EP0000665A1 - Récupération du rhodium à partir des résidus de distillation d'hydroformylation avec un ligand triaryle phosphite - Google Patents
Récupération du rhodium à partir des résidus de distillation d'hydroformylation avec un ligand triaryle phosphite Download PDFInfo
- Publication number
- EP0000665A1 EP0000665A1 EP78300204A EP78300204A EP0000665A1 EP 0000665 A1 EP0000665 A1 EP 0000665A1 EP 78300204 A EP78300204 A EP 78300204A EP 78300204 A EP78300204 A EP 78300204A EP 0000665 A1 EP0000665 A1 EP 0000665A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- rhodium
- still heel
- heel
- still
- triaryl phosphite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
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- 239000010948 rhodium Substances 0.000 title claims abstract description 216
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 title claims abstract description 200
- 229910052703 rhodium Inorganic materials 0.000 title claims abstract description 198
- 239000003446 ligand Substances 0.000 title claims abstract description 52
- 238000007037 hydroformylation reaction Methods 0.000 title claims abstract description 24
- 229910019142 PO4 Inorganic materials 0.000 title claims abstract description 7
- 239000010452 phosphate Substances 0.000 title claims abstract description 7
- 238000011084 recovery Methods 0.000 title description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 title description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims abstract description 46
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 44
- 238000000034 method Methods 0.000 claims abstract description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000002244 precipitate Substances 0.000 claims abstract description 27
- 239000002253 acid Substances 0.000 claims abstract description 22
- 239000000203 mixture Substances 0.000 claims abstract description 21
- 229960000583 acetic acid Drugs 0.000 claims abstract description 17
- -1 phosphate compound Chemical class 0.000 claims abstract description 15
- 238000001556 precipitation Methods 0.000 claims abstract description 15
- 238000005406 washing Methods 0.000 claims abstract description 14
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 239000003960 organic solvent Substances 0.000 claims abstract description 11
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910001882 dioxygen Inorganic materials 0.000 claims abstract description 10
- 239000002243 precursor Substances 0.000 claims abstract description 10
- 229930195735 unsaturated hydrocarbon Natural products 0.000 claims abstract description 10
- 239000012362 glacial acetic acid Substances 0.000 claims abstract description 7
- 230000001590 oxidative effect Effects 0.000 claims abstract description 6
- 239000012535 impurity Substances 0.000 claims abstract description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 31
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 31
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- 239000003054 catalyst Substances 0.000 claims description 21
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 11
- 230000003647 oxidation Effects 0.000 claims description 11
- 238000007254 oxidation reaction Methods 0.000 claims description 11
- 239000001301 oxygen Substances 0.000 claims description 11
- 229910052760 oxygen Inorganic materials 0.000 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 8
- 239000003638 chemical reducing agent Substances 0.000 claims description 7
- 229910003450 rhodium oxide Inorganic materials 0.000 claims description 7
- 239000012279 sodium borohydride Substances 0.000 claims description 7
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 7
- SJLOMQIUPFZJAN-UHFFFAOYSA-N oxorhodium Chemical compound [Rh]=O SJLOMQIUPFZJAN-UHFFFAOYSA-N 0.000 claims description 6
- 229910019603 Rh2O3 Inorganic materials 0.000 claims description 5
- 238000009835 boiling Methods 0.000 claims 2
- 239000000126 substance Substances 0.000 claims 2
- 239000011541 reaction mixture Substances 0.000 abstract description 8
- 238000001035 drying Methods 0.000 abstract description 3
- 238000010791 quenching Methods 0.000 abstract description 3
- 230000000171 quenching effect Effects 0.000 abstract description 2
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 20
- 239000002585 base Substances 0.000 description 17
- 238000004090 dissolution Methods 0.000 description 15
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 12
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
- 235000011054 acetic acid Nutrition 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 229910052698 phosphorus Inorganic materials 0.000 description 6
- 239000011574 phosphorus Substances 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 125000000962 organic group Chemical group 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- PFCHFHIRKBAQGU-UHFFFAOYSA-N 3-hexanone Chemical compound CCCC(=O)CC PFCHFHIRKBAQGU-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 125000006267 biphenyl group Chemical group 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 150000002903 organophosphorus compounds Chemical class 0.000 description 2
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 230000000717 retained effect Effects 0.000 description 2
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 2
- IMBQFRVNELCSTF-UHFFFAOYSA-N 2-ethenyl-5-methyl-1,3-dioxane Chemical compound CC1COC(C=C)OC1 IMBQFRVNELCSTF-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 125000004802 cyanophenyl group Chemical group 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- XLGKKDZDZBIMRD-UHFFFAOYSA-N dimethyl phenyl phosphite Chemical compound COP(OC)OC1=CC=CC=C1 XLGKKDZDZBIMRD-UHFFFAOYSA-N 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- MGTBVMLDICPIJJ-UHFFFAOYSA-N ethyl bis(2-methylphenyl) phosphite Chemical compound C=1C=CC=C(C)C=1OP(OCC)OC1=CC=CC=C1C MGTBVMLDICPIJJ-UHFFFAOYSA-N 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000006194 liquid suspension Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- YOKJIBSKGIPPJU-UHFFFAOYSA-N tris(2-cyanophenyl) phosphite Chemical compound N#CC1=CC=CC=C1OP(OC=1C(=CC=CC=1)C#N)OC1=CC=CC=C1C#N YOKJIBSKGIPPJU-UHFFFAOYSA-N 0.000 description 1
- AMGMFFUMIJRDGW-UHFFFAOYSA-N tris(4-chlorophenyl) phosphite Chemical compound C1=CC(Cl)=CC=C1OP(OC=1C=CC(Cl)=CC=1)OC1=CC=C(Cl)C=C1 AMGMFFUMIJRDGW-UHFFFAOYSA-N 0.000 description 1
- VDAQOERDAAOXQV-UHFFFAOYSA-N tris(4-methoxyphenyl) phosphite Chemical compound C1=CC(OC)=CC=C1OP(OC=1C=CC(OC)=CC=1)OC1=CC=C(OC)C=C1 VDAQOERDAAOXQV-UHFFFAOYSA-N 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
Classifications
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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
- B01J31/4046—Regeneration or reactivation of catalysts containing metals containing iron group metals, noble metals or copper containing noble metals containing rhodium
-
- 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
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1845—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
- B01J31/185—Phosphites ((RO)3P), their isomeric phosphonates (R(RO)2P=O) and RO-substitution derivatives thereof
-
- 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
-
- 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
- C01G55/001—Preparation involving a liquid-liquid extraction, an adsorption or an ion-exchange
-
- 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
-
- 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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
- C22B3/32—Carboxylic acids
-
- 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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
- C22B3/38—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds containing phosphorus
- C22B3/383—Tervalent phosphorus oxyacids, esters thereof
-
- 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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
- C22B3/38—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds containing phosphorus
- C22B3/384—Pentavalent phosphorus oxyacids, esters thereof
- C22B3/3846—Phosphoric acid, e.g. (O)P(OH)3
-
- 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
- B01J2231/32—Addition reactions to C=C or C-C triple bonds
- B01J2231/321—Hydroformylation, metalformylation, carbonylation or hydroaminomethylation
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/464—Rhodium
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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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- 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
- B01J31/0201—Oxygen-containing compounds
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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
-
- 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
Definitions
- This invention relates to a process for recovering rhodium from a still heel from the hydroformylation of olefins. More specifically, this invention relates to a process for recovering rhodium from a still heel from the hydroformylation of olefins in the presence of triaryl phosphite ligands and a rhodium complex catalyst and to the products of the recovery process.
- Rhodium metal is known in the art at a catalyst in hydroformylation reactions. In such reactions the rhodium may be complexed with various ligands to render it catalytically active.
- U.S. Patent 3,998,622 there is disclosed a method for preparing a novel rhodium metal form from a still heel from the hydroformylation of olefins where the ligand in the catalyst complex is a trialkyl phosphorus compound.
- Patent 3,998,622 with a triaryl phosphorus ligand does not result in the recovery of at least 90% of the rhodium nor does it produce a rhodium that can be readily dissolved in a triaryl phosphite ligand catalyst solution.
- a process has been found for recovering the rhodium, that is present in a still heel from the hydroformylation of an unsaturated hydrocarbon, in a form that can be solubilized in carbon monoxide and a triaryl phosphite ligand, said still heel comprising rhodium triaryl phosphite complex catalyst, triaryl phosphite ligand and high boilers, said process comprising
- the thus recovered rhodium is a useful material per se or as an intermediate in a process for preparing a highly soluble rhodium that is useful as a catalyst in the hydroformylation of an unsaturated hydrocarbon.
- the rhodium thus precipitated has an extremely low dissolution in a triaryl phosphite ligand and carbon monoxide.
- the rhodium In.order for the precipitated rhodium to be dissolvable to any great extent in said ligand and carbon monoxide, the rhodium must be converted from the zero valent form to Rh 2 O 3 . Further, treatment of the rhodium precipitate can achieve even higher levels of dissolution of at least 95% by weight.
- rhodium thus precipitated is washed with a solvent-acid solution with a pH of from 3 to 4 and then oxidized to Rh 2 0 3 to render it dissolvable in a triaryl phosphite ligand and carbon monoxide. Dissolution of the thus oxidized rhodium of at least 90% by weight is attained.
- Dissolution of the thus precipitated rhodium if merely washed with the solvent-acid but without oxidation to Rh 2 0 3 is attained only to the extent of less than 5% by weight. Dissolution of the thus precipitated rhodium, after merely oxidizing the rhodium to Rh 2 O 3 is attained only to the extent of less than 20% by weight.
- rhodium oxide that is at least 95% by weight dissolvable in a triaryl phosphite ligand and carbon monoxide.
- the rhodium precipitated from (c) above is separated and treated to solubilize it by washing the separated rhodium precipitate with a solvent-acid solution having a pH of 3 to 4 to remove residual still heel; treating the rhodium with an alkaline reducing solution that will reduce trivalent rhodium organo phosphorus impurities to zero valent rhodium; quenching the rhodium with glacial acetic acid to destroy any residual reducing solution; separating the rhodium; washing the rhodium with an aqueous acetic-acid solution with a pH of from 3..0 to 4.0; drying the rhodium in an inert atmosphere at a temperature of from 250° to 400°C; and oxidizing the rhodium with oxygen at a temperature of from 300° to 900°C to convert the rhodium to Rh 2 0 3 .
- the thus treated rhodium is in the form of Rh 2 O 3 and is at least 90% by weight dissolvable (preferably at least 95% by weight dissolvable) in a triaryl phosphite ligand in the presence of carbon monoxide to form a catalyst complex used in the hydroformylation of unsaturated hydrocarbons.
- the process of the present invention can result in the recovery of at least 90% by weight of the rhodium present in the still heel (preferably at least 99% by weight), and after further treatment, wherein the rhodium is converted to a form soluble in CO and a triaryl phosphite ligand can result in the recovery of rhodium that is to the extent of at least 90% by weight dissolvable (preferably at least 95% dissolvable).
- the rhodium triaryl phosphite complex catalyst that is present in still heels of this invention is a homogeneous catalyst solution comprising rhodium and biphyllic ligands complexed with carbon monoxide and hydrogen through coordinate bonding.
- the biphyllic ligands are triaryl phosphite compounds of the formula wherein R 1 , R 2 and R 3 are the same or different aryl groups having 1 to 12 carbon atoms. Representative examples of such aryl groups include phenyl, tolyl, p-chlorophenyl, diphenyl and cyanophenyl.
- Representa- tive examples of the ligand include triphenyl phosphite, tri(p-chlorophenyl) phosphite, tri(cyanophenyl) phosphite, tri(p-methoxyphenyl) phosphite, tri(diphenyl) phosphite,dimethyl phenyl phosphite, ethyl ditolyl phosphite and other combinations within the scope of the above formula.
- the preferred ligand. is triphenyl phosphite.
- the phosphite ligand forms a complex with rhodium and carbon monoxide as described in U.S. Patent 3,527,809 and the complex catalyzes the hydroformylation reaction of unsaturated hydrocarbons from which the still heel of the present invention is derived.
- An excess of the phosphite over that which is required to complex the rhodium in the hydroformylation reactions described herein must be used in order to favor linear vs. branched hydroformylation.
- the excess ligand is also necessary to insure the stability of the rhodium catalyst through the hydroformylation reaction.
- the still heel referred to herein is a heel or tail that remains after the distillation of the reaction product from the hydroformylation of unsaturated hydrocarbons, e.g., olefinic cyclic acetals, conducted in the presence of hydrogen, carbon monoxide and a rhodium triaryl phosphite ligand complex catalyst.
- the reaction product of said hydroformylation which has been distilled to remove cyclic acetal aldehyde product comprises unreacted olefinic cyclic acetals, excess ligand, a rhodium triaryl phosphite complex catalyst and high boilers.
- the still heel of the process of this invention is thus a residual tail from said distillation.
- rhodium triaryl phosphite complex catalyst is meant a' coordination compound of rhodium in complex combination with carbon monoxide, hydrogen and a triaryl phosphite ligand.
- the pH of the still heel is acidic. The pH may range from 1.0 to about 8.0.
- Hydroformylation reactions from which the still heel of the present invention are derived, are reactions of unsaturated hydrocarbons, e.g., olefinic cyclic acetals, with hydrogen and carbon monoxide in the presence of a rhodium triaryl phosphite complex catalyst at temperatures and pressures well known in the art.
- Rhodium triaryl phosphite complex catalysts used are solubilized complexes of rhodium in combination with carbon monoxide, hydrogen and trialkyl phosphite ligand.
- the residue of high boilers, rhodium triaryl phosphite complex catalyst and ligand are usually recycled back to the hydroformylation reaction until high boilers accumulate to the point where a small portion of the still heel must be purged to maintain the high boilers at a constant concentration.
- the value of rhodium is such tha.teconomics do not permit the discarding of all or any significant portion of the purged still heel.
- the process of the present invention permits the recovery of at least 90% by weight of the rhodium (at certain higher concentration ranges at least 99% by weight).
- the rhodium recovered is purified to convert it to a form that is highly soluble in a triaryl phosphite ligand and carbon monoxide.
- the rhodium, after purification is at least 90% soluble and most preferably at least 95% soluble in a triaryl phosphite ligand and carbon monoxide.
- the still heel of the present invention is obtained by first charging commercially available Rh 6 (CO) 16 into a pressure vessel with an olefinic starting material, e.g., 2-vinyl-5-methyl-l,3-dioxane,. solvent and ligand. After flushing with nitrogen, the pressure vessel is sealed and pressurized with carbon monoxide and hydrogen to 35 to 150 psig at a hydrogen to carbon monoxide ratio of 1:1 and after a period of time the reaction is complete.
- the product consists of various aldehydes, unreacted starting material, cyclic acetals, ligand, rhodium complex catalyst and high boilers.
- Rhodium recovered by the process of the present invention and converted to the form of Rh 2 0 3 from this residue of HB, ligand and rhodium complex catalyst was added to triphenyl phosphite and carbon monoxide at a pressure of 4,000 psig and was at least 90% by weight converted to a homogeneous complex solution at 150° to 175°C.
- the dissolution can be accomplished at any pressure of carbon monoxide, e.g., from atmospheric to 10,000 psig. Generally, carbon monoxide pressures of from 200 to 5,000 psig are sufficient.
- the organic solvent in the pretreatment step of the process of this invention must be compatible with the still heel.
- the organic solvent is mixed into the still heel to lower its viscosity and to solubilize the water added in the still heel. Any compatible organic solvent or any mixture thereof that will reduce the viscosity of the still heel and solubilize the water may be used.
- Low molecular weight alcohols and ketones are suitable solvents. Methanol, acetone and methyl ethyl ketone are preferred organic solvents.
- organic solvents include methanol, methyl ethyl ketone, acetone, ethanol, propanol, isopropanol, diethyl ketone, methyl propyl ketone, ethyl propyl ketone and mixtures thereof.
- Oxygen gas or a precursor thereof is used in the pretreatment step of the process of the present invention to oxidize the triphenyl phosphite ligand to triphenyl phosphate.
- a precursor of oxygen gas is any compound which, under the conditions indicated herein, will yield oxygen gas and will not contaminate the rhodium.
- Representative examples of a precursor of oxygen gas include hydrogen peroxide and ozone.
- the preferred precursor is hydrogen peroxide because of its availability. The amount of oxygen or precursor depends on the still heel and the amount of triphenyl phosphite present.
- an excess of oxygen or of a precursor thereof over that amount required to oxidize the triphenyl phosphite to triphenyl phosphate is required because of decomposition reactions and other reactions that occur with other organic materials.
- the amount of the excess is not critical, but is regulated based on convenience and economy.
- the amount of water depends on the still heel.
- the water defined herein includes water in the base solution as well as water added as such.
- the amount of water required in the pretreatment step must generally be at least 5 ml per 100 g of still heel.
- the upper limit of water is that amount of water that will not cause the still heel to separate into two liquid phases.
- the water added must be enough to maximize the rhodium precipitated but less than enough water to cause the formation of two liquid phases.
- the maximum amount of water is dependent on the solubility of the water in the organic solvent and the amount of said solvent. It was found to be preferable to use 36 to 40 ml of water per 100 g of still heel treated with 53 ml of methanol.
- the base for adjusting the pH of the still heel of the present invention may be any base material that is soluble in the still heel water mixture of the present invention and that will not form any interfering precipitation.
- the base may be weak or strong.
- sodium hydroxide or salts of weak acids and strong bases can be used.
- Organic bases such as the quaternary ammonium hydroxides also are suitable for bases, e.g., tetramethyl ammonium hydroxide.
- the preferred base is selected from the group consisting of alkali metal hydroxide and alkaline earth metal hydroxides.
- the most preferred base is the alkali metal hydroxides of which sodium or potassium hydroxide are most preferred.
- the amount of base required will vary depending on the particular still heel utilized. Generally, the amount of base required will be that amount that will give the reaction mixture, after rhodium is precipitated from the still heel, solvent, water and oxygen mixture a pH of from 2 to 7, preferably 3 to 6. An excess of base will reduce the percent of the rhodium recovered from the rhodium available in the still heel. Depending on the nature of the still heel, the pH may be such that no base need be added.
- the mixture of still heel, organic solvent, water, base and oxidant is heated to a temperature of 0° to 85°C, preferably 20° to 85°C until the triaryl phosphite ligand is oxidized to the corresponding phosphate compound.
- Pretreatment with oxygen gas at 50 psig and 75°C will completely oxidize the ligand in 60 minutes. Hydrogen peroxide at 75°C is equally effective in 15 minutes.
- a sample of the pretreated mixture after heating to from 0° to 80°C is tested by gas chromatograph to determine when the triaryl phosphite is oxidized to the corresponding phosphate.
- the second heating of the pretreated still heel mixture for the purpose of precipitating the rhodium at 115° to 175°C is preferable under an atmosphere or vapor space of inert gas.
- the vapor space before the heating step thus is preferably filled with an inert gas which preferably is nitrogren.
- the preferred temperature range is from about 150° to about 165°C.
- the time at the temperatures indicated can vary from 15 minutes to 120 minutes.
- the yield of rhodium recovered is lower. Longer periods are operable, but the benefits " in rhodium recovered are not proportional to the time of reaction. Thus, greater reaction time yields smaller increases in recovery than when the time is between 15 minutes and 120 minutes.
- the shodlen may be most conveniently separated from the still heel centrifuging or filtration. Separation by centrifuge or filter is well known in the art.
- the thus recovered rhodium precipitate is washed with the solvent-acid solution and then oxidized to convert the zero valent rhodium to Rh 2 0 3 with oxygen at atmospheric or higher pressures and temperatures of from 300° to 900°C to permit the dissolution of the recovered rhodium in the triaryl phosphite ligand.
- the thus recovered rhodium precipitate is further treated before oxidation to improve its dissolution in the triaryl phosphite ligand.
- the rhodium precipitate that was separated from the still heel is washed with the solvent-acid solution with a pH of from 3 to 4 for the purpose of removing residual still heel from the surface of the rhodium.
- the residual still heel on the surface of the rhodium recovered will affect the solubility of the rhodium in carbon monoxide and ligand.
- the presence of the rather small amounts of trivalent rhodium organo phosphorus impurities on the surface of the recovered rhodium are sufficient to prevent greater than 90% by weight solubility of the recovered rhodium.
- the recovered rhodium can be made at least 90% by weight dissolvable in the ligand by merely oxidizing to Rh 2 O 3 after the solvent-acid washing.
- the solvent acid solution is a polution of a solvent as defined above.
- Preferred solvents are methanol and acetone.
- the acid may be any acid. However, glacial acetic acid is preferred because of its ease in attaining the desired pH range and because it leaves no undesired residual on drying. Little to no water is present in the solvent-acid solution. Acids such as hydrochloric and nitric require so little amounts to achieve the desired pH that the amount of water present can easily be minimal.
- the recovered rhodium can be further purified to increase its dissolution in ligand.
- the washed rhodium is treated with an alkaline reducing solution that will reduce the trivalent rhodium organo phosphorus impurity to zero valent rhodium.
- Any reducing agent which will reduce the trivalent rhodium to zero valent rhodium can be used.
- the amount of reducing agent is that amount that will convert all the trivalent rhodium present to zero valent rhodium.
- the preferred reducing agent is sodium borohydride.
- the amount of trivalent rhodium present that must be converted to zero valent rhodium is relatively small but its conversion is essential to achieving a rhodium that is at least 95% soluble in the triaryl phosphite ligand.
- the temperature is from 25° to 75°C for this reducing step.
- the reducing solution is made alkaline with a base (as defined hereinbefore) to stabilize the reducing solution.
- a base as defined hereinbefore
- sodium hydroxide is added to stabilize NaBH 4 to prevent spontaneous decomposition that may occur under acid conditions.
- the thus treated rhodium is quenched with glacial acetic acid.
- the glacial acetic acid neutralizes the-base, destroys residual reducing agent and quickly achieves a pH between 3 and 4 and preferably about 3.2 that permits rhodium agglomeration and ease in separating the rhodium from the liquid suspension that results. If not agglomerated, some rhodium is lost or not recovered.
- the second separation of the rhodium may be by any means within the skill of the art. However, centrifuging and filtration are preferred.
- the thus separated rhodium is washed with water containing sufficient acetic acid to bring the pH of the wash water to from 3 to 4.
- the washing permits the rhodium to be retained in agglomerated form thereby making separation easier.
- the washing is continued until the rhodium is free of sodium salts such as, for example, sodium acetate and sodium phosphate.
- the above described solvent-acid solution at a pH of from 3 to 4 may also be used to wash the thus separated rhodium. However, in such a case, the amount used is greater than the aqueous acetic acid wash in order to remove said sodium salts.
- the washed rhodium is dried in an inert atmosphere at a temperature of from 250° to 450°C, preferably 325° to 350°C, until all water and acetic acid are removed.
- the time necessary to remove all water and acetic acid may vary depending on the thickness of the rhodium and the temperature used. For example, 30 minutes in an inert atmosphere of argon at 325°C was required to remove all water and acetic acid from a 100 mg sample of rhodium 1 mm thick.
- the dried rhodium is oxidized with oxygen gas at 300 0 to 900 ° C to Rh203.
- Oxidation of the rhodium to Rh 2 0 3 is essential for obtaining essentially complete dissolution of the rhodium oxide in the presence of triaryl phosphite and carbon monoxide.
- Temperatures below 300°C will not result in the formation of Rh 2 0 3 while the temperatures above 900°C result in dissociation of the Rh 2 0 3 .
- the pre- . ferred temperature is 450° to 900°C and most preferably the temperature range is 525° to 650°C.
- Oxidation of the rhodium to Rh 2 0 3 may be at atmospheric pressure or higher pressures. Generally, at higher pressures lower temperatures may be used to maximize conversion to Rh 2 0 3 . For example, at 1 atmosphere of oxygen and 625°C after 1 hour, 94% of the rhodium was converted to Rh203, while at 136 atmospheres of oxygen and 525°C after 16 hours, 100% of the rhodium was converted to Rh 2 0 3 .
- the process of the present invention decreases in efficiency or percent of rhodium recovered as the amount of rhodium in the still heel decreases. It was found that where the rhodium concentration in the still heel was 50 ppm or more, a recovery of at least 90% by weight of the rhodium in the still heel could be achieved of which at least 90% by weight could be treated to render it soluble in a triaryl phosphorus ligand and carbon monoxide.
- the contents of the autoclave after being cooled to room temperature, were centrifuged to separate the precipitated rhodium black (finely divided zero valent rhodium) from the liquid phase.
- the pH of the filtrate' was 3.4.
- the precipitate contained 99.5% of the rhodium in the still heel.
- the precipitate after the separation was washed free of still heel with methanol adjusted to a pH of 3.2 with acetic acid.
- the rhodium present in small concentration as Rh +3 organo phosphorus compounds was reduced to metallic rhodium by treatment with sodium borohydride.
- One hundred milligrams of methanol-washed precipitate was treated at room temperature with 20 ml of a solution containing 200 mg sodium borohydride dissolved in 0.lN sodium hydroxide.
- the precipitate was washed free of caustic and the accompanying sodium salts with an initial quench using glacial acetic acid followed by water washings (adjusted to a pH of 3.2 with acetic acid).
- the rhodium content of the precipitate was 99.5%.
- the rhodium was dried in an inert (argon) gas stream at 350°C for 30 minutes followed by oxidation in 100% oxygen for 2 hours at 650°C.
- the rhodium present in the rhodium oxide represented 99+% of the soluble rhodium originally present in the still heel.
- the rhodium oxide recovered in Example 1 was dissolved by converting it to the carbonyl triphenyl phosphite complex in the following manner: Thirty milligrams of oxidized rhodium from Example 1 and 3 ml of triphenyl phosphite were heated in a shaker tube at 175°C for 4 hours in the presence of 4,000 psig carbon monoxide. This procedure resulted in the dissolution of 99+% of the rhodium. The soluble rhodium exhibited normal catalytic activity when it was used in the hydroformylation of 2-vinyl-5-methyl-l, 3-dioxane.
- the precipitation and treatment of rhodium from a still heel was performed according to the procedure in Example 1 with the exception that no hydrogen peroxide was used.
- the rhodium content of the precipitate from ten different still heels ranged from 35% to 90% due to the presence of Rh +3 organo phosphorus compound.'
- the precipitate contained 99% of the rhodium present in the still heel.
- the precipitation of rhodium from a still heel was performed according to the procedure in Example 1.
- the precipitate was 98% rhodium; it contained 99.5% of the rhodium present in the still heel.
- the precipitate was washed free of a still heel with methanol (pH 3.2), and oxidized with oxygen at 650°C at 1 atmosphere for 4 hours, but no sodium borohydride treatment was used.
- methanol pH 3.2
- oxidized with oxygen at 650°C at 1 atmosphere for 4 hours but no sodium borohydride treatment was used.
- Ninety-five percent of the rhodium was dissolved in triphenyl phosphite and carbon monoxide.
- the treatment without sodium borohydride did not result in a rhodium as highly dissolvable as with the borohydride.
- the precipitation of rhodium from a still heel was performed according to the procedure in Example 1 with the exception that tetramethylammonium hydroxide was used as the base instead of sodium hydroxide.
- the precipitate contained 99.4% of the rhodium present in the still heel.
- the precipitation of rhodium from a still heel was performed according to the procedure in Example 1 with the exception that methyl ethyl ketone was used instead of methanol.
- the precipitate contained 98.5% of the rhodium present in the still heel.
- the precipitation of rhodium from a still heel was performed according to the procedure in Example 1 with the exception that the hydrogen peroxide pretreatment of the still heel was replaced with oxygen treatment at 50 psig and 75°C for 1.5 hours.
- the precipitate contained 96.3% of the rhodium present in the still heel.
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Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US82004677A | 1977-07-28 | 1977-07-28 | |
US820046 | 1977-07-28 |
Publications (1)
Publication Number | Publication Date |
---|---|
EP0000665A1 true EP0000665A1 (fr) | 1979-02-07 |
Family
ID=25229741
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP78300204A Withdrawn EP0000665A1 (fr) | 1977-07-28 | 1978-07-26 | Récupération du rhodium à partir des résidus de distillation d'hydroformylation avec un ligand triaryle phosphite |
Country Status (5)
Country | Link |
---|---|
US (1) | US4135911A (fr) |
EP (1) | EP0000665A1 (fr) |
JP (1) | JPS5426218A (fr) |
CA (1) | CA1109274A (fr) |
IT (1) | IT1097450B (fr) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0049781A1 (fr) * | 1980-09-24 | 1982-04-21 | Union Carbide Corporation | Réactivation d'un complexe de rhodium utilisé comme catalyseur d'hydroformylation |
EP2410626A1 (fr) | 2010-07-22 | 2012-01-25 | Alstom Grid SAS | Ligne de transport d'électricite a isolation gazeuse |
CN104248994A (zh) * | 2013-06-25 | 2014-12-31 | 中国石油化工股份有限公司 | 羰基化铑膦催化剂的活性恢复方法 |
Families Citing this family (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4196096A (en) * | 1979-02-12 | 1980-04-01 | Eastman Kodak Company | Process for regeneration of rhodium hydroformylation catalysts |
DE2911193C2 (de) * | 1979-03-22 | 1981-12-17 | W.C. Heraeus Gmbh, 6450 Hanau | Verfahren zur Wiedergewinnung von Rhodium |
GB2048862B (en) * | 1979-05-11 | 1983-06-15 | Mitsubishi Chem Ind | Process for the hydroformylation of olefins |
JPS5850234B2 (ja) * | 1980-10-23 | 1983-11-09 | 三菱化学株式会社 | 第8族貴金属固体錯体の取得方法 |
US4400547A (en) * | 1981-04-10 | 1983-08-23 | Eastman Kodak Company | Hydroformylation process utilizing an unmodified rhodium catalyst and the stabilization and regeneration thereof |
US4434240A (en) | 1981-11-16 | 1984-02-28 | The Halcon Sd Group, Inc. | Recovery of noble metal values from carbonylation residues |
ATE16475T1 (de) * | 1982-06-11 | 1985-11-15 | Davy Mckee London | Hydroformylierungsverfahren. |
DE3371067D1 (en) * | 1982-06-11 | 1987-05-27 | Davy Mckee London | Hydroformylation process |
US4547595A (en) * | 1982-09-02 | 1985-10-15 | Ashland Oil, Inc. | Method of reactivating Group VIII anionic hydroformylation catalysts |
DE3833427A1 (de) * | 1988-10-01 | 1990-04-05 | Hoechst Ag | Verfahren zur rueckgewinnung von rhodium |
US5208194A (en) * | 1992-02-25 | 1993-05-04 | Arco Chemical Technology, L.P. | Recovery of group VIII transition metals from organic solutions using acidic ion-exchange resins |
US5773665A (en) * | 1996-07-01 | 1998-06-30 | Elf Atochem North America, Inc. | Hydroformylation process with separation and recycle of active rhodium catalyst |
CZ283697A3 (cs) * | 1996-09-11 | 1998-04-15 | Mitsubishi Chemical Corporation | Způsob přípravy roztoku komplexu rhodia a jeho použití |
US7935173B1 (en) | 2010-07-23 | 2011-05-03 | Metals Recovery Technology Inc. | Process for recovery of precious metals |
CN102373335B (zh) * | 2010-08-27 | 2013-08-14 | 中国石油化工股份有限公司 | 一种从失活铑膦络合催化剂中回收铑的方法 |
CN111278560B (zh) | 2017-11-13 | 2023-07-21 | 陶氏技术投资有限责任公司 | 从氢甲酰化方法回收铑的方法 |
BE1030097B1 (nl) * | 2021-12-24 | 2023-07-25 | Indaver Nv | Werkwijze voor het optimaliseren van vloeibare farmacochemische en/of fijnchemische afvalstoffen omvattende organische solventen en edelmetalen |
BE1030099B1 (nl) * | 2021-12-24 | 2023-07-25 | Indaver Nv | Werkwijze voor het screenen van vloeibare farmacochemische en/of fijnchemische afvalstoffen omvattende organische solventen en edelmetalen |
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US3547964A (en) * | 1968-07-24 | 1970-12-15 | Union Oil Co | Group viii noble metal catalyst recovery |
US3998622A (en) * | 1975-12-23 | 1976-12-21 | E. I. Du Pont De Nemours And Company | Rhodium from hydroformylation still heels |
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CA879601A (en) * | 1971-08-31 | Ruhrchemie Aktiengesellschaft | Process for separating and recovering rhodium catalysts from products of hydroformylation | |
US3071551A (en) * | 1960-03-28 | 1963-01-01 | Abbott Lab | High temperature regeneration of rhodium catalyst |
DE1295537B (de) * | 1967-10-25 | 1969-05-22 | Ruhrchemie Ag | Verfahren zur Wiedergewinnung von Rhodium aus den durch Umsetzung von ungesaettigten Verbindungen mit Kohlenoxid und Wasserstoff erhaltenen Hydroformylierungsprodukten |
US3539634A (en) * | 1967-11-09 | 1970-11-10 | Union Oil Co | Recovery of catalyst in oxo process |
DE1290535C2 (de) * | 1968-01-31 | 1975-11-20 | Ruhrchemie Ag, 4200 Oberhausen | Verfahren zur abtrennung und wiedergewinnung von rhodium aus hydroformylierungsprodukten |
DE1945574B2 (de) * | 1968-09-14 | 1975-01-23 | Mitsubishi Chemical Industries, Ltd., Tokio | Verfahren zur Rückgewinnung eines Rhodiumkatalysators aus einem Oxo-Reaktionsprodukt |
JPS535879B2 (fr) * | 1973-08-14 | 1978-03-02 | ||
US3901822A (en) * | 1973-11-14 | 1975-08-26 | Fmc Corp | Process of regenerating a noble metal hydrogenation catalyst used in hydrogen peroxide production by the anthraquinone process |
US3899442A (en) * | 1974-01-31 | 1975-08-12 | Us Agriculture | Recovery and reactivation of rhodium hydroformylation catalysts |
DE2448005C2 (de) * | 1974-10-09 | 1983-10-20 | Basf Ag, 6700 Ludwigshafen | Verfahren zur Regenerierung von Rhodium oder Iridium enthaltenden Katalysatoren aus Destillationsrückständen von Hydroformylierungsgemischen |
-
1978
- 1978-05-12 US US05/905,200 patent/US4135911A/en not_active Expired - Lifetime
- 1978-07-26 CA CA308,179A patent/CA1109274A/fr not_active Expired
- 1978-07-26 EP EP78300204A patent/EP0000665A1/fr not_active Withdrawn
- 1978-07-27 IT IT26186/78A patent/IT1097450B/it active
- 1978-07-28 JP JP9167078A patent/JPS5426218A/ja active Pending
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
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US3547964A (en) * | 1968-07-24 | 1970-12-15 | Union Oil Co | Group viii noble metal catalyst recovery |
US3998622A (en) * | 1975-12-23 | 1976-12-21 | E. I. Du Pont De Nemours And Company | Rhodium from hydroformylation still heels |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0049781A1 (fr) * | 1980-09-24 | 1982-04-21 | Union Carbide Corporation | Réactivation d'un complexe de rhodium utilisé comme catalyseur d'hydroformylation |
EP2410626A1 (fr) | 2010-07-22 | 2012-01-25 | Alstom Grid SAS | Ligne de transport d'électricite a isolation gazeuse |
CN104248994A (zh) * | 2013-06-25 | 2014-12-31 | 中国石油化工股份有限公司 | 羰基化铑膦催化剂的活性恢复方法 |
Also Published As
Publication number | Publication date |
---|---|
US4135911A (en) | 1979-01-23 |
IT1097450B (it) | 1985-08-31 |
CA1109274A (fr) | 1981-09-22 |
IT7826186A0 (it) | 1978-07-27 |
JPS5426218A (en) | 1979-02-27 |
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