GB2054394A - Method for recovering a catalyst from a homogeneous catalytic reaction system - Google Patents
Method for recovering a catalyst from a homogeneous catalytic reaction system Download PDFInfo
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- GB2054394A GB2054394A GB8023823A GB8023823A GB2054394A GB 2054394 A GB2054394 A GB 2054394A GB 8023823 A GB8023823 A GB 8023823A GB 8023823 A GB8023823 A GB 8023823A GB 2054394 A GB2054394 A GB 2054394A
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- 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
- B01J31/40—Regeneration or reactivation
- B01J31/4015—Regeneration or reactivation of catalysts containing metals
- B01J31/4069—Regeneration or reactivation of catalysts containing metals involving extraction with coordinating ionic liquids or supercritical fluids, e.g. CO2
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D11/00—Solvent extraction
- B01D11/02—Solvent extraction of solids
- B01D11/0203—Solvent extraction of solids with a supercritical fluid
-
- 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
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/20—Carbonyls
-
- 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
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
-
- 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
- B01J31/40—Regeneration or reactivation
- B01J31/4015—Regeneration or reactivation of catalysts containing metals
- B01J31/4023—Regeneration or reactivation of catalysts containing metals containing iron group metals, noble metals or copper
- B01J31/4038—Regeneration or reactivation of catalysts containing metals containing iron group metals, noble metals or copper containing noble metals
-
- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/34—Other additions, e.g. Monsanto-type carbonylations, addition to 1,2-C=X or 1,2-C-X triplebonds, additions to 1,4-C=C-C=X or 1,4-C=-C-X triple bonds with X, e.g. O, S, NH/N
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- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0202—Polynuclearity
- B01J2531/0205—Bi- or polynuclear complexes, i.e. comprising two or more metal coordination centres, without metal-metal bonds, e.g. Cp(Lx)Zr-imidazole-Zr(Lx)Cp
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0202—Polynuclearity
- B01J2531/0211—Metal clusters, i.e. complexes comprising 3 to about 1000 metal atoms with metal-metal bonds to provide one or more all-metal (M)n rings, e.g. Rh4(CO)12
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
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- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/824—Palladium
Abstract
A method for recovering a catalyst comprising a coordination compound of a noble metal from a homogeneous catalytic reaction system comprises contacting the homogeneous catalytic reaction system with a fluid which has a critical temperature of from 0 to 100 DEG C and which is inert to said reaction system, at a temperature higher than the critical temperature of said fluid and under a pressure higher than the critical pressure of said fluid extract said reaction product(s) but not said catalyst into said fluid. Preferably the fluid is brought into contact with said reaction mixture at a temperature which is from 1 to 50 DEG C higher than the critical temperature of the fluid. The fluid may be ethane, ethylene, fluoromethane- chlorotrifluoromethane, carbon dioxide, nitrous oxide or xenon and the coordination compound may be of platinum, palladium, rhodium or ruthenium.
Description
SPECIFICATION
Method for recovering a catalyst from a homogeneous catalytic reaction system
The present invention relates to a method for recovering a catalyst including a non-volatile coordination compound of a noble metal from a homogeneous catalytic reaction system containing reaction products and the catalyst.
Recently, economization of resources and energies has come to be emphasized in the field of chemical industry as in other fields. To carry out a reaction at a high selectivity and to adopt milder reaction conditions lead to a contribution in economizing resources and energies. In order to carry out a reaction at a high selectivity and under milder reaction conditions, a homogeneous catalytic reaction is superior to a heterogeneous catalytic reaction as has been elucidated in several practical examples.
Accordingly, studies on the homogeneous catalytic reactions, particularly on those in which a coordination compound of noble metal is used as a catalyst are now actively carrying out. For instance, it has been well known that a catalyst including a coordination compound of rhodium has played an important role in the case of bringing methanol into reaction with carbon monoxide to synthesize acetic acid.
Further, there are many examples of studies in which organic coordination compounds of noble metals, for instance, platinum, palladium, rhodium and ruthenium are used in the synthesis of terpenetype compounds and steroid-type compounds.
Although these catalysts including coordination compounds of noble metals are excellent in their catalytic specificities, it is more difficult to recover them from the reaction products than in the case of heterogeneous catalytic reactions. Particularly, in the cases where the reaction product has a high boiling point or it is thermally unstable, the method of recovering the catalyst from the reaction product becomes a problem. In extreme cases, even though the reaction itself proceeds favorably, the catalyst cannot be re-used because of the absence of a pertenent method for recovering the catalyst from the reaction system containing the reaction products and the catalyst.
Generally, it can be said that there are scarcely any problems in recovering a catalyst from the reaction system wherein a heterogeneous catalytic reaction has been carried out. On the other hand, in the case where a catalyst including a coordination compound of a noble metal is to be recovered from a homogeneous catalytic reaction system containing reaction mixture and the catalyst, there are many problems to be solved.
Hitherto, as a means for recovering or separating the catalyst from the reaction mixture of a homogeneous catalytic reaction system, extraction, crystallization or distillation has been utilized. However, in carrying out the recovery or separation by extraction, it is extremely difficult to find out convenient solvents which are able to selectively extract substantially either the catalyst or the reaction product. In addition, an additional operation of solvent recovery becomes necessary together with a problem of solvent loss in the recovering step.
In another method of recovery or separation by crystallization, it is very difficult to recover the catalyst completely from the reaction product. It is advantageous to separate or isolate the reaction product from the reaction system by distillation in the case where the vapour pressure of the catalyst is sufficiently low and the reaction product boils at a relatively low temperature. On the other hand, in the case where the reaction product has a high boiling point or it is thermally unstable, an extremely high vacuum must be applied to the distilling system for the prevention of decomposition, degradation or denaturation of the reaction product.For instance, in the case where a compound of a calculated boiling point at an ordinary pressure (760 mmHg) of 350"C (boiling point of about 1200C/0.08 mmHg), which is denatured at a temperature over 120"C is synthesized by a homogeneous catalytic reaction in the presence of a catalyst of a noble metal coordination compound, it is necessary to apply a high vacuum of lower than 0.1 mmHg. Besides, this value of vacuum is determined at the top of the distilling tower.
Besides, in the case where by-products boiling at a higher temperature than the boiling point of the main product are present in the reaction product, a still higher vacuum is required in order to distill the reaction product at the bottom of the distilling column. The application of such a high degree of vacuum is not practical industrially.
Moreover, since there are many cases where such a catalyst including a coordination compound of a noble metal is thermally unstable, the method utilizing distillation has a fear of not only the loss of the reaction product but also the loss of the catalyst. For instance, since bis - [tri - (o - tolyl) phosphine] palladium which can be exemplified as a catalyst of a coordination compound of a noble metal decomposes at a temperature of higher than 200 C, the temperature of its distillation should be restricted.
In addition, although the degraded or decomposed catalyst is possibly recovered as a metal and also the new catalyst is possibly obtained by coordination of ligands to the thus recovered metal, however, since the catalyst comprising a coordination compound of a noble metal is generally very much expensive and so the loss due to the degradation or decomposition of the catalyst affects the production cost very much, the separation or recovery of the catalyst under the conditions under which the catalyst may be degraded or decomposed is not practical.
That is, as has been described above, a satisfactory method by which the catalyst including a coordination compound of a noble metal and the reaction product in a reaction system containing the catalyst and the reaction product can be advantageously separated has not yet been proposed, and accordingly, it will be said that there is still an unsolved part in the industrial utilization of the catalyst including a coordination compound of a noble metal, which is considered to be advantageous from the viewpoint of reaction itself.
In general, when a gas is brough into contact with a solid or a liquid, the amount of the solid or the liquid, which shifts to the gas phase at a normal temperature and under a normal pressure is extremely small. However, in the case where an appropriate gas is chosen as a fluid and the gas is brought into the conditions of more than critical temperature and pressure, the amount of a solid or a liquid shifting to the gas phase increases rapidly.
The phenomenon will be explained in an instance of a two-compartment system consisting of p-iodochloro-benzene and ethylene as follows (refer to "The Principle of Gas Extraction" by P. F. M. Paul and W. S. Wise, Publ. by Mills and Boon Ltd, London, 1971):
When ethylene and p-iodochlorobenzene are brought into contact with each other at a temperature of 25 C under a normal pressure, the amount of p-iodochlorobenzene shifting to ethylene is only 0.006 glNI of ethylene, however, at the same temperature of 250C and under a pressure of 90 atm, the amount is 50 g/NI of ethylene. By the way, the critical temperature and pressure of ethylene are, respectively 9.9 C and 50.5 atm.
According to British Patent No. 1,057,911, a compound of which the vapour pressure is very small such as ammonium chloride or sulfuric acid scarcely shifts into ethylene even when brought into contact with ethylene under a pressure of 200 atm to an extent to be detected.
The inventors of the present invention have paid an attention to the above-mentioned facts and by bringing the above-mentioned reaction mixture of a
homogeneous catalytic reaction system containing the above-mentioned catalyst including a coordina
tion compound of a noble metal into contact with a
gas chemically inert to the above-mentioned reac
tion system, which has been brought into a tempera
ture higher than the critical temperature thereof and
a pressure higher than the critical pressure thereof they have found that the catalyst and the product of the above-mentioned reaction were advantageously separated from the reaction mixture, and has arrived atthe present invention.
It is an object of the present invention to provide a method for recovering a catalyst including a nonvolatile coordination compound of a noble metal from a reaction mixture containing the reaction product produced in a homogeneous catalytic reaction system.
According to the method, a gas (orfluid) having a critical temperature in a range of O to 1000C and being inert to the above-mentioned reaction product is brought into contact with the above-mentioned homogeneous catalytic reaction system at a regulated temperature above its critical temperature and under a regulated pressure above its critical pressure in an extracting apparatus to extract the reaction product into the gas as a fluid and the gas thus loaded with the reaction product is removed from the extracting apparatus to leave the abovementioned catalyst as it is within the extracting apparatus.
in the drawing, the single figure is a flow chart illustrating one embodiment of the present invention.
The followings are the detailed explanation of the present invention.
According to the present invention, in a homogeneous catalytic reaction using a non-volatile coordination compound of a noble metal as a catalyst, the product of the catalytic reaction is profitably separated from the reaction mixture even when the reaction product is thermally unstable and boils at a high temperature, and also the catalyst is favourably recovered from the reaction mixture.
Solubility of a solid or liquid substance into a fluid in a state of pressure and temperature over its respective critical values is determined by the physical properties, the temperature and the pressure of the fluid, and in general, the solubility is larger as the pressure of the fluid is higher and, in the range over the critical temperature of the fluid, as the temperature of the fluid is closer to its critical temperature.
Accordingly, the conditions on the contact of the reaction mixture and the above-mentioned fluid in the present invention are as follows:
In the first place, although the pressure is preferably as higher as possible overthe critical pressure of the gas used as a fluid, however, in sonsideration of economy, it is preferably in a range of 50 to 200 atm. In the second place, the temperature must be higher than the critical temperature of the gas as a fluid but is preferably as low as possible, and so the temperature is higher than the critical temperature of the gas by 1 to 500C, preferably 1 to 25 C. The gas used as a fluid in the present invention can be selected from a broad range of gases provided it is chemically inert to the reaction mixture and reaction system.From the stand point of economizing energy consumption, a gas of too low critical temperature is not preferable. For instance, nitrogen (critical temperature = Tc of -147.00C), helium (Tc of-267.9'C) and methane (Tc of -82.10C) are desirable because of their chemical inertness, however, in the actual case where such a gas is brought into contact with the reaction mixture containing a catalyst including a coordination compound of a noble metal in order to shift the reaction product from the mixture into the gas used as a fluid at a temperature close to room temperature, the difference between this temperature and the critical temperature is so large that the amount of the reaction product shifted to the fluid is extremely small. That is why the gas of too low critical temperature is not practical.
Accordingly, in the present invention, the gas for use as a fluid has been selected from the group consisting of those which have respective critical temperatures of 0 to 1 00 C from the major view point that the operation of separation is possibly carried out at a temperature around room temperature. Table 1 shows the gases usable as a fluid in the present invention as well as their critical values.
Table 1: Critical temperatures and pressures
of gases used as fluids
Gas Critical Critical
temperature ( C) pressure (atm)
Ethylene 9.9 50.5
Ethane 32.3 48.2
Carbon dioxide 31.0 72.9
Methyl fluoride 44.6 58.0
Chlorotrifluoromethane 53 40.3
Nitrous oxide 36.5 71.7
Xenon 16.6 58.2
In the next place, the coordination compound of a noble metal used as a catalyst in the present invention is selected from the hitherto used coordination compounds of platinum, palladium, rhodium or ruthenium, exemplified by, for instance, bis - [ tri - (o tolyl) phosphine] palladium:
tetrakis- (triphenylphosphine) palladium:
tetrarhodium dodecarbonyl: [ Rh(CO)3#4, and rhodium dicarbonyl chloride dimer: [ Rh(CO)2CI2.
In addition, in the present invention, as are shown in Examples, the separation of the reaction product from reaction system containing the catalyst is particularly and effectively carried out in the case where the reaction product has a boiling point of higher than 200 C or has more than two carbon-carbon unsaturated bondings in its molecule.
The followings were the explanation of the concrete procedures for separating the reaction product and the catalyst from the reaction mixture obtained by a homogeneous catalytic reaction carried out in the presence of a catalyst including a coordination compound of a noble metal according to the present invention:
Into an extracting apparatus 2, the reaction mixture in a liquid state 1 obtained by the abovementioned homogeneous catalytic reaction is introduced, and a gas 4 compressed to a state of higher than its critical pressure by a compressor 3 is then
introduced into the extracting apparatus 4 as a fluid to be brought into contact with the liquid reaction mixture 1. The device 5 is a control valve of flow rate of the fluid.The content of the extracting apparatus 2 is stirred by suitable means for obtaining a sufficient contact between the reaction mixture and the fluid at a state of higher than its critical temperature and its cirtical pressure.
On contacting, the reaction product is shifted to the fluid at a state of temperaure and pressure, both being higher than its respective critical values, and then the fluid thus containing the reaction product is led to a gas-liquid separator 7 via a pressure controlling valve 6 with a reduced pressure by the valve 6.
In this operation of pressure reduction, it is not necessary to reduce the pressure of the fluid to normal state, but it is enough to reduce to a value lower than its critical pressure where the dissolving capability of the fluid to the reaction product becomes to zero practically. Then, the reaction product separates out from the fluid which has lost its dissolving capability, and the thus separated product is recovered in the gas-liquid separator 7 and removed as the final product 8. The thus separated fluid is recycled to the compressor 3 to be returned to the state of temperature and pressure, both being over its respective critical values for the repeated utilization in extraction in the extracting apparatus 2.
The present invention is exemplified by the following Examples, however, is not restricted to the
Examples herein described.
Example 1:
Into an autoclave, 62 g of ethylene glycol, 2.869 of bis[tri - (o - tolyl) phosphine] palladium and 216 g of butadiene were introduced and a reaction was carried out at a temperaure of 850C for 5 hours to obtain 281.09 of a liquid yellow in colour. The major components of the reaction mixture are as follows::
Major components Boiling Composition point ( C) (% by weight) 1,3,7 - octatriene 125 32.6 ethylene glycol mono - (2, 7 - octadienyl) 260 35.5 ether ethylene glycol di - (2, 7 - octadienyl) 330 16.7 ether In addition, the concentration of palladium in the
above-mentioned reaction mixture was 1,500 ppm.
Ethane was introduced into the above-mentioned autoclave maintained at a temperature of 400C and still containing the reaction mixture, at a pressure of 65 atm and a flow rate of 7 N liters/hour while maintaining a vigorous stirring to have a contact between ethane and the reaction mixture in the autoclave.
The ethane used as a fluid for extraction, containing the dissolved reaction product and at a state of temperature and pressure, both being over its respective critical values was led to the gas-liquid separator maintained at a normal state of temperature and pressure via the device for preventing entrainment of splash and the pressure-controlling valve, and was separated from the reaction products. The rate of extraction was 10 ml of the reaction product per 100 N liters of ethane. No palladium was detected in the liquid collected in the gas-liquid separator by atomic absorption analysis, the fact informing the sole shift ofthe reaction products to ethan at a state of temperature and pressure, both being over the respective critical values.
After continuing the extraction until the amount of the reaction product became 275 g in the separator 7, ethylene glycol and butadiene were added to the catalyst remained in the autoclave and the content of the autoclave was heated to 85 C. finding out that the reaction proceeded for 5 hours. From the above-mentioned result it was found that the catalytic activity of the originally added catalyst was not impaired by the operation of extraction abovementioned.
Example 2:
Into an autoclave, 446 g of butadiene, 5.9 g of bis
Ltri - (o-tolyl) phosphine] palladium and 181 g of acetaidehyde were introduced, and the mixture was brought into reaction at 40 C for 7 hours to obtain 578 g of a liquid yellow in colour.
The composition of the reaction mixture was determined by gaschrnmatography as follows:
Determined components Boiling Composition point ( C) (% by weight) 1,3,7-octatriene 125 1.0 2,5-divinyl-6-methyltetra- - 2.0 hydropyrane 1 - methyl - 2 - vinyl - 4,6 - heptadiene - 210 89.9 1 -ol 1 - methyl - 2 - vinyl - 4,6 - heptadienyl - 2.1 acetate While maintaining the thus formed reaction mix
ture containing the reaction products at a tempera
ture of 45 C, ethane was blown into it at a pressure of
70 atm and at a rate of 10 N liters/hours under a
vigorous stirring to bring the ethane into contact
with the reaction mixture. The ethane in a state of
pressure and temperature, both being higherthan those respective critical values, was led to the gas
liquid separator maintained at normal temperature and pressure via the preventing means of entrainment of splash and a pressure-controlling valve, and the reaction products separated out with in the separator. The rate of extraction was 11 ml of the reaction product per 100 N liter of ethane. No palladium was detected in a liquid remaining in the separator by atomic absorption analysis informing that only the reaction products shifted to ethane.
Example 3:
After introducing 78 g of butadiene, 110 g of 1 methyl - 2 - vinyl - 4,6 - heptadiene - 1 - ol and 1.519 of tetrakis - (triphenyl - phosphine) palladium into an autoclave, carbon monoxide was added under pressure and the reaction was carried out at a temperature of 85 C for 16 hours. After the reaction was over, unreacted carbon monoxide and butadiene were removed and a liquid yellow in colour was obtained amounting to 203 g.The major components of the yellow liquid were as follows:
Components Boiling Composition point ("C) (% by weight) ~ 1,3,7 - octatriene 125 2.7 1 - methyl - 2-vinyl -4,6 - heptadiene - 210 5.2 1 -ol 1 - methyl -2 - vinyl - 4,6 - heptadienyl 320 92.1 3,8 - nonadienoate The concentration of palladium in the reaction mixture was 680 ppm by atomic absorption analysis.
When treating the reaction mixture with ethan under the same conditions as in Example 1, a liquid not containing palladium was obtained in an amount of 197 g.
Example 4:
After introducing 50 ml of the reaction product of
Example 1 into an autoclave with a capacity of 200 ml, xenon was introduced into the autoclave, while stirring the content of the autoclave at 1,000 rpm, at room temperature of 22 C at a rate of 10 N liters per hour under a pressure of 75 atm. The xenon in a state of temperature and pressure both being higher than the respective critical values, was led to a gasliquid separator maintained at normal temperature and pressure via a preventing device ofentrainmentof splash and a pressure-controlling valve. The reaction products were separated within the separator. The rate of extraction was 11.5 ml of the products per 100 N liters of xenon. No palladium was detected in the reaction products in the gas-liquid separator by atomic absorption analysis.
Claims (10)
1. A method for recovering a catalyst comprising a coordination compound of a noble metal from a reaction mixture containing reaction products formed in a homogeneous catalytic reaction system, which method comprises contacting said reaction system with a fluid, which has a critical temperature of from 0 to 1000C and which is inert to said reaction system, at a temperature higher than the critical temperature of said fluid and under a pressure higher than the critical pressure of said fluid to extract said reaction product(s) but not said catalyst into said fluid.
2. A method according to claim 1,wherein said fluid is brought into contact with said reaction mixture at a temperature which is from 1 to 50"C higher than the critical temperature of the fluid.
3. A method according to claim 1 or 2, wherein said fluid is ethane, ethylene, fluoromethane, chlorotrifluoromethane, carbondioxide, nitrous oxide or xenon.
4. A method according to any one of the preceding claims, wherein said reaction product(s) consists of or include at least one compound which boils at a temperature higher than 200"C.
5. A method according to any one of the preceding claims, wherein said reaction product(s) consists of or include at least one unsaturated compound having two or more unsaturated carbon to carbon bonds.
6. A method according to any one of the preceding claims, wherein said catalyst is non-volatile.
7. A method according to claim 6, wherein said catalyst is an organic coordination compound of platinum, palladium, rhodium or ruthenium.
8. A method according to any one of the preceding claims, which is effected in the reactor in which said homogeneous catalytic reaction occurs.
9. A method according to any one of claims 1 to 7 which is effected in apparatus substantially as hereinbefore described with reference to and as illustrated in the accompanying drawing.
10. A method according to claim 1 substantially as hereinbefore described in any one of the Examples.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9342479A JPS5621651A (en) | 1979-07-23 | 1979-07-23 | Separating catalyst from homogeneous catalytic reaction system |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB2054394A true GB2054394A (en) | 1981-02-18 |
| GB2054394B GB2054394B (en) | 1983-05-05 |
Family
ID=14081911
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB8023823A Expired GB2054394B (en) | 1979-07-23 | 1980-07-21 | Method for recovering a catalyst from a homogeneous catalytic reaction system |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JPS5621651A (en) |
| DE (1) | DE3027233A1 (en) |
| GB (1) | GB2054394B (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4476237A (en) * | 1981-05-28 | 1984-10-09 | The Halcon Sd Group, Inc. | Separation of tars from carbonylation reaction mixtures |
| US4476238A (en) * | 1981-05-28 | 1984-10-09 | The Halcon Sd Group, Inc. | Separation of tars from carbonylation reaction mixtures |
| US4556644A (en) * | 1981-08-31 | 1985-12-03 | Hoechst Aktiengesellschaft | Process for purifying and recovering contaminated catalyst solution obtained in the carbonylation of methyl acetate and/or dimethylether |
| US4568653A (en) * | 1978-07-29 | 1986-02-04 | Basf Aktiengesellschaft | Working up of hydroformylation or carbonylation reaction mixtures |
| US4605811A (en) * | 1980-05-31 | 1986-08-12 | Helmut Tiltscher | Process for restoring or maintaining the activity of heterogeneous catalysts for reactions at normal and low pressures |
| EP0380911A1 (en) * | 1989-01-28 | 1990-08-08 | Hoechst Aktiengesellschaft | Process for the purification and recovery of a catalyst solution contaminated in the carbonylation of methanol and/or methyl acetate and/or dimethyl ether |
| US5198598A (en) * | 1991-07-19 | 1993-03-30 | Henkel Kommanditgesellschaft Auf Aktien | Telomerization process of a conjugated alkadiene with a polyol |
| US5206396A (en) * | 1990-07-25 | 1993-04-27 | Henkel Research Corporation | Telomerization of 1,3-butadiene |
| US5236909A (en) * | 1990-07-25 | 1993-08-17 | Henkel Research Corporation | Octyl ethers and octadienyl ethers |
| CN114377429A (en) * | 2021-12-24 | 2022-04-22 | 陕西聚泰新材料科技有限公司 | Process for removing organic matters and/or elemental sulfur from supported waste catalyst |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5062888A (en) * | 1973-10-06 | 1975-05-29 |
-
1979
- 1979-07-23 JP JP9342479A patent/JPS5621651A/en active Pending
-
1980
- 1980-07-18 DE DE19803027233 patent/DE3027233A1/en not_active Withdrawn
- 1980-07-21 GB GB8023823A patent/GB2054394B/en not_active Expired
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4568653A (en) * | 1978-07-29 | 1986-02-04 | Basf Aktiengesellschaft | Working up of hydroformylation or carbonylation reaction mixtures |
| US4605811A (en) * | 1980-05-31 | 1986-08-12 | Helmut Tiltscher | Process for restoring or maintaining the activity of heterogeneous catalysts for reactions at normal and low pressures |
| US4476237A (en) * | 1981-05-28 | 1984-10-09 | The Halcon Sd Group, Inc. | Separation of tars from carbonylation reaction mixtures |
| US4476238A (en) * | 1981-05-28 | 1984-10-09 | The Halcon Sd Group, Inc. | Separation of tars from carbonylation reaction mixtures |
| US4556644A (en) * | 1981-08-31 | 1985-12-03 | Hoechst Aktiengesellschaft | Process for purifying and recovering contaminated catalyst solution obtained in the carbonylation of methyl acetate and/or dimethylether |
| EP0380911A1 (en) * | 1989-01-28 | 1990-08-08 | Hoechst Aktiengesellschaft | Process for the purification and recovery of a catalyst solution contaminated in the carbonylation of methanol and/or methyl acetate and/or dimethyl ether |
| US5047377A (en) * | 1989-01-28 | 1991-09-10 | Hoechst Aktiengesellschaft | Process for the purification and recovery of the contaminated solution of the catalyst produced on carbonylation of methanol and/or methyl acetate and/or dimethyl ether |
| US5206396A (en) * | 1990-07-25 | 1993-04-27 | Henkel Research Corporation | Telomerization of 1,3-butadiene |
| US5236909A (en) * | 1990-07-25 | 1993-08-17 | Henkel Research Corporation | Octyl ethers and octadienyl ethers |
| US5198598A (en) * | 1991-07-19 | 1993-03-30 | Henkel Kommanditgesellschaft Auf Aktien | Telomerization process of a conjugated alkadiene with a polyol |
| CN114377429A (en) * | 2021-12-24 | 2022-04-22 | 陕西聚泰新材料科技有限公司 | Process for removing organic matters and/or elemental sulfur from supported waste catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5621651A (en) | 1981-02-28 |
| GB2054394B (en) | 1983-05-05 |
| DE3027233A1 (en) | 1981-01-29 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |