USRE34281E - Removal of iodine or ioidide impurities - Google Patents
Removal of iodine or ioidide impurities Download PDFInfo
- Publication number
- USRE34281E USRE34281E US07/831,889 US83188992A USRE34281E US RE34281 E USRE34281 E US RE34281E US 83188992 A US83188992 A US 83188992A US RE34281 E USRE34281 E US RE34281E
- Authority
- US
- United States
- Prior art keywords
- carboxylic acid
- acid anhydride
- iodine
- anhydride
- treated
- 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.)
- Expired - Lifetime
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- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 229910052740 iodine Inorganic materials 0.000 title claims abstract description 17
- 239000011630 iodine Substances 0.000 title claims abstract description 17
- 239000012535 impurity Substances 0.000 title claims abstract description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 29
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims abstract description 26
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 claims abstract description 24
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 23
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims abstract description 19
- WFDIJRYMOXRFFG-UHFFFAOYSA-N acetic acid anhydride Natural products CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims abstract description 13
- 230000006315 carbonylation Effects 0.000 claims abstract description 12
- 238000005810 carbonylation reaction Methods 0.000 claims abstract description 12
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical group [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims abstract description 10
- -1 heterocyclic aromatic nitrogen compound Chemical class 0.000 claims abstract description 6
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical group [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 claims abstract description 6
- 229910017464 nitrogen compound Inorganic materials 0.000 claims abstract description 5
- 229940071536 silver acetate Drugs 0.000 claims abstract description 5
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 6
- 238000004821 distillation Methods 0.000 claims description 5
- JKFYKCYQEWQPTM-UHFFFAOYSA-N 2-azaniumyl-2-(4-fluorophenyl)acetate Chemical compound OC(=O)C(N)C1=CC=C(F)C=C1 JKFYKCYQEWQPTM-UHFFFAOYSA-N 0.000 claims description 3
- 229910021612 Silver iodide Inorganic materials 0.000 claims description 3
- 235000019260 propionic acid Nutrition 0.000 claims description 3
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 3
- 229940045105 silver iodide Drugs 0.000 claims description 3
- 239000002516 radical scavenger Substances 0.000 abstract description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 5
- 229910052703 rhodium Inorganic materials 0.000 description 5
- 239000010948 rhodium Substances 0.000 description 5
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 5
- 229910052709 silver Inorganic materials 0.000 description 5
- 239000004332 silver Substances 0.000 description 5
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 3
- 238000013459 approach Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000003947 neutron activation analysis Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical group CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- 150000001341 alkaline earth metal compounds Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- GQZXNSPRSGFJLY-UHFFFAOYSA-N hydroxyphosphanone Chemical compound OP=O GQZXNSPRSGFJLY-UHFFFAOYSA-N 0.000 description 1
- 229940046817 hypophosphorus acid Drugs 0.000 description 1
- BVJUXXYBIMHHDW-UHFFFAOYSA-N iodane Chemical compound I.I BVJUXXYBIMHHDW-UHFFFAOYSA-N 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000002000 scavenging effect Effects 0.000 description 1
- 150000003378 silver Chemical class 0.000 description 1
- XXNUGDMAINQNIH-UHFFFAOYSA-M silver;propanoate;propanoic acid Chemical compound [Ag+].CCC(O)=O.CCC([O-])=O XXNUGDMAINQNIH-UHFFFAOYSA-M 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/487—Separation; Purification; Stabilisation; Use of additives by treatment giving rise to chemical modification
-
- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S203/00—Distillation: processes, separatory
- Y10S203/06—Reactor-distillation
Definitions
- the present invention relates to a process for removing iodine or iodide impurities from the products of carbonylation processes.
- the present invention relates to the removal of iodine or iodide impurities from carboxylic acid or carboxylic acid anhydrides prepared by the rhodium catalysed carbonylation of alcohols, olefins or esters.
- rhodium/iodide catalysts to effect the carbonylation of alcohols (eg methanol to acetic acid), olefins (eg ethylene to propionic acid) and esters (e.g. methyl acetate to acetic anhydride) is well known. It is also known that the carboxylic acid or carboxylic acid anhydride products tend to retain iodide, in the forms of iodine or soluble iodides, which must be subsequently removed.
- alcohols eg methanol to acetic acid
- olefins eg ethylene to propionic acid
- esters e.g. methyl acetate to acetic anhydride
- U.S. Pat. No. 4,029,553 describes a distillation process for generating high purity acetic acid containing less than 20 parts per billion iodide.
- U.S. Pat. No. 3,772,156 discloses a two column distillation process in which the crude acetic acid is contacted with an alkali or alkaline earth metal compound either alone or in combination with hypophosphorus acid.
- U.S. Pat. No. 3,709,795 discloses a process for removing halide impurities from acetic acid which involves the use of a strong inorganic oxidising agent such as potassium permanganate. Whilst effective, this latter process is not easy to carry out commercially.
- U.S. Pat. No. 4,664,753 discloses a particularly effective method of removing iodine and soluble iodide impurities from the products of carbonylation processes. This patent describes contacting the product with a mixture of (a) an alkyl or aryl phosphine or a heterocyclic aromatic nitrogen compound and (b) a metal selected from copper, silver, zinc or cadmium.
- the present invention provides a process for removing iodine or soluble iodide impurities from a carboxylic acid or carboxylic acid anhydride, the carboxylic acid or carboxylic acid anhydride having been produced by a carbonylation process, which process comprises step (a) treating impure carboxylic acid or carboxylic acid anhydride containing iodine or soluble iodide impurities with an unsupported scavenger at a temperature of between 20° and 250° C.
- the invention solves the problems by selecting from U.S. Pat. No. 4,664,753 a metal (silver) which is more effective without a phosphine or heterocyclic aromatic nitrogen compound. This is unexpected because U.S. Pat. No. 4,664,753 suggests (see Examples 1 and 3) that a phosphine is needed in order to obtain a product of high purity.
- the silver salt can be any one which will react with iodide to generate insoluble silver iodide.
- the salt should be soluble in the carboxylic acid or carboxylic acid anhydride. It is most preferred, if possible to use a silver salt having an anion corresponding to the carboxylic acid being treated. Thus for acetic acid, silver acetate is most preferred whilst for propionic acid silver propionate should be used.
- suspensions of silver salts if the silver salt is insoluble or sparingly soluble in the liquid medium being purified. In these cases, it is preferred that the suspension is finely divided.
- the process of the present invention is particularly suitable for treating carboxylic acids or carboxylic acid anhydrides having up to 300 ppm iodine or soluble iodide impurities.
- the silver is recovered from the process as silver iodide which can either be disposed of or treated to regenerate the appropriate silver salt.
- the scavenger and the carboxylic acid or carboxylic acid anhydride are kept in contact until substantially all the iodine or iodide is scavenged.
- a suitable contact time is one in the range 10 to 100 minutes.
- the mixture may be stirred or otherwise agitated if desired.
- the process of the present invention is able to reduce the level of iodine or soluble iodide impurities to levels in the order of less than 100 parts per billion, preferably to less than 20 parts par billion.
- the process of the present invention is particularly suitable for use in purifying (a) acetic acid produced by rhodium/iodide catalysed methanol carbonylation, (b) propionic acid produced by rhodium/iodide catalysed ethylene carbonylation and (c) acetic anhydride produced by rhodium/iodide catalysed carbonylation of methyl acetate.
- the process is equally applicable to kettles for processes using carboxylic acids and carboxylic acid anhydride feedstocks in conjunction with iodide sensitive catalysts (e.g. vinyl acetate monomer production).
- a 500 ml three necked round bottomed flask was equipped with a Eurotherm controlled heating mantle, a thermo-couple pocket, two wide bore taps--one connected to a Liebig condenser and the other to a stillhead condenser and receiver.
- the flask was charged with 450 ml of the impure acetic acid (iodide level as determined by neutron activation analysis), the prerequisite amount of scavenger and a few antibumping granules. Both the condenser and the distillation apparatus were purged with nitrogen.
- the apparatus With the tap open to the condenser only, the apparatus was brought to a gentle reflux (simmer). After 1 hour the second tap was opened and the first closed. The reflux was increased to rapid distillation of the treated acetic acid. The experiment was terminated when 90% of the acetic acid had been collected. The distilled acetic acid was analysed for total iodide content (by neutron activation analysis).
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- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Treating Waste Gases (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
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Abstract
A process for removing iodine or soluble iodide impurities from a carboxylic acid or carboxylic acid anhydride, the carboxylic acid or carboxylic acid anhydride having been by a carbonylation process. The process includes: step (a) treating impure carboxylic acid or carboxylic acid anhydride containing iodine or soluble iodide impurities with an unsupported scavenger at a temperature of between 20° and 250° C. and step (b) thereafter separating the treated carboxylic acid or carboxylic acid anhydride from the scavenger. The scavenger is a silver salt in the absence of a trialkyl phosphine, a triaryl phosphine and a heterocyclic aromatic nitrogen compound. The preferred scavenger for acetic acid and acetic anhydride is silver acetate.
Description
The present invention relates to a process for removing iodine or iodide impurities from the products of carbonylation processes. In particular the present invention relates to the removal of iodine or iodide impurities from carboxylic acid or carboxylic acid anhydrides prepared by the rhodium catalysed carbonylation of alcohols, olefins or esters.
The uss of rhodium/iodide catalysts to effect the carbonylation of alcohols (eg methanol to acetic acid), olefins (eg ethylene to propionic acid) and esters (e.g. methyl acetate to acetic anhydride) is well known. It is also known that the carboxylic acid or carboxylic acid anhydride products tend to retain iodide, in the forms of iodine or soluble iodides, which must be subsequently removed.
A number of methods have been developed to effect iodide removal and some are operated commercially on plant using carbonylation technology. U.S. Pat. No. 4,029,553 describes a distillation process for generating high purity acetic acid containing less than 20 parts per billion iodide. A different approach is described in U.S. Pat. No. 3,772,156 which discloses a two column distillation process in which the crude acetic acid is contacted with an alkali or alkaline earth metal compound either alone or in combination with hypophosphorus acid. Finally U.S. Pat. No. 3,709,795 discloses a process for removing halide impurities from acetic acid which involves the use of a strong inorganic oxidising agent such as potassium permanganate. Whilst effective, this latter process is not easy to carry out commercially.
Other approaches of interest include the use of a silver ionexchange resin (EP No. 196173) and the use of a peracid (DE No. 3612504)
U.S. Pat. No. 4,664,753 discloses a particularly effective method of removing iodine and soluble iodide impurities from the products of carbonylation processes. This patent describes contacting the product with a mixture of (a) an alkyl or aryl phosphine or a heterocyclic aromatic nitrogen compound and (b) a metal selected from copper, silver, zinc or cadmium.
A problem arises with the approach described in U.S. Pat. No. 4,664,753 in that when such a two component system is employed there is a possibility of contaminating the carbonylation product with the first of the above mentioned components. Hence the problem to be solved is the prevention of such contamination whilst maintaining an efficient scavenging system.
Accordingly, the present invention provides a process for removing iodine or soluble iodide impurities from a carboxylic acid or carboxylic acid anhydride, the carboxylic acid or carboxylic acid anhydride having been produced by a carbonylation process, which process comprises step (a) treating impure carboxylic acid or carboxylic acid anhydride containing iodine or soluble iodide impurities with an unsupported scavenger at a temperature of between 20° and 250° C. and step (b) thereafter separating the treated carboxylic acid or carboxylic acid anhydride from the scavenger characterised in that the scavenger consists of a silver salt in the absence of a trialkyl phosphine, a triaryl phosphine and a heterocyclic aromatic nitrogen compound.
The invention solves the problems by selecting from U.S. Pat. No. 4,664,753 a metal (silver) which is more effective without a phosphine or heterocyclic aromatic nitrogen compound. This is unexpected because U.S. Pat. No. 4,664,753 suggests (see Examples 1 and 3) that a phosphine is needed in order to obtain a product of high purity.
The silver salt can be any one which will react with iodide to generate insoluble silver iodide. Preferably, the salt should be soluble in the carboxylic acid or carboxylic acid anhydride. It is most preferred, if possible to use a silver salt having an anion corresponding to the carboxylic acid being treated. Thus for acetic acid, silver acetate is most preferred whilst for propionic acid silver propionate should be used.
It is also possible to use suspensions of silver salts if the silver salt is insoluble or sparingly soluble in the liquid medium being purified. In these cases, it is preferred that the suspension is finely divided.
The process of the present invention, is particularly suitable for treating carboxylic acids or carboxylic acid anhydrides having up to 300 ppm iodine or soluble iodide impurities. The silver is recovered from the process as silver iodide which can either be disposed of or treated to regenerate the appropriate silver salt. The scavenger and the carboxylic acid or carboxylic acid anhydride are kept in contact until substantially all the iodine or iodide is scavenged. For a process operating under a preferred temperature in the range 80° to 150° C., a suitable contact time is one in the range 10 to 100 minutes. The mixture may be stirred or otherwise agitated if desired. Typically the process of the present invention is able to reduce the level of iodine or soluble iodide impurities to levels in the order of less than 100 parts per billion, preferably to less than 20 parts par billion.
The process of the present invention is particularly suitable for use in purifying (a) acetic acid produced by rhodium/iodide catalysed methanol carbonylation, (b) propionic acid produced by rhodium/iodide catalysed ethylene carbonylation and (c) acetic anhydride produced by rhodium/iodide catalysed carbonylation of methyl acetate. However, the process is equally applicable to kettles for processes using carboxylic acids and carboxylic acid anhydride feedstocks in conjunction with iodide sensitive catalysts (e.g. vinyl acetate monomer production).
The invention will now be illustrated by reference to the following Examples.
A 500 ml three necked round bottomed flask was equipped with a Eurotherm controlled heating mantle, a thermo-couple pocket, two wide bore taps--one connected to a Liebig condenser and the other to a stillhead condenser and receiver. The flask was charged with 450 ml of the impure acetic acid (iodide level as determined by neutron activation analysis), the prerequisite amount of scavenger and a few antibumping granules. Both the condenser and the distillation apparatus were purged with nitrogen.
With the tap open to the condenser only, the apparatus was brought to a gentle reflux (simmer). After 1 hour the second tap was opened and the first closed. The reflux was increased to rapid distillation of the treated acetic acid. The experiment was terminated when 90% of the acetic acid had been collected. The distilled acetic acid was analysed for total iodide content (by neutron activation analysis).
Compare a silver acetate salt with copper (II) acetate and two scavenger systems according to U.S. Pat. No. 4,664,753. Examples A to C do not constitute part of the invention. The results (Table 1) show the unexpected superiority of silver acetate in the absence of a phosphine.
TABLE 1
______________________________________
Ex- Initial
Final
am- % w/w Iodide
Iodide % Re-
ple Scavenger Scavenger (ppb) (ppb) moval
______________________________________
1 Silver Acetate
0.03 991 50 ± 2
95
A Silver 0.03 662 653 ± 40
0
Acetate + of each
Triphenyl-
phosphine
B Copper (II) 0.03 991 850 ± 100
0
Acetate
C Copper (II) 0.03 1380 800 ± 47
42
Acetate + of each
Triphenyl-
phosphine
______________________________________
Claims (7)
1. A process for removing iodine or soluble iodide impurities from a carboxylic acid or carboxylic acid anhydride, the carboxylic acid or carboxylic acid anhydride having been produced by a carbonylation process, which process consists essentially of (a) treating the carboxylic acid or carboxylic acid anhydride containing iodine or soluble iodide impurities with a soluble silver salt in the absence of a trialkyl phosphine, a triaryl phosphine and a heterocyclic nitrogen compound, and step (b) thereafter separating the treated carboxylic acid and carboxylic acid anhydride by distillation from silver iodide produced in step (a), wherein the impure carboxylic acid or carboxylic acid anhydride contains .[.at least.]. .Iadd.up to .Iaddend.300 parts per million by weight in total of iodine and soluble iodide impurities and the treated carboxylic acid or carboxylic acid anhydride contains less than 100 parts per billion by weight in total of iodine and soluble iodide impurities.
2. The process as claimed in claim 1 wherein the silver salt is silver acetate.
3. The process as claimed in claim 1 wherein the silver salt is the silver salt of the carboxylic acid or carboxylic acid anhydride which is treated.
4. The process as claimed in claim 1 wherein the carboxylic acid or carboxylic acid anhydride is chosen from the group consisting of acetic acid, propionic acid and acetic anhydride.
5. The process as claimed in claim 1 wherein the step (a) is carried out at a temperature in the range 80°-150° C.
6. The process as claimed in claim 1 wherein the carboxylic acid or carboxylic acid anhydride is treated with the silver salt for a period of time in the range from 10 to 100 minutes.
7. The process as claimed in claim 1 wherein the treated carboxylic acid or carboxylic acid anhydride contains less than 20 parts per billion by weight in total of iodine and soluble iodide impurities.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB8822661 | 1988-09-27 | ||
| GB888822661A GB8822661D0 (en) | 1988-09-27 | 1988-09-27 | Removal of iodine/iodide impurities |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US07/409,126 Reissue US4975155A (en) | 1988-09-27 | 1989-09-19 | Removal of iodine or iodide impurities |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| USRE34281E true USRE34281E (en) | 1993-06-15 |
Family
ID=10644313
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US07/409,126 Ceased US4975155A (en) | 1988-09-27 | 1989-09-19 | Removal of iodine or iodide impurities |
| US07/831,889 Expired - Lifetime USRE34281E (en) | 1988-09-27 | 1992-02-06 | Removal of iodine or ioidide impurities |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US07/409,126 Ceased US4975155A (en) | 1988-09-27 | 1989-09-19 | Removal of iodine or iodide impurities |
Country Status (12)
| Country | Link |
|---|---|
| US (2) | US4975155A (en) |
| EP (1) | EP0361785B1 (en) |
| JP (1) | JP2820977B2 (en) |
| KR (1) | KR0133668B1 (en) |
| CN (1) | CN1027163C (en) |
| AT (1) | ATE109450T1 (en) |
| AU (1) | AU612514B2 (en) |
| CA (1) | CA1311247C (en) |
| DE (1) | DE68917240T2 (en) |
| ES (1) | ES2057139T3 (en) |
| GB (1) | GB8822661D0 (en) |
| NO (1) | NO172434C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5916422A (en) | 1994-08-12 | 1999-06-29 | Daicel Chemical Industries, Ltd. | Method of purifying acetic acid |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB9022787D0 (en) * | 1990-10-19 | 1990-12-05 | British Petroleum Co Plc | Process |
| GB9100216D0 (en) * | 1991-01-05 | 1991-02-20 | Bp Chem Int Ltd | Process |
| GB9120902D0 (en) * | 1991-10-02 | 1991-11-13 | Bp Chem Int Ltd | Purification process |
| GB9211671D0 (en) * | 1992-06-02 | 1992-07-15 | Bp Chem Int Ltd | Process |
| EP1114814A3 (en) * | 1999-12-29 | 2003-01-22 | Haldor Topsoe A/S | Method for the reduction of iodine compounds from a process stream |
| CN101676927B (en) | 2008-09-18 | 2012-06-06 | 山东新北洋信息技术股份有限公司 | Magcard bit-density control device and control method |
| CN104045548B (en) * | 2013-03-14 | 2016-08-10 | 中国石油化工股份有限公司 | A kind of remove the method for Trace Iodine in acetic acid |
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| US3658467A (en) * | 1969-07-28 | 1972-04-25 | Atomic Energy Commission | System for total iodine retention |
| US3772156A (en) * | 1971-11-19 | 1973-11-13 | Monsanto Co | Purification of acetic acid streams by distillation |
| DE3329781A1 (en) * | 1983-08-18 | 1985-02-28 | Hoechst Ag, 6230 Frankfurt | METHOD FOR SEPARATING IODINE AND ITS COMPOUNDS FROM CARBONYLATION PRODUCTS OBTAINED FROM CARBONYLATING DIMETHYL ETHER, METHYL ACETATE OR METHANOL |
| EP0196173A1 (en) * | 1985-03-07 | 1986-10-01 | Celanese Corporation | Removal of iodide compounds from non-aqueous organic media |
| EP0217191A1 (en) * | 1985-09-30 | 1987-04-08 | Hoechst Aktiengesellschaft | Process for the separation of iodine and its compounds from carbonylation products obtained by the carbonylation of dimethyl ether, methyl acetate or methanol |
| EP0296584A2 (en) * | 1987-06-24 | 1988-12-28 | Union Carbide Corporation | Removal of halides from carboxylic acids |
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| US3709795A (en) | 1970-02-02 | 1973-01-09 | Monsanto Co | Purification of carboxylic acids by chemical treatment and distillation |
| US4029553A (en) | 1975-07-28 | 1977-06-14 | Monsanto Company | Purification of acetic acid streams by distillation |
| DE3331548A1 (en) * | 1983-09-01 | 1985-03-21 | Hoechst Ag, 6230 Frankfurt | METHOD FOR SEPARATING IODINE AND ITS COMPOUNDS FROM CARBONYLATION PRODUCTS OBTAINED FROM CARBONYLATING DIMETHYL ETHER, METHYL ACETATE OR METHANOL |
-
1988
- 1988-09-27 GB GB888822661A patent/GB8822661D0/en active Pending
-
1989
- 1989-09-19 US US07/409,126 patent/US4975155A/en not_active Ceased
- 1989-09-20 AU AU41635/89A patent/AU612514B2/en not_active Ceased
- 1989-09-21 AT AT89309597T patent/ATE109450T1/en not_active IP Right Cessation
- 1989-09-21 DE DE68917240T patent/DE68917240T2/en not_active Expired - Fee Related
- 1989-09-21 ES ES89309597T patent/ES2057139T3/en not_active Expired - Lifetime
- 1989-09-21 EP EP89309597A patent/EP0361785B1/en not_active Expired - Lifetime
- 1989-09-22 CA CA000612580A patent/CA1311247C/en not_active Expired - Lifetime
- 1989-09-25 JP JP1246617A patent/JP2820977B2/en not_active Expired - Lifetime
- 1989-09-26 NO NO893816A patent/NO172434C/en unknown
- 1989-09-27 KR KR1019890013910A patent/KR0133668B1/en not_active Expired - Fee Related
- 1989-09-27 CN CN89107524A patent/CN1027163C/en not_active Expired - Fee Related
-
1992
- 1992-02-06 US US07/831,889 patent/USRE34281E/en not_active Expired - Lifetime
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3658467A (en) * | 1969-07-28 | 1972-04-25 | Atomic Energy Commission | System for total iodine retention |
| US3772156A (en) * | 1971-11-19 | 1973-11-13 | Monsanto Co | Purification of acetic acid streams by distillation |
| DE3329781A1 (en) * | 1983-08-18 | 1985-02-28 | Hoechst Ag, 6230 Frankfurt | METHOD FOR SEPARATING IODINE AND ITS COMPOUNDS FROM CARBONYLATION PRODUCTS OBTAINED FROM CARBONYLATING DIMETHYL ETHER, METHYL ACETATE OR METHANOL |
| US4664753A (en) * | 1983-08-18 | 1987-05-12 | Hoechst Aktiengesellschaft | Process for separating iodine and its compounds from the carbonylation products obtained by subjecting dimethylether, methyl acetate or methanol to a carbonylation reaction |
| EP0196173A1 (en) * | 1985-03-07 | 1986-10-01 | Celanese Corporation | Removal of iodide compounds from non-aqueous organic media |
| US4615806A (en) * | 1985-03-07 | 1986-10-07 | Celanese Corporation | Removal of iodide compounds from non-aqueous organic media |
| US4615806B1 (en) * | 1985-03-07 | 1994-05-03 | Hoechst Co American | Removal of iodide compounds from non-aqueous organic media |
| EP0217191A1 (en) * | 1985-09-30 | 1987-04-08 | Hoechst Aktiengesellschaft | Process for the separation of iodine and its compounds from carbonylation products obtained by the carbonylation of dimethyl ether, methyl acetate or methanol |
| EP0296584A2 (en) * | 1987-06-24 | 1988-12-28 | Union Carbide Corporation | Removal of halides from carboxylic acids |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5916422A (en) | 1994-08-12 | 1999-06-29 | Daicel Chemical Industries, Ltd. | Method of purifying acetic acid |
Also Published As
| Publication number | Publication date |
|---|---|
| NO172434C (en) | 1993-07-21 |
| CN1027163C (en) | 1994-12-28 |
| EP0361785B1 (en) | 1994-08-03 |
| ATE109450T1 (en) | 1994-08-15 |
| KR0133668B1 (en) | 1998-04-21 |
| AU4163589A (en) | 1990-04-05 |
| CA1311247C (en) | 1992-12-08 |
| EP0361785A3 (en) | 1991-10-09 |
| NO172434B (en) | 1993-04-13 |
| NO893816D0 (en) | 1989-09-26 |
| JP2820977B2 (en) | 1998-11-05 |
| ES2057139T3 (en) | 1994-10-16 |
| US4975155A (en) | 1990-12-04 |
| DE68917240T2 (en) | 1994-11-24 |
| AU612514B2 (en) | 1991-07-11 |
| CN1041357A (en) | 1990-04-18 |
| DE68917240D1 (en) | 1994-09-08 |
| NO893816L (en) | 1990-03-28 |
| KR900004667A (en) | 1990-04-12 |
| GB8822661D0 (en) | 1988-11-02 |
| EP0361785A2 (en) | 1990-04-04 |
| JPH02129142A (en) | 1990-05-17 |
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