CA2092049C - Process for the recovery of rhodium from residues of carbonylation reactions - Google Patents
Process for the recovery of rhodium from residues of carbonylation reactions Download PDFInfo
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- CA2092049C CA2092049C CA 2092049 CA2092049A CA2092049C CA 2092049 C CA2092049 C CA 2092049C CA 2092049 CA2092049 CA 2092049 CA 2092049 A CA2092049 A CA 2092049A CA 2092049 C CA2092049 C CA 2092049C
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- acetic anhydride
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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
- B01J31/02—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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G55/00—Compounds of ruthenium, rhodium, palladium, osmium, iridium, or platinum
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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
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/20—Carbonyls
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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
- B01J31/16—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
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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
- B01J31/4023—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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/54—Preparation of carboxylic acid anhydrides
- C07C51/573—Separation; Purification; Stabilisation; Use of additives
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B11/00—Obtaining noble metals
- C22B11/04—Obtaining noble metals by wet processes
- C22B11/042—Recovery of noble metals from waste materials
- C22B11/048—Recovery of noble metals from waste materials from spent catalysts
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/009—General processes for recovering metals or metallic compounds from spent catalysts
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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
- 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
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/822—Rhodium
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- 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
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- 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
- Y02P20/584—Recycling of catalysts
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- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The present invention relates to a process for the recovery of rhodium from acetic anhydride-containing residues, which are produced in the carbonylation of methanol and/or methyl acetate and/or dimethyl ether. A
carboxylic acid having 2 to 5 carbon atoms is added to the residue, the mixture is heated, 1 to 10 mol of methanol per mol of acetic anhydride are added, the constituents boiling more readily than the carboxylic acid are distilled off, the mixture is cooled and the rhodium-containing residue is separated.
carboxylic acid having 2 to 5 carbon atoms is added to the residue, the mixture is heated, 1 to 10 mol of methanol per mol of acetic anhydride are added, the constituents boiling more readily than the carboxylic acid are distilled off, the mixture is cooled and the rhodium-containing residue is separated.
Description
~(~9~04~
Process for the recovery of rhodium from residues of carbonylation reactions The present invention relates to a process for the recovery of rhodium from residues of carbonylation reactions. The term carbonylation generally denotes the introduction of a carbonyl group into an organic compound. Some of the most important carbonylations, and also those carried out industrially, are the synthesis of aldehydes by reaction of olefins with carbon monoxide and hydrogen and the synthesis of carboxylic acids and anhydrides of carboxylic acids by reaction of alcohols and/or esters and/or ethers with carbon monoxide. These carbonylations conventionally only proceed as insertion reactions in the presence of metal carbonyls and carbonyl complexes which catalyse these reactions.
In the context of the present invention, carbonylation is taken to mean the reaction of methanol and/or methyl acetate and/or dimethyl ether with carbon monoxide.
Acetic acid and acetic anhydride are produced in this case. The preparation of acetic acid from methanol and carbon monoxide using cobalt carbonyl catalysts together with an iodine converter, on the one hand, and rhodium carbonyl catalysts together with an iodine promoter, on the other hand, is described in Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, Volume A1, pages 47-50, VCH Verlagsgesellschaft Weinheim (1985). A brief description of the preparation of acetic anhydride by the reaction of methyl acetate or dimethyl ether in the presence of rhodium and nickel compounds which, activated by methyl iodide, hydrogen iodide, LiI, I2 or other iodides, are suitable catalysts, is given in Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, Volume A1, pages 72-74, VCH Verlagsgesellschaft Weinheim (1985).
Whereas the carbonylation of methyl acetate directly delivers acetic anhydride, the reaction of dimethyl ether with carbon monoxide leads first to methyl acetate, which is then converted to acetic anhydride by renewed reaction with carbon monoxide.
Process for the recovery of rhodium from residues of carbonylation reactions The present invention relates to a process for the recovery of rhodium from residues of carbonylation reactions. The term carbonylation generally denotes the introduction of a carbonyl group into an organic compound. Some of the most important carbonylations, and also those carried out industrially, are the synthesis of aldehydes by reaction of olefins with carbon monoxide and hydrogen and the synthesis of carboxylic acids and anhydrides of carboxylic acids by reaction of alcohols and/or esters and/or ethers with carbon monoxide. These carbonylations conventionally only proceed as insertion reactions in the presence of metal carbonyls and carbonyl complexes which catalyse these reactions.
In the context of the present invention, carbonylation is taken to mean the reaction of methanol and/or methyl acetate and/or dimethyl ether with carbon monoxide.
Acetic acid and acetic anhydride are produced in this case. The preparation of acetic acid from methanol and carbon monoxide using cobalt carbonyl catalysts together with an iodine converter, on the one hand, and rhodium carbonyl catalysts together with an iodine promoter, on the other hand, is described in Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, Volume A1, pages 47-50, VCH Verlagsgesellschaft Weinheim (1985). A brief description of the preparation of acetic anhydride by the reaction of methyl acetate or dimethyl ether in the presence of rhodium and nickel compounds which, activated by methyl iodide, hydrogen iodide, LiI, I2 or other iodides, are suitable catalysts, is given in Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, Volume A1, pages 72-74, VCH Verlagsgesellschaft Weinheim (1985).
Whereas the carbonylation of methyl acetate directly delivers acetic anhydride, the reaction of dimethyl ether with carbon monoxide leads first to methyl acetate, which is then converted to acetic anhydride by renewed reaction with carbon monoxide.
The mixtures of substances produced in the carbonylation are worked up by distillation, the carbonylation catalysts originally used collecting the residues caused by the distillation. The recovery of metals, in particular rhodium, from these residues is an important component of the overall process.
EP 0 210 017 A1 relates to a process for the recovery of rhodium from residues which are produced in the rhodium/lithium-catalyzed carbonylation of esters and ethers in the presence of an iodide. The residue is treated with an alcohol, in particular with a tertiary alcohol, such as tert-butanol or tert-amyl alcohol, a carboxylic acid or an ester of a carboxylic acid at elevated temperature. In this case, a solid is precipitated which virtually completely contains the rhodium complex. To separate off tar-like constituents, the precipitated solid is extracted using specific solvents, for example alkanes, cycloalkanes or ethers.
The use of primary or secondary alcohols to precipitate the rhodium-containing solid leads to a significantly lower rhodium recovery.
EP 0 240 703 relates to a process for the recovery of rhodium, the contaminated catalyst solution produced in the carbonylation of methyl acetate and/or dimethyl ether being freed from organic residues by a liquid/liquid extraction using dialkyl ethers and alcohols each having 1 to 4 carbon atoms . The ether phase is then treated with iodine and/or methyl iodide, the catalyst complex precipitating in the course of this is separated off and the organic phase is separated by distillation.
The process has proved itself, but requires a comparatively high expenditure.
EP 0 210 017 A1 relates to a process for the recovery of rhodium from residues which are produced in the rhodium/lithium-catalyzed carbonylation of esters and ethers in the presence of an iodide. The residue is treated with an alcohol, in particular with a tertiary alcohol, such as tert-butanol or tert-amyl alcohol, a carboxylic acid or an ester of a carboxylic acid at elevated temperature. In this case, a solid is precipitated which virtually completely contains the rhodium complex. To separate off tar-like constituents, the precipitated solid is extracted using specific solvents, for example alkanes, cycloalkanes or ethers.
The use of primary or secondary alcohols to precipitate the rhodium-containing solid leads to a significantly lower rhodium recovery.
EP 0 240 703 relates to a process for the recovery of rhodium, the contaminated catalyst solution produced in the carbonylation of methyl acetate and/or dimethyl ether being freed from organic residues by a liquid/liquid extraction using dialkyl ethers and alcohols each having 1 to 4 carbon atoms . The ether phase is then treated with iodine and/or methyl iodide, the catalyst complex precipitating in the course of this is separated off and the organic phase is separated by distillation.
The process has proved itself, but requires a comparatively high expenditure.
DE 32 08 060 Al, published on November 4, 1982, describes a process for the recovery of noble metals from residues of carbonylation reactions, the residue first being treated in a first stage with an alcohol, preferably methanol, and then being freed from low boilers at a temperature of no more than 25°C. An amine is added to the remaining residue and the rhodium is separated off by multiple extraction using a halogen acid. The process requires numerous working steps and requires a high expenditure in terms of equipment in the separation off of the low boilers by distillation proceeding under high vacuum. In addition, the extraction using halogen acids is associated with disadvantages because of the directions to be complied with on handling halogen acids and halogenated solvents.
The object is therefore to provide a process which avoids the above-mentioned disadvantages, can be carried out industrially in a simple manner, uses conventional auxiliary materials and, moreover, ensures a high recovery of rhodium.
This object is achieved by means of a process for the recovery of rhodium from acetic anhydride-containing residues which are produced in the carbonylation of one or more of methanol, methyl acetate, and dimethyl ether, which comprises adding a carboxylic acid having 2 to 5 carbon atoms to the acetic anhydride-containing residues, heating the acetic anhydride-containing residues with the added carboxylic acid to to 100°C, adding 1 to 10 mol of methanol per mol of acetic anhydride, following reaction of the acetic anhydride with methanol, removing constituents boiling more readily than the carboxylic acid by distillation, cooling the distillate residue 30 to a temperature <_ 50°C and separating the precipitated rhodium-containing solid from the distillation residue.
. ,, 3a 2 0 9 2 0 4 9 The residue produced in the carbonylation of methanol and/or methyl acetate and/or dimethyl ether conventionally contains, in addition to subsidiary r. ' . J
The object is therefore to provide a process which avoids the above-mentioned disadvantages, can be carried out industrially in a simple manner, uses conventional auxiliary materials and, moreover, ensures a high recovery of rhodium.
This object is achieved by means of a process for the recovery of rhodium from acetic anhydride-containing residues which are produced in the carbonylation of one or more of methanol, methyl acetate, and dimethyl ether, which comprises adding a carboxylic acid having 2 to 5 carbon atoms to the acetic anhydride-containing residues, heating the acetic anhydride-containing residues with the added carboxylic acid to to 100°C, adding 1 to 10 mol of methanol per mol of acetic anhydride, following reaction of the acetic anhydride with methanol, removing constituents boiling more readily than the carboxylic acid by distillation, cooling the distillate residue 30 to a temperature <_ 50°C and separating the precipitated rhodium-containing solid from the distillation residue.
. ,, 3a 2 0 9 2 0 4 9 The residue produced in the carbonylation of methanol and/or methyl acetate and/or dimethyl ether conventionally contains, in addition to subsidiary r. ' . J
amounts of high-boiling components, as main constituents acetic acid and acetic anhydride. The residue contains 10 to 60, in particular 15 to 50, preferably 20 to 40~ by weight of acetic anhydride. Furthermore, the residue has comparatively low quantities of rhodium. It contains 200 to 2000, in particular 250 to 1500, preferably 280 to 1000 ppm of rhodium. A carboxylic acid is added to the residue in an amount such that the residue contains 10 to 150, in particular 30 to 120, preferably 50 to 100 ppm of rhodium.
Suitable carboxylic acids are acetic acid, propionic acid, n-butyric acid, isobutyric acid, n-valeric acid, 2-methyl butyric acid and 3-methyl butyric acid., Acetic acid is particularly suitable as the carboxylic acid.
The residue with the added carboxylic acid is then heated to a temperature of 30 to 100, in particular 35 to 90, preferably 40 to 80°C. Methanol is then added to the heated residue with the added carboxylic acid. The required amount of methanol is based on the amount of acetic anhydride present in the residue. 1 to 10 mol of methanol, in particular 1.5 to 7, preferably 2 to 6, mol of methanol are added per mol of acetic anhydride.
The mixture is then reacted until the acetic anhydride has reacted to a sufficient extent. The constituents boiling more readily than the carboxylic acid, that is methyl acetate and, possibly, excess methanol, are then separated off by distillation. The distillation can be carried out at elevated temperature in a range from 50 to 200°C.
After separating off the constituents boiling more readily than the carboxylic acid, the distillation residue is cooled to a temperature s 50, in particular _<
40, preferably s 35, particularly preferably s 30°C.
Suitable carboxylic acids are acetic acid, propionic acid, n-butyric acid, isobutyric acid, n-valeric acid, 2-methyl butyric acid and 3-methyl butyric acid., Acetic acid is particularly suitable as the carboxylic acid.
The residue with the added carboxylic acid is then heated to a temperature of 30 to 100, in particular 35 to 90, preferably 40 to 80°C. Methanol is then added to the heated residue with the added carboxylic acid. The required amount of methanol is based on the amount of acetic anhydride present in the residue. 1 to 10 mol of methanol, in particular 1.5 to 7, preferably 2 to 6, mol of methanol are added per mol of acetic anhydride.
The mixture is then reacted until the acetic anhydride has reacted to a sufficient extent. The constituents boiling more readily than the carboxylic acid, that is methyl acetate and, possibly, excess methanol, are then separated off by distillation. The distillation can be carried out at elevated temperature in a range from 50 to 200°C.
After separating off the constituents boiling more readily than the carboxylic acid, the distillation residue is cooled to a temperature s 50, in particular _<
40, preferably s 35, particularly preferably s 30°C.
After cooling, a rhodium-containing precipitate is produced, whose composition is not known more precisely.
Apparently it is a mixture of metallic rhodium and a rhodium complex which contains, in addition to carbon monoxide and iodide, a further phosphorus-containing ligand, in particular a trialkyl phosphine. After filtration, this precipitate can be converted into a dissolved form, just as can a metallic wall coating remaining in the reaction vessel, by treatment with acetic acid and trialkyl phosphine or trialkyl phosphenium halide with addition of carbon monoxide in a short time at a temperature of 60 to 90°C. The resulting solution can then be returned as catalyst into the carbonylation process.
The following example supports the invention without restricting it.
Experimental Section Example 50.0 g of a residue which contains 330 ppm of rhodium and 0.131 mol of acetic anhydride are placed in a round flask and 187.9 g of acetic acid are added with stirring. The homogeneous mixture resulting from this is heated to 40°C
and 8.4 g (0.262 mol) of methanol are added in the course of 15 minutes . The mixture is reacted for a further 60 minutes with stirring and then the low-boiling fractions are distilled off up to a temperature of 109°C (measured at the head of the distillation unit). 32.2 g of distillate are produced. The residue is cooled to 20°C
and stirred for 20 hours. The precipitated rhodium-containing solid is then separated by filtration. 1.33 mg of rhodium, i.e. 8.1~ by weight of the rhodium originally used are still homogeneously dissolved in the mother liquor produced.
X09?049 _ 6 _ The solid filtered off is returned into the round flask, 60.0 g of acetic acid and 6.0 g of methyl tri-n-butyl-phosphonium iodide are added and the mixture is stirred for 60 minutes at 80°C with carbon monoxide being passed through. A clear, homogeneous solution is produced having a rhodium content of 14.65 mg, corresponding to 88.8 by weight of the rhodium amount originally used.
Apparently it is a mixture of metallic rhodium and a rhodium complex which contains, in addition to carbon monoxide and iodide, a further phosphorus-containing ligand, in particular a trialkyl phosphine. After filtration, this precipitate can be converted into a dissolved form, just as can a metallic wall coating remaining in the reaction vessel, by treatment with acetic acid and trialkyl phosphine or trialkyl phosphenium halide with addition of carbon monoxide in a short time at a temperature of 60 to 90°C. The resulting solution can then be returned as catalyst into the carbonylation process.
The following example supports the invention without restricting it.
Experimental Section Example 50.0 g of a residue which contains 330 ppm of rhodium and 0.131 mol of acetic anhydride are placed in a round flask and 187.9 g of acetic acid are added with stirring. The homogeneous mixture resulting from this is heated to 40°C
and 8.4 g (0.262 mol) of methanol are added in the course of 15 minutes . The mixture is reacted for a further 60 minutes with stirring and then the low-boiling fractions are distilled off up to a temperature of 109°C (measured at the head of the distillation unit). 32.2 g of distillate are produced. The residue is cooled to 20°C
and stirred for 20 hours. The precipitated rhodium-containing solid is then separated by filtration. 1.33 mg of rhodium, i.e. 8.1~ by weight of the rhodium originally used are still homogeneously dissolved in the mother liquor produced.
X09?049 _ 6 _ The solid filtered off is returned into the round flask, 60.0 g of acetic acid and 6.0 g of methyl tri-n-butyl-phosphonium iodide are added and the mixture is stirred for 60 minutes at 80°C with carbon monoxide being passed through. A clear, homogeneous solution is produced having a rhodium content of 14.65 mg, corresponding to 88.8 by weight of the rhodium amount originally used.
Claims (19)
1. A process for the recovery of rhodium from acetic anhydride-containing residues which are produced in the carbonylation of one or more of methanol, methyl acetate, and dimethyl ether, which comprises adding a carboxylic acid having
2 to 5 carbon atoms to the acetic anhydride-containing residues, heating the acetic anhydride-containing residues with the added carboxylic acid to 30 to 100°C, adding 1 to 10 mol of methanol per mol of acetic anhydride, following reaction of the acetic anhydride with methanol, removing constituents boiling more readily than the carboxylic acid by distillation, cooling the distillate residue to a temperature ~ 50°C and separating the precipitated rhodium-containing solid from the distillation residue.
2. The process as claimed in claim 1, wherein the acetic anhydride-containing residues contains 10 to 60% by weight of acetic anhydride.
2. The process as claimed in claim 1, wherein the acetic anhydride-containing residues contains 10 to 60% by weight of acetic anhydride.
3. The process as claimed in claim 1, wherein the acetic anhydride-containing residues contains 15 to 50% by weight of anhydride.
4. The process as claimed in claim 1, wherein the acetic anhydride-containing residues contains 20 to 40% by weight of anhydride.
5. The process as claimed in claims 1 to 4, wherein the acetic anhydride-containing residues contains 200 to 2000 ppm of rhodium.
6. The process as claimed in any one of claims 1 to 4, wherein the acetic anhydride-containing residues contains 250 to 1500 ppm of rhodium.
7. The process as claimed in any one of claims 1 to 4, wherein the acetic anhydride-containing residues contains 280 to 1000 ppm of rhodium.
8. The process as claimed in any one of claims 1 to 7, wherein carboxylic acid is added to the acetic anhydride-containing residues so that the acetic anhydride-containing residues contains 10 to 150 ppm of rhodium.
9. The process as claimed in any one of claims 1 to 7, wherein carboxylic acid is added to the acetic anhydride-containing residues so that the acetic anhydride-containing residues contains 30 to 120 ppm of rhodium.
10. The process as claimed in any one of claims 1 to 7, wherein carboxylic acid is added to the acetic anhydride-containing residues so that the acetic anhydride-containing residues contains 50 to 100 ppm of rhodium.
11. The process as claimed in any one of claims 1 to 10, wherein the carboxylic acid is acetic acid.
12. The process as claimed in any one of claims 1 to 11, wherein the acetic anhydride-containing residues with the added carboxylic acid is heated to a temperature of 35 to 90°C.
13. The process as claimed in any one of claims 1 to 11, wherein the acetic anhydride-containing residues with the added carboxylic acid is heated to a temperature of 40 to 80°C.
14. The process as claimed in any one of claims 1 to 13, wherein 1.5 to 7 mol of methanol are added per mol of acetic anhydride.
15. The process as claimed in any one of claims 1 to 13, wherein 2 to 6 mol of methanol are added per mol of acetic anhydride.
16. The process as claimed in any one of claims 1 to 15, wherein the constituents methyl acetate and methanol boiling more readily than the carboxylic acid, are separated off by distillation.
17. The process as claimed in any one of claims 1 to 16, wherein, after separating off the constituents boiling more readily than the carboxylic acid, the mixture is cooled to a temperature ~ 40°C.
18. The process as claimed in any one of claims 1 to 16, wherein, after separating off the constituents boiling more readily than the carboxylic acid, the mixture is cooled to a temperature ~ 35°C.
19. The process as claimed in any one of claims 1 to 16, wherein, after separating off the constituents boiling more readily than the carboxylic acid, the mixture is cooled to a temperature ~ 30°C.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP4210027.5 | 1992-03-27 | ||
| DE19924210027 DE4210027A1 (en) | 1992-03-27 | 1992-03-27 | Process for the recovery of rhodium from carbonylation reaction residues |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2092049A1 CA2092049A1 (en) | 1993-09-28 |
| CA2092049C true CA2092049C (en) | 2000-10-31 |
Family
ID=6455190
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2092049 Expired - Fee Related CA2092049C (en) | 1992-03-27 | 1993-03-19 | Process for the recovery of rhodium from residues of carbonylation reactions |
Country Status (11)
| Country | Link |
|---|---|
| EP (1) | EP0564862A1 (en) |
| JP (1) | JPH0784629B2 (en) |
| KR (1) | KR100251252B1 (en) |
| CN (1) | CN1077908A (en) |
| AU (1) | AU656844B2 (en) |
| BR (1) | BR9301283A (en) |
| CA (1) | CA2092049C (en) |
| DE (1) | DE4210027A1 (en) |
| MX (1) | MX9301572A (en) |
| TW (1) | TW212144B (en) |
| ZA (1) | ZA931987B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004058402A2 (en) * | 2002-12-23 | 2004-07-15 | Eastman Chemical Company | Process for the recovery of phosphorus and iodine containing catalyst components |
| BE1030095B1 (en) * | 2021-12-24 | 2023-07-26 | Indaver Nv | METHOD FOR PROCESSING LIQUID PHARMACOCHEMICAL AND/OR FINE CHEMICAL WASTE MATERIALS CONTAINING ORGANIC SOLVENTS AND PRECIOUS METALS |
| BE1030097B1 (en) * | 2021-12-24 | 2023-07-25 | Indaver Nv | Method for optimizing liquid pharmacochemical and/or fine chemical wastes comprising organic solvents and precious metals |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE591195C (en) * | 1931-04-25 | 1934-01-18 | Consortium Elektrochem Ind | Process for separating liquid mixtures of acetic anhydride, acetic acid and water |
| DE1290535C2 (en) * | 1968-01-31 | 1975-11-20 | Ruhrchemie Ag, 4200 Oberhausen | PROCESS FOR SEPARATION AND RECOVERY OF RHODIUM FROM HYDROFORMYLATION PRODUCTS |
| US4340569A (en) * | 1981-03-06 | 1982-07-20 | The Halcon Sd Group, Inc. | Treatment of carbonylation residues |
| US4434241A (en) * | 1982-09-27 | 1984-02-28 | Eastman Kodak Company | Catalyst recovery process from tar from carbonylation reactions |
| US4578368A (en) * | 1985-05-06 | 1986-03-25 | Eastman Kodak Company | Catalyst recovery process |
| US4659682A (en) * | 1985-07-08 | 1987-04-21 | The Halcon Sd Group, Inc. | Recovery of noble metal values from carbonylation residues |
| US4605541A (en) * | 1985-08-26 | 1986-08-12 | The Halcon Sd Group, Inc. | Recovery of noble metal values from carbonylation residues using immiscible liquids |
| DE3610603A1 (en) * | 1986-03-29 | 1987-10-01 | Hoechst Ag | METHOD FOR CLEANING AND RECOVERY OF THE POLLUTED CATALYST SOLUTION RESULTING FROM CARBONYLATING METHYL ACETATE AND / OR DIMETHYL ETHER |
| GB8618710D0 (en) * | 1986-07-31 | 1986-09-10 | Bp Chem Int Ltd | Recovering metals |
| US4950629A (en) * | 1988-12-27 | 1990-08-21 | Eli Lilly And Company | Process for catalyst recovery |
| DE3903909A1 (en) * | 1989-02-10 | 1990-08-16 | Hoechst Ag | METHOD FOR REMOVING METALLIC CORROSION PRODUCTS FROM A POLLUTED CATALYST SOLUTION RESULTING FROM CARBONYLATING METHANOL AND / OR METHYL ACETATE AND / OR DIMETHYL ETHER |
-
1992
- 1992-03-27 DE DE19924210027 patent/DE4210027A1/en not_active Withdrawn
-
1993
- 1993-02-27 TW TW82101425A patent/TW212144B/en active
- 1993-03-18 EP EP19930104407 patent/EP0564862A1/en not_active Withdrawn
- 1993-03-19 KR KR1019930004234A patent/KR100251252B1/en not_active IP Right Cessation
- 1993-03-19 ZA ZA931987A patent/ZA931987B/en unknown
- 1993-03-19 CA CA 2092049 patent/CA2092049C/en not_active Expired - Fee Related
- 1993-03-19 MX MX9301572A patent/MX9301572A/en not_active IP Right Cessation
- 1993-03-19 JP JP6046393A patent/JPH0784629B2/en not_active Expired - Lifetime
- 1993-03-24 BR BR9301283A patent/BR9301283A/en not_active IP Right Cessation
- 1993-03-25 CN CN93103475A patent/CN1077908A/en active Pending
- 1993-03-26 AU AU35451/93A patent/AU656844B2/en not_active Ceased
Also Published As
| Publication number | Publication date |
|---|---|
| CA2092049A1 (en) | 1993-09-28 |
| KR100251252B1 (en) | 2000-04-15 |
| JPH0784629B2 (en) | 1995-09-13 |
| KR930019557A (en) | 1993-10-18 |
| JPH0641653A (en) | 1994-02-15 |
| TW212144B (en) | 1993-09-01 |
| DE4210027A1 (en) | 1993-09-30 |
| ZA931987B (en) | 1993-10-19 |
| AU3545193A (en) | 1993-09-30 |
| AU656844B2 (en) | 1995-02-16 |
| MX9301572A (en) | 1993-11-01 |
| CN1077908A (en) | 1993-11-03 |
| BR9301283A (en) | 1993-10-05 |
| EP0564862A1 (en) | 1993-10-13 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| MKLA | Lapsed |