WO2005107945A1 - Process for the removal of corrosion metals from carbonylation catalyst solutions - Google Patents
Process for the removal of corrosion metals from carbonylation catalyst solutions Download PDFInfo
- Publication number
- WO2005107945A1 WO2005107945A1 PCT/GB2005/001216 GB2005001216W WO2005107945A1 WO 2005107945 A1 WO2005107945 A1 WO 2005107945A1 GB 2005001216 W GB2005001216 W GB 2005001216W WO 2005107945 A1 WO2005107945 A1 WO 2005107945A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- process according
- carbonylation
- resin
- catalyst
- alkali
- Prior art date
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 96
- 238000005810 carbonylation reaction Methods 0.000 title claims abstract description 92
- 230000006315 carbonylation Effects 0.000 title claims abstract description 76
- 238000000034 method Methods 0.000 title claims abstract description 60
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 43
- 239000002184 metal Substances 0.000 title claims abstract description 43
- 238000005260 corrosion Methods 0.000 title claims abstract description 37
- 230000007797 corrosion Effects 0.000 title claims abstract description 37
- 150000002739 metals Chemical class 0.000 title description 8
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 61
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 28
- 229910052741 iridium Inorganic materials 0.000 claims abstract description 28
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000003513 alkali Substances 0.000 claims abstract description 27
- 239000000356 contaminant Substances 0.000 claims abstract description 24
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 20
- 239000010948 rhodium Substances 0.000 claims abstract description 20
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims abstract description 20
- 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 claims abstract description 19
- 239000003729 cation exchange resin Substances 0.000 claims abstract description 19
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 75
- 239000011347 resin Substances 0.000 claims description 62
- 229920005989 resin Polymers 0.000 claims description 62
- -1 alkaline earth metal salt Chemical class 0.000 claims description 27
- 229910052783 alkali metal Inorganic materials 0.000 claims description 25
- 150000001340 alkali metals Chemical class 0.000 claims description 24
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 21
- 229910052744 lithium Inorganic materials 0.000 claims description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 12
- 229910052708 sodium Inorganic materials 0.000 claims description 11
- 239000011734 sodium Substances 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 10
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 claims description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 8
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical group [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 8
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 8
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 8
- 238000011068 loading method Methods 0.000 claims description 8
- 229910052707 ruthenium Inorganic materials 0.000 claims description 8
- 239000007791 liquid phase Substances 0.000 claims description 7
- 229910052762 osmium Inorganic materials 0.000 claims description 6
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 229910052702 rhenium Inorganic materials 0.000 claims description 5
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000011651 chromium Substances 0.000 claims description 3
- 238000010924 continuous production Methods 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- 229920001568 phenolic resin Polymers 0.000 claims description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- 238000009833 condensation Methods 0.000 claims description 2
- 230000005494 condensation Effects 0.000 claims description 2
- SLGWESQGEUXWJQ-UHFFFAOYSA-N formaldehyde;phenol Chemical compound O=C.OC1=CC=CC=C1 SLGWESQGEUXWJQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 239000011572 manganese Substances 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 1
- MYRTYDVEIRVNKP-UHFFFAOYSA-N divinylbenzene Substances C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims 1
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 9
- 239000011777 magnesium Substances 0.000 description 7
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000003426 co-catalyst Substances 0.000 description 6
- 229910052749 magnesium Inorganic materials 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000000376 reactant Substances 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 6
- 150000001298 alcohols Chemical class 0.000 description 5
- 238000011065 in-situ storage Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 5
- 150000001350 alkyl halides Chemical class 0.000 description 4
- 150000001735 carboxylic acids Chemical class 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- YZUPZGFPHUVJKC-UHFFFAOYSA-N 1-bromo-2-methoxyethane Chemical compound COCCBr YZUPZGFPHUVJKC-UHFFFAOYSA-N 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 3
- 150000001242 acetic acid derivatives Chemical class 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 150000004694 iodide salts Chemical class 0.000 description 3
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical group [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 3
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 3
- 235000011285 magnesium acetate Nutrition 0.000 description 3
- 239000011654 magnesium acetate Substances 0.000 description 3
- 229940069446 magnesium acetate Drugs 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000001632 sodium acetate Substances 0.000 description 3
- 235000017281 sodium acetate Nutrition 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 229910001516 alkali metal iodide Inorganic materials 0.000 description 2
- 229910001619 alkaline earth metal iodide Inorganic materials 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 235000009518 sodium iodide Nutrition 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- OKJPEAGHQZHRQV-UHFFFAOYSA-N Triiodomethane Natural products IC(I)I OKJPEAGHQZHRQV-UHFFFAOYSA-N 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229940023913 cation exchange resins Drugs 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 150000001983 dialkylethers Chemical class 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 description 1
- IAQLJCYTGRMXMA-UHFFFAOYSA-M lithium;acetate;dihydrate Chemical compound [Li+].O.O.CC([O-])=O IAQLJCYTGRMXMA-UHFFFAOYSA-M 0.000 description 1
- 230000000116 mitigating effect Effects 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 238000011027 product recovery Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
Classifications
-
- 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
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/74—Regeneration or reactivation of catalysts, in general utilising ion-exchange
-
- 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
- B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
- B01J39/04—Processes using organic exchangers
-
- 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
- C07C51/47—Separation; Purification; Stabilisation; Use of additives by solid-liquid treatment; by chemisorption
-
- 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
Definitions
- the present invention relates to the removal of corrosion metal contaminants from carbonylation catalyst solutions comprising a carbonylation catalyst such as iridium, rhodium or mixtures thereof.
- a carbonylation catalyst such as iridium, rhodium or mixtures thereof.
- the production of acetic acid by the carbonylation of methanol in the presence of an iridium catalyst and a promoter such as ruthenium is well known and is described, for example, in EP-A-0752406, EP-A-0849248, EP-A-0849249, and EP-A- 1002785.
- PCT patent application, WO 97/15544 describes a process for treating low water content carbonylation catalyst solutions which contain rhodium and an alkali metal to remove metallic corrosion products.
- the process comprises contacting the catalyst solution with an ion exchange resin and a sufficient amount of water to decrease the concentration of alkali metal ions to optimize removal of corrosion metal products.
- the carbonylation reaction composition from the reactor is passed to a flash zone for separation into a vapour fraction and a liquid fraction which comprises the majority of the catalyst components.
- This carbonylation catalyst solution is generally recycled back to the reactor.
- An iridium or an iridium/rhodium catalysed process is susceptible to small changes in alkali metal concentration and thus increases in the alkali metal concentration is likely to reduce the carbonylation rate and may cause a significant reduction in the rate.
- a rhodium catalysed process can tolerate greater concentrations of alkali metal however fluctuations in the alkali metal concentration will cause the carbonylation reaction rate to vary resulting in non-steady operation which is both undesirable and uneconomic. It has now been found that by partially loading a cation exchange resin with alkali/alkaline earth metal, the concentration of the alkali/alkaline earth metal in the carbonylation solution can be maintained thereby eliminating or at least mitigating the aforementioned disadvantages.
- the present invention provides a process for the removal of corrosion metal contaminants from a carbonylation catalyst solution comprising a carbonylation catalyst selected from iridium, rhodium and mixtures thereof, an alkali and/or alkaline earth metal and corrosion metal contaminants which process comprises contacting said catalyst solution with a cation exchange resin having its active sites partially loaded with a sufficient amount of alkali and/or alkaline earth metal to maintain the concentration of said alkali and or alkaline earth metal in the catalyst solution and recovering a catalyst solution of reduced corrosion metal contaminant content.
- the process of the present invention is particularly applicable to the removal of corrosion metal contaminants from carbonylation catalyst solutions obtained from carbonylation processes employing in the carbonylation reaction composition either an iridium carbonylation catalyst, a rhodium carbonylation catalyst or a combination of iridium and rhodium carbonylation catalysts and also an alkali or alkaline earth metal salt capable of generating iodide ions in-situ.
- the carbonylation catalyst solution is derived from the liquid phase carbonylation of alcohols and/or reactive derivatives thereof, such as ethers, esters, halides or mixtures thereof to produce carboxylic acids, preferably, acetic acid in the presence of an iridium carbonylation catalyst, a rhodium carbonylation catalyst or a combination of iridi ⁇ m and rhodium carbonylation catalysts, an alkyl halide co-catalyst and an alkali metal or alkaline earth metal salt capable of generating iodide ions in-situ such as an alkali metal or alkaline earth metal iodide or an alkali metal or alkaline earth metal acetate.
- alcohols and/or reactive derivatives thereof such as ethers, esters, halides or mixtures thereof to produce carboxylic acids, preferably, acetic acid in the presence of an iridium carbonylation catalyst, a rhodium carbonylation catalyst or a combination of
- a catalyst promoter such as ruthenium, rhenium or osmium may also be present in the carbonylation reaction composition.
- the carbonylation catalyst solution may be obtained from the liquid phase carbonylation of alcohols and/or reactive derivatives thereof in the presence of a rhodium catalyst and an alkali/alkaline earth metal salt capable of generating iodide ions in-situ under substantially anhydrous conditions to produce a carboxylic anhydride such as acetic anhydride or a mixture of a carboxylic anhydride and a carboxylic acid such as a mixture of acetic anhydride and acetic acid.
- the carbonylation catalyst solution to be treated by the process of the present invention comprises an iridium carbonylation catalyst, a rhodium carbonylation catalyst or a mixture thereof.
- Suitable iridium carbonylation catalysts are described, for example in EP-A-0 643 034 and EP 0 752406.
- Suitable rhodium carbonylation catalysts are described, for example, in EP-A-0 161 874 and US 6,211,405.
- the carbonylation catalyst solution treated in the process of the present invention comprises an iridium carbonylation catalyst
- the catalyst solution may further . comprise one or more catalyst promoters.
- Suitable promoters are selected from ruthenium, osmium and rhenium, and are more preferably selected from ruthenium and osmium. Ruthenium is the most preferred promoter. Examples of suitable promoters are described, for example, in EP-A-0 643 034 and EP 0 752406.
- the carbonylation reaction composition comprises a source of alkali metal and/or alkaline, earth metal such as salts capable of generating iodide ions in-situ. Suitable salts include alkali metal or alkaline earth metal iodides and alkali metal or alkaline earth metal acetates.
- the alkali metal salt is lithium iodide, lithium acetate, sodium iodide or sodium acetate.
- Suitable alkaline earth metal salts are the iodides or acetates of calcium or magnesium.
- the carbonylation catalyst solution may also comprise unconverted carbonylation reactant, for example alcohols, ethers, halides or mixtures thereof.
- the reactant may comprise C ⁇ to do alcohols, such as methanol; dialkyl ethers wherein the alkyl groups independently have 1 to 10 carbon atoms, for example dimethyl ether; alkyl halides having 1 to 10 carbon atoms such as methyl iodide and esters of Ci to Cio alcohols with C 2 to C ⁇ carboxylic acids, for example, methyl acetate.
- carboxylic acids water is required as co-reactant for ether or ester reacta ⁇ ts.
- methanol and/or methyl acetate are used as reactants.
- the carbonylation catalyst solution treated in the process of the present invention may also comprise an alkyl halide co-catalyst such as methyl iodide.
- concentration of the alkyl halide co-catalyst, such as methyl iodide, in the liquid carbonylation reaction composition is in the range 1 to 20% by weight, preferably 2 to 16% by weight.
- the carbonylation catalyst solution may comprise a solvent compatible with the carbonylation process from which the catalyst solution is derived and which is also compatible with the cation exchange resin.
- the carboxylic acid to be produced is acetic acid
- the solvent may be acetic acid.
- the catalyst solution may also comprise water.
- Water may be formed in situ in the carbonylation reaction composition, for example, by' the esterification reaction between methanol reactant and acetic acid product.
- the concentration of water in process streams containing catalyst system for recycle to the carbonylation reaction zones is preferably maintained at a concentration of at least 0.5 % by weight.
- the carboxylic acid may comprise a carboxylic acid having 1 to 10 carbon atoms and is preferably acetic acid.
- carbonylation processes operate at 100 -300° C and at elevated pressure (15 to 200 barg) with a partial pressure of carbon monoxide of 2-30 atmospheres and may be carried out in one or more reaction zones.
- the process of the present invention is particularly applicable to the removal of corrosion metal contaminants from a carbonylation catalyst solution comprising an iridium carbonylation catalyst, methyl iodide co-catalyst, water, acetic acid, methyl acetate, at least one promoter selected from ruthenium, osmium and rhenium and an alkali and/or alkaline earth metal.
- the cation exchange resins suitable for use in the process of the present invention may be either of the strong-acid or the weak-acid type in the alkali or alkaline earth metal form. Any alkali metal or alkaline earth metal cation is acceptable provided the corresponding alkali'metal or alkaline earth metal cation is employed in the alkali metal or alkaline earth metal salt capable of generating iodide ions.
- a cation exchange resin in its lithium, sodium, calcium or magnesium form is employed. Both strong-acid and weak-acid type resins are available commercially.
- the strong-acid type resin may be a sulphonated styrene- divinylbenzene copolymer or a phenol-formaldehyde condensation polymer.
- the weak-acid type resin may be a copolymer of acrylic or methacrylic acid or esters or the corresponding nitriles or a phenolic resin.
- the cation exchange resin for use in the present invention is a strong-acid type resin.
- the resin may be either a macroreticular type resin or a gel-type resin.
- the cation exchange resin may be converted to its alkali/alkaline earth metal form by contacting the resin with a solution of an alkali/alkaline earth metal salt, such as a solution of alkali metal acetate or iodide, for example lithium or sodium acetate or lithium or sodium iodide or a solution of the iodides or acetates of an alkaline earth metal such as the acetates or iodides of magnesium or calcium. Suitable procedures are well known in the art.
- the amount of alkali metal or alkaline earth metal salt added to the resin should be such that the loaded resin has greater than 0 but less than 100% of its active sites loaded with the alkali metal and/or alkaline earth metal.
- the exact degree of loading onto the resin required to maintain the concentration of alkali/alkaline earth metal in the catalyst solution will depend on the amount of alkali/alkaline earth metal employed in the carbonylation reaction solution, the specific alkali metal or alkaline earth metal to be loaded onto the resin because different metals will have a different degree of affinity for a resin, the fiowrate through the resin bed and the operating temperature of the resin bed.
- the resin suitably has >0 to 60% of its active sites loaded with lithium ions, such as 30 to 55% of its active sites.
- the resin suitably has >0 to 60% of its active sites loaded with sodium ions, such as 30 to 55% of its active sites.
- the contacting of the cation exchange resin in its alkali metal or alkaline earth metal form with the carbonylation catalyst solution may be carried out using any suitable conventional procedure and equipment.
- the carbonylation catalyst solution is passed through a fixed-bed of the resin.
- the rate of flow of the catalyst solution through the fixed-bed of resin during the corrosion metal removal process will, in general, be that recommended by the resin manufacturer and may typically be up to about 20 bed volumes per hour.
- the contacting of the carbonylation catalyst solution with the cation exchange resin in its alkali/alkaline earth metal form may be carried out at any suitable temperature above the freezing point of the catalyst solution and below the temperature at which the resin and/or the catalyst solution exhibits undesirable decomposition. If temperatures above the boiling point of the catalyst solution are employed, then the contacting should be carried out under pressure to maintain the catalyst solution in the liquid phase.
- the contacting temperature may be in the range 0° to 110° C such as 10° to 100° C.
- pressure is not a critical variable.
- the contacting operation may be carried out at atmospheric pressure or a pressure slightly above atmospheric but superatmospheric or sub-atmospheric pressures may be employed if desired.
- the cation exchange resin in its alkali metal or alkaline earth metal form When the cation exchange resin in its alkali metal or alkaline earth metal form has reached its capacity for corrosion metal contaminants it may firstly be rinsed with a liquid compatible with carbonylation processes, for example, carboxylic acid to remove residual carbonylation catalyst solution and then regenerated.
- the cation exchange resin may be regenerated by the methods recommended by the manufacturers to displace the retained corrosion metal contaminants.
- a solution of carboxylic acid such as acetic acid and alkali metal or alkaline earth metal acetate, such as lithium acetate, sodium acetate or magnesium acetate may be used to regenerate the resin.
- the corrosion metal contaminant removal process of the present invention may be operated as a batch or as a continuous process, preferably, as a continuous process.
- more than one resin bed is provided so that whilst the carbonylation catalyst solution is being passed through one resin bed, one or more other resin beds are being regenerated.
- the process of the present invention is particularly applicable to the removal of corrosion metal contaminants such as iron, nickel, chromium, manganese and molybdenum, preferably, iron and nickel.
- Each corrosion metal contaminant may be present in the carbonylation reaction composition in an amount up to its limit of solubility. Typically, this maybe up to 10,000 ppm by weight of metal.
- the amount of each corrosion metal removed from the catalyst solution will depend upon the initial concentration of the corrosion metal, the degree of alkali metal or alkaline earth metal loading on the resin, the capacity of the resin, and operating conditions such as flow rate of the catalyst solution, reactor composition and temperature of the resin bed.
- a liquid-phase carbonylation reaction is generally carried out in one or more reaction zones.
- the carbonylation reaction is the carbonylation of methanol and/or a reactive derivative thereof and is carried out in the presence of an iridium and/or rhodium carbonylation catalyst, an alkali metal salt capable of generating iodide ions, methyl iodide co-catalyst and optionally a promoter, and a finite concentration of water
- the product will be acetic acid.
- the crude acetic acid product may be recovered from a reaction zone by flash separation.
- flash separation the carbonylation reaction composition is passed to a flashing zone via a flashing valve.
- the flash separation zone may be an adiabatic flash vessel or may have additional heating means.
- the carbonylation catalyst solution comprising the majority of the catalyst and, if employed, the majority of the promoter, is separated from a vapour fraction comprising acetic acid, carbonylatable reactant, water and methyl iodide co-catalyst and non-condensable gases such as nitrogen, carbon monoxide, hydrogen and carbon dioxide; at least a portion of the the carbonylation catalyst solution is recycled to the reaction zone and the vapour fraction is passed to one or more purification stages as desired to recover acetic acid product.
- the build-up of corrosion metal contaminants in the carbonylation reaction composition can be reduced.
- a slipstream of catalyst solution is removed from the flash separation zone and treated according to the process of the present invention to remove corrosion metal contaminants and provide a catalyst solution having reduced corrosion metal contaminants which is recycled to the carbonylation reactor.
- the present invention will now be illustrated by way of example only and with reference to the following Examples.
- Lithium acetate solution prepared by adding 460 g LiOAc.2H 2 O to 2.5 kg (95/5 wt% acetic acid/water solution) was passed through a bed containing 500 ml of pre-soaked Amberlyst 15 at a liquid hour space velocity (LHSN) of 4 h "1 . The resin was then washed with water and oven-dried at 100°C for 24 hours. The loaded resin contained 2.6 wt% Li. Resins loaded with 0%, 25%, 50%, 75% and 100%> lithium were prepared by mixing together appropriate amounts of the 2.6wt% lithium loaded resin with unloaded Amberlyst 15.
- the solution was pumped at 1.0 l.h "1 through a bed containing 100 ml of resin. Samples were taken after 2, 4, 6, 8 and 10 bed volumes of feed had passed through the bed and analysed for Li, Fe and ⁇ i content. The intial concentration of Li and the corrosion metals and the results of the Examples are given in Table 1. Examples 6 to 10 The procedure of Examples 1 to 5 was repeated except that in the preparation of the carbonylation solution 23. Og of magnesium acetate was used instead of lithium acetate. The initial metal concentrations and results of the Examples are given in Table 2.
- a 50:50 mixture of Amberjet 1500 and Amberjet 1200Na (both strong acid gel type resins commercially available from Rohm & Haas; Amberjet 1200Na having sodium on the active sites) was prepared.
- a catalyst solution obtained from the flash zone of an acetic acid reaction system comprising acetic acid, iridium, methyl iodide, methyl acetate, sodium, corrosion metals and water was passed through a 30 ml volume of the resin bed at a flow rate of 300 ml h "1 .
- Fig. 2 illustrates that a cation exchange resin partially loaded with sodium does not significantly alter the sodium concentration in the reactor.
Abstract
Description
Claims
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US11/587,339 US8242040B2 (en) | 2004-05-07 | 2005-03-31 | Process for the removal of corrosion metals from carbonylation catalyst solutions |
KR1020067023202A KR101132996B1 (en) | 2004-05-07 | 2005-03-31 | Process for the removal of corrosion metals from carbonylation catalyst solutions |
EP05729557A EP1742739A1 (en) | 2004-05-07 | 2005-03-31 | Process for the removal of corrosion metals from carbonylation catalyst solutions |
RSP-2006/0615A RS20060615A (en) | 2004-05-07 | 2005-03-31 | Process for the removal of corrosion metals from carbonylation catalyst solutions |
JP2007512308A JP4856629B2 (en) | 2004-05-07 | 2005-03-31 | Method for removing corrosive metals from carbonylation catalyst solutions |
CA2562698A CA2562698C (en) | 2004-05-07 | 2005-03-31 | Process for the removal of corrosion metals from carbonylation catalyst solutions |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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GBGB0410289.3A GB0410289D0 (en) | 2004-05-07 | 2004-05-07 | Process |
GB0410289.3 | 2004-05-07 |
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WO2005107945A1 true WO2005107945A1 (en) | 2005-11-17 |
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PCT/GB2005/001216 WO2005107945A1 (en) | 2004-05-07 | 2005-03-31 | Process for the removal of corrosion metals from carbonylation catalyst solutions |
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US (1) | US8242040B2 (en) |
EP (1) | EP1742739A1 (en) |
JP (1) | JP4856629B2 (en) |
KR (1) | KR101132996B1 (en) |
CN (1) | CN100479922C (en) |
CA (1) | CA2562698C (en) |
GB (1) | GB0410289D0 (en) |
MY (1) | MY146270A (en) |
RS (1) | RS20060615A (en) |
RU (1) | RU2381836C2 (en) |
UA (1) | UA92320C2 (en) |
WO (1) | WO2005107945A1 (en) |
Cited By (4)
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---|---|---|---|---|
WO2009074774A2 (en) * | 2007-12-13 | 2009-06-18 | Bp P.L.C. | Catalyst recovery process |
US9409163B2 (en) | 2010-12-30 | 2016-08-09 | Celanese International Corporation | Purification of acetic acid product streams |
WO2016209927A1 (en) | 2015-06-23 | 2016-12-29 | Lyondellbasell Acetyls, Llc | Silver loaded halide removal resins for treating halide containing solutions |
US10067113B2 (en) | 2014-02-28 | 2018-09-04 | LyondellBasell Acetyis, LLC | Acetic acid production process |
Families Citing this family (6)
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JP5254338B2 (en) * | 2008-07-30 | 2013-08-07 | 旭化成ケミカルズ株式会社 | Method and apparatus for producing cycloolefin |
US8697908B2 (en) * | 2011-05-05 | 2014-04-15 | Celanese International Corporation | Removal of amine compounds from carbonylation process stream containing corrosion metal contaminants |
WO2016077672A1 (en) * | 2014-11-14 | 2016-05-19 | Celanese International Corporation | Processes for improving acetic acid yield by removing iron |
JP6786308B2 (en) * | 2016-08-30 | 2020-11-18 | 月島環境エンジニアリング株式会社 | Regeneration method of cation exchange resin, treatment method of liquid to be treated, and treatment equipment containing cation exchange resin |
CN107141213A (en) * | 2017-05-24 | 2017-09-08 | 北京三聚环保新材料股份有限公司 | A kind of method of acetic acid synthesis from methanol carbonylation |
CN110078612B (en) * | 2019-06-06 | 2021-09-07 | 上海华谊(集团)公司 | Method for purifying catalyst circulating liquid |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4007130A (en) * | 1975-12-29 | 1977-02-08 | Monsanto Company | Catalyst regeneration method |
EP0265140A1 (en) * | 1986-10-14 | 1988-04-27 | Hoechst Celanese Corporation | Process for regenerating a carbonylation catalyst solution to remove corrosion metals |
US5124290A (en) * | 1990-10-30 | 1992-06-23 | Hoechst Aktiengesellschaft | Process for removing metallic corrosion products from carbonylation reactions carried out under anhydrous conditions |
EP0618185A1 (en) * | 1993-03-22 | 1994-10-05 | BP Chemicals Limited | Process for the removal of corrosion metal contaminants from liquid compositions |
WO1997015544A1 (en) * | 1995-10-27 | 1997-05-01 | Hoechst Celanese Corporation | Process for improving productivity of a carbonylation catalyst solution by removing corrosion metals |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB9122168D0 (en) | 1991-10-18 | 1991-11-27 | Bp Chem Int Ltd | Process |
FR2703351A1 (en) * | 1993-03-31 | 1994-10-07 | Rhone Poulenc Chimie | Process for the preparation of carboxylic acids or the corresponding esters in the presence of a catalyst based on rhodium and iridium. |
GB9503383D0 (en) | 1995-02-21 | 1995-04-12 | Bp Chem Int Ltd | Process |
US7476307B2 (en) * | 2003-10-10 | 2009-01-13 | Halox Technologies, Inc. | Systems and methods for generating chlorine dioxide |
-
2004
- 2004-05-07 GB GBGB0410289.3A patent/GB0410289D0/en not_active Ceased
-
2005
- 2005-03-31 KR KR1020067023202A patent/KR101132996B1/en active IP Right Grant
- 2005-03-31 JP JP2007512308A patent/JP4856629B2/en not_active Expired - Fee Related
- 2005-03-31 US US11/587,339 patent/US8242040B2/en active Active
- 2005-03-31 EP EP05729557A patent/EP1742739A1/en not_active Withdrawn
- 2005-03-31 WO PCT/GB2005/001216 patent/WO2005107945A1/en active Application Filing
- 2005-03-31 RS RSP-2006/0615A patent/RS20060615A/en unknown
- 2005-03-31 CN CNB2005800142637A patent/CN100479922C/en active Active
- 2005-03-31 CA CA2562698A patent/CA2562698C/en not_active Expired - Fee Related
- 2005-03-31 UA UAA200612758A patent/UA92320C2/en unknown
- 2005-03-31 RU RU2006143154/04A patent/RU2381836C2/en not_active IP Right Cessation
- 2005-05-06 MY MYPI20052049A patent/MY146270A/en unknown
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4007130A (en) * | 1975-12-29 | 1977-02-08 | Monsanto Company | Catalyst regeneration method |
EP0265140A1 (en) * | 1986-10-14 | 1988-04-27 | Hoechst Celanese Corporation | Process for regenerating a carbonylation catalyst solution to remove corrosion metals |
US5124290A (en) * | 1990-10-30 | 1992-06-23 | Hoechst Aktiengesellschaft | Process for removing metallic corrosion products from carbonylation reactions carried out under anhydrous conditions |
EP0618185A1 (en) * | 1993-03-22 | 1994-10-05 | BP Chemicals Limited | Process for the removal of corrosion metal contaminants from liquid compositions |
WO1997015544A1 (en) * | 1995-10-27 | 1997-05-01 | Hoechst Celanese Corporation | Process for improving productivity of a carbonylation catalyst solution by removing corrosion metals |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2009074774A2 (en) * | 2007-12-13 | 2009-06-18 | Bp P.L.C. | Catalyst recovery process |
EP2075070A1 (en) * | 2007-12-13 | 2009-07-01 | BP Chemicals Limited | Catalyst recovery process |
WO2009074774A3 (en) * | 2007-12-13 | 2009-11-05 | Bp P.L.C. | Catalyst recovery process |
RU2484900C2 (en) * | 2007-12-13 | 2013-06-20 | Бп П.Л.К. | Method of extracting catalyst |
US9409163B2 (en) | 2010-12-30 | 2016-08-09 | Celanese International Corporation | Purification of acetic acid product streams |
US10067113B2 (en) | 2014-02-28 | 2018-09-04 | LyondellBasell Acetyis, LLC | Acetic acid production process |
WO2016209927A1 (en) | 2015-06-23 | 2016-12-29 | Lyondellbasell Acetyls, Llc | Silver loaded halide removal resins for treating halide containing solutions |
Also Published As
Publication number | Publication date |
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US8242040B2 (en) | 2012-08-14 |
JP2007536082A (en) | 2007-12-13 |
RU2006143154A (en) | 2008-06-20 |
MY146270A (en) | 2012-07-31 |
KR20070009669A (en) | 2007-01-18 |
RU2381836C2 (en) | 2010-02-20 |
CN1950148A (en) | 2007-04-18 |
JP4856629B2 (en) | 2012-01-18 |
CN100479922C (en) | 2009-04-22 |
KR101132996B1 (en) | 2012-04-09 |
EP1742739A1 (en) | 2007-01-17 |
CA2562698C (en) | 2013-06-04 |
UA92320C2 (en) | 2010-10-25 |
GB0410289D0 (en) | 2004-06-09 |
CA2562698A1 (en) | 2005-11-17 |
US20070298960A1 (en) | 2007-12-27 |
RS20060615A (en) | 2008-06-05 |
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