbon, hydrogen, halogen or oxygen, not substituted in position 17 beta by a carbon atom, e.g. estrane, androstane
- C07J1/0003—Androstane derivatives
- C07J1/0011—Androstane derivatives substituted in position 17 by a keto group
-
- 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
- B01J3/00—Processes of utilising sub-atmospheric or super-atmospheric pressure to effect chemical or physical change of matter; Apparatus therefor
- B01J3/008—Processes carried out under supercritical conditions
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07J—STEROIDS
- C07J1/00—Normal steroids containing carbon, hydrogen, halogen or oxygen, not substituted in position 17 beta by a carbon atom, e.g. estrane, androstane
- C07J1/0051—Estrane derivatives
- C07J1/0059—Estrane derivatives substituted in position 17 by a keto group
-
- 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
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Definitions
- the invention relates to a method for the rapid thermal excitation of a chemical reaction in a solution which is in a supercritically fluid state during the reaction, with the steps according to the preamble of claim 1.
- reaction partner is to be interpreted to such an extent that it also includes a substance which is only reacted with itself in the desired reaction or which is broken down or converted during the reaction.
- a supercritically fluid state is to be understood as a fluid, that is to say non-solid, state which occurs in pure substances above a critical temperature T c and above a critical pressure p c .
- T c critical temperature
- p c critical pressure
- the rapid thermal excitation which is faster than the half-life in a method according to the preamble of claim 1 of the desired reaction, the aim is to run one of several possible chemical reactions of all the reactants present, which is dominant in the region of the relatively high reaction temperature over the other possible reactions, with high selectivity, ie high relative yield of a desired reaction product allow.
- US Pat. No. 5,151,533 describes a process for the preparation of 1,3,5-estradiene (10) -3-ol-17-one (estrone) by pyrolysis of 1,4-androstadiene-3,17-dione (ADD). known in the presence of 1,2,3,4-tetrahydronaphthalene (tetralin) as a hydrogen donor.
- ADD 1,2,3,4-tetrahydronaphthalene
- superheated tetralin is mixed to a fluid temperature well above a desired reaction temperature of 450 ° C-700 ° C in a mixing zone with a solution of ADD in tetralin preheated only to a prereaction temperature of up to 300 ° C in order to make the ADD very quickly to be converted into a higher temperature range, in which it can be converted to estrone with high selectivity and good yield, while at lower reaction temperatures it predominantly undesirable ring-opening reactions which do not lead to ⁇ stron.
- the desired pyrolysis reaction is carried out at a pressure of 3.5-300 MPa and the reaction temperature of 450 ° C.-700 ° C., for which purpose a further heating of the reaction mixture is provided in a reactor.
- Another disadvantage of the known method is that the methyl radical which primarily forms during the thermal decomposition of the 1,4-androstadiene-3,17-dione in the compressed supercritically fluid tetraline solution only moves relatively slowly from the second product of this primary dissociation process, a steroid component with radical function in the area of the A-ring, which is to be regarded as an intermediate on the way to the formation of estrone. There is therefore a considerable cage reaction in which 4-methyltrone is produced as an undesirable impurity of the estrone.
- the invention has for its object to provide a method of the type described in the introduction, in which the disadvantages of the prior art are eliminated.
- the process should not lead to tar and soot formation.
- the basic feature of the new method is that the composition of the fluid is adjusted so that the fluid is chemically stable at the fluid temperature.
- This means that the fluid can be kept at the fluid temperature for a long period of time without loss of fluid and in particular without soot and tar formation.
- the fluid can also be overheated much more clearly with respect to the reaction temperature than was previously possible.
- the fluid temperature can be chosen so high that the reactant is heated to the reaction temperature solely by mixing with the fluid and no further heating of the mixture is required to reach the reaction temperature.
- the reaction temperature is reached quasi-instantaneously , the rate at which the temperature of the reaction partner rises is limited only by the mixing process with the fluid. From the beginning, the reactions which proceed with the highest selectivity at this reaction temperature are preferred to undesired side reactions, the selectivity of which is higher at lower temperatures.
- suitable fluids for use in the new process are carbon dioxide, water, ammonia and mixtures thereof.
- Carbon dioxide is stable even at very high temperatures, at least up to 1300 ° C, and in the supercritically fluid state it is a largely inert solvent for many organic substances. It also has no corrosive effects on common pressure reactor materials in the supercritically fluid state. Water and ammonia can dissociate at elevated temperatures, but are stable in their pure form. Depending on the desired reaction, they can not only be inert solvents but also reactants of the reaction in the supercritically fluid state.
- the variants in which the fluid is not a reaction partner of the reaction are particularly preferred in the new process.
- carbon dioxide is preferred as the economically available fluid, especially since carbon dioxide as a waste product from chemical processes is inexpensive and almost unlimitedly available. Due to the high diffusivity of the supercritically fluid carbon dioxide, decay products that primarily occur in a multi-stage reaction can quickly separate from one another, so that the probability of cage reactions is low.
- the fluid can be mixed with a reaction mixture which, in addition to the at least one reaction partner, contains at least one further reaction partner or a solvent.
- the reaction solution may also contain reaction aids.
- the reaction mixture with which the fluid is mixed is preferably a liquid reaction solution, on the one hand to ensure rapid complete mixing with the superheated fluid and on the other hand to maintain the reaction mixture at a high pressure corresponding to the superheated fluid at a relatively low prereaction temperature.
- the reaction mixture it is also possible for the reaction mixture to be a fluid reaction solution which, like the superheated fluid, which will always be in the supercritically fluid state, is in a supercritical fluid state even before it is mixed.
- reaction partner which can be brought to the higher temperature without undesired decomposition or other side reactions, should first be mixed with the fluid.
- the reactants comprise 1, 4-androstadiene-3, 17-dione (ADD) and a hydrogen donor.
- the hydrogen donor is again preferably 1, 2, 3, 4-tetrahydronaphthalene (tetralin).
- tetralin 4-tetrahydronaphthalene
- the tetralin is not used for the actual or sole formation of the supercritically fluid solution in which the reactants are located, but is instead in a mixed solution with the fluid.
- the carbon dioxide as a fluid eliminates all problems associated with the tetralin as a fluid so far.
- the particularly low viscosity of supercritically fluid carbon dioxide which is under the same pressure and temperature conditions and with a similarly reduced density by more than an order of magnitude less than that of tetralin, leads to very rapid diffusion of the primary methyl radical, so that undesired reaction products not significant from cage reactions.
- the low viscosity of supercritically fluid carbon dioxide is advantageous from a fluid dynamics point of view, since it allows short residence times of the supercritically fluid solution at the reaction temperature in a reactor and favors the formation of a turbulent flow.
- Such a turbulent flow has advantages not only in the case of mixing with reaction partners, but also in the subsequent continued mixing of the solution in which the desired reaction takes place.
- the fluid temperature higher than the reaction temperature by at least 200 K, in particular even by at least 500 K. Even the larger temperature difference of 500 K can be easily achieved for most reactions when using carbon dioxide as the fluid.
- the prereaction temperature is preferably around at least 200 K, in particular around at least 300 K, below the reaction temperature. A lower temperature difference between the pre-reaction and the reaction temperature is preferred than between the reaction and the fluid temperature, so that the reactants in the solution in which the desired reaction takes place do not have to be diluted too much by the fluid in order to separate them from the Raise pre-reaction temperature to the reaction temperature.
- the reaction temperature resulting from the pre-reaction temperature and the fluid temperature itself depends on the mass ratio of the fluid to the reaction partners and on the respective heat capacities, with any heat of solution and, at different pressures, also the temperature-pressure dependencies.
- the mass ratio of carbon dioxide to ADD / hydrogen donor solution in the new process for the production of estrone is expediently in the range from 1 to 10.
- the concentration of the ADD in the ADD / hydrogen donor solution when using tetralin as solvent and as hydrogen donor are values between 50 g ADD / kg solution and the saturation concentration of the ADD in tetralin (at room temperature).
- the preferred concentration range is between 100 g and 300 g ADD / kg solution in tetralin.
- the temperature range for the desired reaction temperature is in the range from 550 ° C to 650 ° C. In individual cases, it can also reach up to 750 ° C.
- the reaction temperature is to be determined primarily according to the criterion of obtaining a high yield of the desired reaction products. This results in the above concrete values for the manufacture of Estron. So that the supercritically fluid state of the solution for the reaction is established, however, it is very important to ensure that the reaction temperature is at least above the lower of the critical temperatures of the relevant fluid phase components, which is the critical temperature of the carbon dioxide of 31 ° C is. It is preferred if the reaction temperature is at least as high as the highest critical temperature of the relevant fluid phase components. This here is that of tetralin at 446 ° C. Both values are significantly exceeded by the preferred reaction temperatures for the production of estrone.
- the pressure to be set for the reaction in the supercritically fluid solution is at least above the lower of the critical pressures of the relevant fluid phase components, i.e. here of carbon dioxide and tetralin, so that the lower critical pressure is that of the tetralin of 3.5 MPa. It is preferred if the pressure to be set is at least as high as the highest critical pressure of the relevant fluid phase components. This is usually that of the fluid. This in turn is typically the critical pressure of the carbon dioxide of 7.4 MPa. A pressure range to be regarded as favorable is between 7.4 and 30 MPa. However, higher pressures up to 200 MPa can also be used.
- the fluid can also be partially mixed with the reactants and not overheated.
- the possibility of adding a reaction partner to the superheated fluid before further reaction partners has already been discussed above.
- Fig. 1 shows an apparatus for performing the method
- Fig. 2 is a plot of the estrone yield in percent over the reaction time for different reaction temperatures.
- the device shown in Fig. 1 for a continuous implementation of the new method has a branch shown here on the left, in which in a mixing container 1 with a Mixer 2 is a mixture of two reactants 3 and 4 is produced.
- the reactants 3 and 4 are ADD and tetralin, the ADD being dissolved in the tetralin.
- This solution is compressed in a compressor 5 to a pressure of 20 MPa, the pressure indication relating to a prereaction temperature of 200 ° C. which can be achieved in a downstream preheater 6.
- carbon dioxide from a pressure vessel 7 is further compressed in a compressor 8, a pressure of 20 MPa based on a temperature of 860 ° C.
- a solution which has a reaction temperature in the range of 550 ° C to 650 ° C due to the thermal energy of the superheated carbon dioxide and the like State is supercritically fluid, the supercritically fluid phase being formed essentially by the carbon dioxide but also partly by the tetralin.
- pyrolysis of the ADD to estrone takes place over a short period of 0.05 to 2 seconds in the presence of tetralin.
- the reaction is terminated by cooling in an unheated and non-insulated capillary leading out of the reactor 10 and by expansion of the supercritically fluid phase into an expansion chamber 11 and the temperature falling below 400.degree.
- the mass flow is regulated via a valve 12.
- the gas flow is used to separate liquid and solid components at normal pressure by means of an ⁇ . 0 ° C held container 16 out.
- the reaction described so far can be modified by adding carbon dioxide to the material stream coming from the left in accordance with an arrow 13, or to the tetralin coming in from the right according to arrow 14. In the latter case, however, care must be taken to ensure that the tetralin is only exposed to the high temperatures of the superheated carbon dioxide for a very short time. Otherwise the tetralin will decompose with the elimination of hydrogen.
- Fig. 2 shows that the yields in the conversion of ADD to estrone can be improved by increasing the reaction temperature and shortening the reaction time.
- the present invention provides the necessary basis for both measures.
- carbon dioxide as a heat carrier
- the entire heat supply for the reactants can be effected only by the C0 2 and thus in a very short time.
- a very high reaction temperature can also be achieved without one of the reactants being thermally stressed beforehand.
- Below a temperature of 300 ° C the tetralin is not converted to any significant extent either alone or in conjunction with the ADD within the usual short dwell times in the preheater or the downstream lines. .
- a thermally rapidly activated reaction in the sense of the present invention, reference can be made to the rapid conversion of an aqueous salt-containing solution into the supercritically fluid state. It is known that aqueous salt solutions develop extremely corrosive properties shortly before reaching the supercritical fluid phase, which make their handling very difficult. By rapidly reaching a supercritical fluid phase in the process of the invention using highly superheated water to heat the aqueous salt solution, the highly corrosive state of the salt solutions can be avoided and other desired thermal reactions can be excited in the aqueous solutions and with a short residence time be carried out in a reactor. LIST OF REFERENCE NUMBERS
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Steroid Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP02730025A EP1379327A1 (fr) | 2001-04-02 | 2002-03-19 | Procede d'activation thermique rapide d'une reaction chimique dans une solution fluide surcritique |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP01108275A EP1247566A1 (fr) | 2001-04-02 | 2001-04-02 | Procédé d'excitation thermique rapide d'une réaction chimique dans une solution fluide supercritique |
EP01108275 | 2001-04-02 | ||
EP02730025A EP1379327A1 (fr) | 2001-04-02 | 2002-03-19 | Procede d'activation thermique rapide d'une reaction chimique dans une solution fluide surcritique |
PCT/EP2002/002985 WO2002078831A1 (fr) | 2001-04-02 | 2002-03-19 | Procede d'activation thermique rapide d'une reaction chimique dans une solution fluide surcritique |
Publications (1)
Publication Number | Publication Date |
---|---|
EP1379327A1 true EP1379327A1 (fr) | 2004-01-14 |
Family
ID=8177019
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP01108275A Withdrawn EP1247566A1 (fr) | 2001-04-02 | 2001-04-02 | Procédé d'excitation thermique rapide d'une réaction chimique dans une solution fluide supercritique |
EP02730025A Withdrawn EP1379327A1 (fr) | 2001-04-02 | 2002-03-19 | Procede d'activation thermique rapide d'une reaction chimique dans une solution fluide surcritique |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP01108275A Withdrawn EP1247566A1 (fr) | 2001-04-02 | 2001-04-02 | Procédé d'excitation thermique rapide d'une réaction chimique dans une solution fluide supercritique |
Country Status (3)
Country | Link |
---|---|
EP (2) | EP1247566A1 (fr) |
DE (1) | DE10291321B4 (fr) |
WO (1) | WO2002078831A1 (fr) |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4338199A (en) * | 1980-05-08 | 1982-07-06 | Modar, Inc. | Processing methods for the oxidation of organics in supercritical water |
DE3931820A1 (de) * | 1989-09-20 | 1991-03-28 | Schering Ag | Verfahren zur herstellung von 3-hydroxyl-1,3,5(10)-estratrien-17-on |
DE4418149A1 (de) * | 1994-05-25 | 1995-11-30 | Bayer Ag | Verfahren zur Herstellung von Styrol-Acrylnitril-Copolymerisaten |
US5663237A (en) * | 1995-06-15 | 1997-09-02 | The University Of Akron | Graft copolymerization in supercritical media |
GB9620745D0 (en) * | 1996-10-04 | 1996-11-20 | Swan Thomas & Co Ltd | Alkylation and acylation reactions |
US6471937B1 (en) * | 1998-09-04 | 2002-10-29 | Praxair Technology, Inc. | Hot gas reactor and process for using same |
-
2001
- 2001-04-02 EP EP01108275A patent/EP1247566A1/fr not_active Withdrawn
-
2002
- 2002-03-19 EP EP02730025A patent/EP1379327A1/fr not_active Withdrawn
- 2002-03-19 WO PCT/EP2002/002985 patent/WO2002078831A1/fr not_active Application Discontinuation
- 2002-03-19 DE DE10291321T patent/DE10291321B4/de not_active Expired - Fee Related
Non-Patent Citations (1)
Title |
---|
See references of WO02078831A1 * |
Also Published As
Publication number | Publication date |
---|---|
DE10291321B4 (de) | 2012-08-30 |
WO2002078831A1 (fr) | 2002-10-10 |
DE10291321D2 (de) | 2004-04-15 |
EP1247566A1 (fr) | 2002-10-09 |
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