EP2763950A2 - Procédé de production d'acide formique par réaction de dioxyde de carbone avec de l'hydrogène - Google Patents
Procédé de production d'acide formique par réaction de dioxyde de carbone avec de l'hydrogèneInfo
- Publication number
- EP2763950A2 EP2763950A2 EP12766684.0A EP12766684A EP2763950A2 EP 2763950 A2 EP2763950 A2 EP 2763950A2 EP 12766684 A EP12766684 A EP 12766684A EP 2763950 A2 EP2763950 A2 EP 2763950A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- phase
- formic acid
- mixture
- tertiary amine
- hydrogenation
- 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- Withdrawn
Links
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 title claims abstract description 331
- 235000019253 formic acid Nutrition 0.000 title claims abstract description 168
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 title claims abstract description 146
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 128
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 64
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 64
- 239000001257 hydrogen Substances 0.000 title claims abstract description 51
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 51
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims description 43
- 238000004519 manufacturing process Methods 0.000 title abstract description 3
- 150000003512 tertiary amines Chemical class 0.000 claims abstract description 342
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 236
- 239000000203 mixture Substances 0.000 claims abstract description 216
- 239000002798 polar solvent Substances 0.000 claims abstract description 146
- 238000004821 distillation Methods 0.000 claims abstract description 121
- 238000005191 phase separation Methods 0.000 claims abstract description 97
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 93
- 238000000605 extraction Methods 0.000 claims abstract description 77
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 74
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 56
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 55
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 39
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims abstract description 30
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims abstract description 30
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 27
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000011541 reaction mixture Substances 0.000 claims abstract description 23
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 22
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 230000000737 periodic effect Effects 0.000 claims abstract description 18
- 125000002015 acyclic group Chemical group 0.000 claims abstract description 14
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 14
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 9
- 125000004429 atom Chemical group 0.000 claims abstract description 7
- 125000005842 heteroatom Chemical group 0.000 claims abstract description 7
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 5
- 239000003054 catalyst Substances 0.000 claims description 248
- 238000000034 method Methods 0.000 claims description 211
- 230000008569 process Effects 0.000 claims description 92
- 238000003776 cleavage reaction Methods 0.000 claims description 52
- 230000007017 scission Effects 0.000 claims description 52
- 239000003446 ligand Substances 0.000 claims description 23
- DIAIBWNEUYXDNL-UHFFFAOYSA-N n,n-dihexylhexan-1-amine Chemical compound CCCCCCN(CCCCCC)CCCCCC DIAIBWNEUYXDNL-UHFFFAOYSA-N 0.000 claims description 13
- 150000002431 hydrogen Chemical class 0.000 claims description 7
- 238000006555 catalytic reaction Methods 0.000 claims description 5
- 238000004227 thermal cracking Methods 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- 125000000753 cycloalkyl group Chemical group 0.000 claims 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims 1
- -1 araliphatic Chemical group 0.000 abstract description 33
- 150000001412 amines Chemical class 0.000 abstract description 30
- 238000012545 processing Methods 0.000 abstract description 4
- 125000003118 aryl group Chemical group 0.000 abstract description 3
- 239000012967 coordination catalyst Substances 0.000 abstract 7
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- 239000012071 phase Substances 0.000 description 414
- 239000003112 inhibitor Substances 0.000 description 45
- 238000006243 chemical reaction Methods 0.000 description 36
- 230000002051 biphasic effect Effects 0.000 description 34
- 238000002474 experimental method Methods 0.000 description 31
- 238000007792 addition Methods 0.000 description 23
- 238000000926 separation method Methods 0.000 description 23
- 230000005764 inhibitory process Effects 0.000 description 22
- 239000007791 liquid phase Substances 0.000 description 17
- 239000002904 solvent Substances 0.000 description 17
- 239000000047 product Substances 0.000 description 16
- 230000005611 electricity Effects 0.000 description 15
- 238000010626 work up procedure Methods 0.000 description 14
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 13
- 239000007788 liquid Substances 0.000 description 13
- 229910052751 metal Inorganic materials 0.000 description 13
- 239000002184 metal Substances 0.000 description 13
- 238000002360 preparation method Methods 0.000 description 13
- 238000004064 recycling Methods 0.000 description 13
- 229910052707 ruthenium Inorganic materials 0.000 description 13
- 238000004448 titration Methods 0.000 description 13
- 238000009826 distribution Methods 0.000 description 12
- XYFCBTPGUUZFHI-UHFFFAOYSA-N phosphine group Chemical group P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 10
- 238000000354 decomposition reaction Methods 0.000 description 10
- 230000036961 partial effect Effects 0.000 description 10
- 229940044613 1-propanol Drugs 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000009835 boiling Methods 0.000 description 8
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 8
- BOUYBUIVMHNXQB-UHFFFAOYSA-N dicyclohexyl(2-dicyclohexylphosphanylethyl)phosphane Chemical compound C1CCCCC1P(C1CCCCC1)CCP(C1CCCCC1)C1CCCCC1 BOUYBUIVMHNXQB-UHFFFAOYSA-N 0.000 description 8
- 239000012455 biphasic mixture Substances 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 230000035484 reaction time Effects 0.000 description 7
- 101001053401 Arabidopsis thaliana Acid beta-fructofuranosidase 3, vacuolar Proteins 0.000 description 6
- 101001053395 Arabidopsis thaliana Acid beta-fructofuranosidase 4, vacuolar Proteins 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- OWFLJHJHQKHZJR-UHFFFAOYSA-N dicyclohexyl(dicyclohexylphosphanylmethyl)phosphane Chemical compound C1CCCCC1P(C1CCCCC1)CP(C1CCCCC1)C1CCCCC1 OWFLJHJHQKHZJR-UHFFFAOYSA-N 0.000 description 6
- 238000004817 gas chromatography Methods 0.000 description 6
- 230000007420 reactivation Effects 0.000 description 6
- 238000007669 thermal treatment Methods 0.000 description 6
- XGCDBGRZEKYHNV-UHFFFAOYSA-N 1,1-bis(diphenylphosphino)methane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CP(C=1C=CC=CC=1)C1=CC=CC=C1 XGCDBGRZEKYHNV-UHFFFAOYSA-N 0.000 description 5
- QFMZQPDHXULLKC-UHFFFAOYSA-N 1,2-bis(diphenylphosphino)ethane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CCP(C=1C=CC=CC=1)C1=CC=CC=C1 QFMZQPDHXULLKC-UHFFFAOYSA-N 0.000 description 5
- WAIPAZQMEIHHTJ-UHFFFAOYSA-N [Cr].[Co] Chemical compound [Cr].[Co] WAIPAZQMEIHHTJ-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 5
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 239000011550 stock solution Substances 0.000 description 5
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 4
- 150000002009 diols Chemical class 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 125000002524 organometallic group Chemical group 0.000 description 4
- 239000012429 reaction media Substances 0.000 description 4
- 238000005070 sampling Methods 0.000 description 4
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 125000005270 trialkylamine group Chemical group 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 239000012454 non-polar solvent Substances 0.000 description 3
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 238000012856 packing Methods 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- 229910052703 rhodium Inorganic materials 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 2
- MCMFEZDRQOJKMN-UHFFFAOYSA-N 1-butylimidazole Chemical compound CCCCN1C=CN=C1 MCMFEZDRQOJKMN-UHFFFAOYSA-N 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 2
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 description 2
- GSCCALZHGUWNJW-UHFFFAOYSA-N N-Cyclohexyl-N-methylcyclohexanamine Chemical compound C1CCCCC1N(C)C1CCCCC1 GSCCALZHGUWNJW-UHFFFAOYSA-N 0.000 description 2
- YJLYANLCNIKXMG-UHFFFAOYSA-N N-Methyldioctylamine Chemical compound CCCCCCCCN(C)CCCCCCCC YJLYANLCNIKXMG-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- JYBWGIWGBANSPY-UHFFFAOYSA-N cyclohexyl(2-cyclohexylphosphanylethyl)phosphane Chemical compound C1CCCCC1PCCPC1CCCCC1 JYBWGIWGBANSPY-UHFFFAOYSA-N 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- GGSUCNLOZRCGPQ-UHFFFAOYSA-N diethylaniline Chemical compound CCN(CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-N 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 239000002815 homogeneous catalyst Substances 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- CLZGJKHEVKJLLS-UHFFFAOYSA-N n,n-diheptylheptan-1-amine Chemical compound CCCCCCCN(CCCCCCC)CCCCCCC CLZGJKHEVKJLLS-UHFFFAOYSA-N 0.000 description 2
- YWWNNLPSZSEZNZ-UHFFFAOYSA-N n,n-dimethyldecan-1-amine Chemical compound CCCCCCCCCCN(C)C YWWNNLPSZSEZNZ-UHFFFAOYSA-N 0.000 description 2
- XTAZYLNFDRKIHJ-UHFFFAOYSA-N n,n-dioctyloctan-1-amine Chemical compound CCCCCCCCN(CCCCCCCC)CCCCCCCC XTAZYLNFDRKIHJ-UHFFFAOYSA-N 0.000 description 2
- OOHAUGDGCWURIT-UHFFFAOYSA-N n,n-dipentylpentan-1-amine Chemical compound CCCCCN(CCCCC)CCCCC OOHAUGDGCWURIT-UHFFFAOYSA-N 0.000 description 2
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 229910052762 osmium Inorganic materials 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- HFPZCAJZSCWRBC-UHFFFAOYSA-N p-cymene Chemical compound CC(C)C1=CC=C(C)C=C1 HFPZCAJZSCWRBC-UHFFFAOYSA-N 0.000 description 2
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- SBYHFKPVCBCYGV-UHFFFAOYSA-N quinuclidine Chemical compound C1CC2CCN1CC2 SBYHFKPVCBCYGV-UHFFFAOYSA-N 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
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- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- RMZAYIKUYWXQPB-UHFFFAOYSA-N trioctylphosphane Chemical compound CCCCCCCCP(CCCCCCCC)CCCCCCCC RMZAYIKUYWXQPB-UHFFFAOYSA-N 0.000 description 2
- XLRPYZSEQKXZAA-OCAPTIKFSA-N tropane Chemical compound C1CC[C@H]2CC[C@@H]1N2C XLRPYZSEQKXZAA-OCAPTIKFSA-N 0.000 description 2
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- 229940043375 1,5-pentanediol Drugs 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- ONVZFCHLOZUXRP-UHFFFAOYSA-N 2-chloro-5-[[4-(3-chlorophenyl)-2,5-dioxopyrrol-3-yl]amino]benzoic acid Chemical compound C1=C(Cl)C(C(=O)O)=CC(NC=2C(NC(=O)C=2C=2C=C(Cl)C=CC=2)=O)=C1 ONVZFCHLOZUXRP-UHFFFAOYSA-N 0.000 description 1
- BZUDVELGTZDOIG-UHFFFAOYSA-N 2-ethyl-n,n-bis(2-ethylhexyl)hexan-1-amine Chemical compound CCCCC(CC)CN(CC(CC)CCCC)CC(CC)CCCC BZUDVELGTZDOIG-UHFFFAOYSA-N 0.000 description 1
- MSXVEPNJUHWQHW-UHFFFAOYSA-N 2-methylbutan-2-ol Chemical group CCC(C)(C)O MSXVEPNJUHWQHW-UHFFFAOYSA-N 0.000 description 1
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- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
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- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 238000002479 acid--base titration Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
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- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- FYGDTMLNYKFZSV-UHFFFAOYSA-N beta-D-Galactopyranosyl-(1->4)-beta-D-galactopyranosyl-(1->4)-D-galactose Chemical compound OC1C(O)C(O)C(CO)OC1OC1C(CO)OC(OC2C(OC(O)C(O)C2O)CO)C(O)C1O FYGDTMLNYKFZSV-UHFFFAOYSA-N 0.000 description 1
- QKSKPIVNLNLAAV-UHFFFAOYSA-N bis(2-chloroethyl) sulfide Chemical compound ClCCSCCCl QKSKPIVNLNLAAV-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
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- 230000008859 change Effects 0.000 description 1
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- 150000003950 cyclic amides Chemical class 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- 239000012973 diazabicyclooctane Substances 0.000 description 1
- VFFDVELHRCMPLY-UHFFFAOYSA-N dimethyldodecyl amine Natural products CC(C)CCCCCCCCCCCN VFFDVELHRCMPLY-UHFFFAOYSA-N 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000007792 gaseous phase Substances 0.000 description 1
- 229910000856 hastalloy Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 238000000622 liquid--liquid extraction Methods 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 1
- 239000011268 mixed slurry Substances 0.000 description 1
- 235000010460 mustard Nutrition 0.000 description 1
- SEQQCNUPFWGKRU-UHFFFAOYSA-N n,n-bis(2-ethylhexyl)aniline Chemical compound CCCCC(CC)CN(CC(CC)CCCC)C1=CC=CC=C1 SEQQCNUPFWGKRU-UHFFFAOYSA-N 0.000 description 1
- YMJRILLOPVDWSS-UHFFFAOYSA-N n,n-di(cycloheptyl)cycloheptanamine Chemical compound C1CCCCCC1N(C1CCCCCC1)C1CCCCCC1 YMJRILLOPVDWSS-UHFFFAOYSA-N 0.000 description 1
- KWBRAQJMAQRVMS-UHFFFAOYSA-N n,n-di(cyclooctyl)cyclooctanamine Chemical compound C1CCCCCCC1N(C1CCCCCCC1)C1CCCCCCC1 KWBRAQJMAQRVMS-UHFFFAOYSA-N 0.000 description 1
- ZQJAONQEOXOVNR-UHFFFAOYSA-N n,n-di(nonyl)nonan-1-amine Chemical compound CCCCCCCCCN(CCCCCCCCC)CCCCCCCCC ZQJAONQEOXOVNR-UHFFFAOYSA-N 0.000 description 1
- HADFMGBFIUSMPK-UHFFFAOYSA-N n,n-di(pentadecyl)pentadecan-1-amine Chemical compound CCCCCCCCCCCCCCCN(CCCCCCCCCCCCCCC)CCCCCCCCCCCCCCC HADFMGBFIUSMPK-UHFFFAOYSA-N 0.000 description 1
- WFVLGDMOCAFNNS-UHFFFAOYSA-N n,n-di(tetradecyl)tetradecan-1-amine Chemical compound CCCCCCCCCCCCCCN(CCCCCCCCCCCCCC)CCCCCCCCCCCCCC WFVLGDMOCAFNNS-UHFFFAOYSA-N 0.000 description 1
- GDSGXRQXKTWBOS-UHFFFAOYSA-N n,n-di(tridecyl)tridecan-1-amine Chemical compound CCCCCCCCCCCCCN(CCCCCCCCCCCCC)CCCCCCCCCCCCC GDSGXRQXKTWBOS-UHFFFAOYSA-N 0.000 description 1
- JEIFGNLZAYFLFL-UHFFFAOYSA-N n,n-di(undecyl)undecan-1-amine Chemical compound CCCCCCCCCCCN(CCCCCCCCCCC)CCCCCCCCCCC JEIFGNLZAYFLFL-UHFFFAOYSA-N 0.000 description 1
- MXHTZQSKTCCMFG-UHFFFAOYSA-N n,n-dibenzyl-1-phenylmethanamine Chemical compound C=1C=CC=CC=1CN(CC=1C=CC=CC=1)CC1=CC=CC=C1 MXHTZQSKTCCMFG-UHFFFAOYSA-N 0.000 description 1
- WBGPDYJIPNTOIB-UHFFFAOYSA-N n,n-dibenzylethanamine Chemical compound C=1C=CC=CC=1CN(CC)CC1=CC=CC=C1 WBGPDYJIPNTOIB-UHFFFAOYSA-N 0.000 description 1
- FZPXKEPZZOEPGX-UHFFFAOYSA-N n,n-dibutylaniline Chemical compound CCCCN(CCCC)C1=CC=CC=C1 FZPXKEPZZOEPGX-UHFFFAOYSA-N 0.000 description 1
- FRQONEWDWWHIPM-UHFFFAOYSA-N n,n-dicyclohexylcyclohexanamine Chemical compound C1CCCCC1N(C1CCCCC1)C1CCCCC1 FRQONEWDWWHIPM-UHFFFAOYSA-N 0.000 description 1
- NILJCGYQNXKIRL-UHFFFAOYSA-N n,n-dicyclopentylcyclopentanamine Chemical compound C1CCCC1N(C1CCCC1)C1CCCC1 NILJCGYQNXKIRL-UHFFFAOYSA-N 0.000 description 1
- COFKFSSWMQHKMD-UHFFFAOYSA-N n,n-didecyldecan-1-amine Chemical compound CCCCCCCCCCN(CCCCCCCCCC)CCCCCCCCCC COFKFSSWMQHKMD-UHFFFAOYSA-N 0.000 description 1
- CIXSDMKDSYXUMJ-UHFFFAOYSA-N n,n-diethylcyclohexanamine Chemical compound CCN(CC)C1CCCCC1 CIXSDMKDSYXUMJ-UHFFFAOYSA-N 0.000 description 1
- LYYLWJOKAQADDU-UHFFFAOYSA-N n,n-dihexadecylhexadecan-1-amine Chemical compound CCCCCCCCCCCCCCCCN(CCCCCCCCCCCCCCCC)CCCCCCCCCCCCCCCC LYYLWJOKAQADDU-UHFFFAOYSA-N 0.000 description 1
- NPHQHSARAVLMCE-UHFFFAOYSA-N n,n-dihexylhexan-1-amine;formic acid Chemical compound [O-]C=O.CCCCCC[NH+](CCCCCC)CCCCCC NPHQHSARAVLMCE-UHFFFAOYSA-N 0.000 description 1
- ZEFLPHRHPMEVPM-UHFFFAOYSA-N n,n-dimethylcyclopentanamine Chemical compound CN(C)C1CCCC1 ZEFLPHRHPMEVPM-UHFFFAOYSA-N 0.000 description 1
- YWFWDNVOPHGWMX-UHFFFAOYSA-N n,n-dimethyldodecan-1-amine Chemical compound CCCCCCCCCCCCN(C)C YWFWDNVOPHGWMX-UHFFFAOYSA-N 0.000 description 1
- SFBHPFQSSDCYSL-UHFFFAOYSA-N n,n-dimethyltetradecan-1-amine Chemical compound CCCCCCCCCCCCCCN(C)C SFBHPFQSSDCYSL-UHFFFAOYSA-N 0.000 description 1
- MMFBQHXDINNBMW-UHFFFAOYSA-N n,n-dipropylaniline Chemical compound CCCN(CCC)C1=CC=CC=C1 MMFBQHXDINNBMW-UHFFFAOYSA-N 0.000 description 1
- QSVSYAXMSWQTGP-UHFFFAOYSA-N n-(2-ethylhexyl)-n-phenylaniline Chemical compound C=1C=CC=CC=1N(CC(CC)CCCC)C1=CC=CC=C1 QSVSYAXMSWQTGP-UHFFFAOYSA-N 0.000 description 1
- WYZDCUGWXKHESN-UHFFFAOYSA-N n-benzyl-n-methyl-1-phenylmethanamine Chemical compound C=1C=CC=CC=1CN(C)CC1=CC=CC=C1 WYZDCUGWXKHESN-UHFFFAOYSA-N 0.000 description 1
- SRENRFDRXNVMKN-UHFFFAOYSA-N n-butyl-n-phenylaniline Chemical compound C=1C=CC=CC=1N(CCCC)C1=CC=CC=C1 SRENRFDRXNVMKN-UHFFFAOYSA-N 0.000 description 1
- XRKQMIFKHDXFNQ-UHFFFAOYSA-N n-cyclohexyl-n-ethylcyclohexanamine Chemical compound C1CCCCC1N(CC)C1CCCCC1 XRKQMIFKHDXFNQ-UHFFFAOYSA-N 0.000 description 1
- JNMBQGIZTCTCRT-UHFFFAOYSA-N n-cyclopentyl-n-methylcyclopentanamine Chemical compound C1CCCC1N(C)C1CCCC1 JNMBQGIZTCTCRT-UHFFFAOYSA-N 0.000 description 1
- ITMSSZATZARZCA-UHFFFAOYSA-N n-ethyl-n-phenylaniline Chemical compound C=1C=CC=CC=1N(CC)C1=CC=CC=C1 ITMSSZATZARZCA-UHFFFAOYSA-N 0.000 description 1
- POMGZMHIXYRARC-UHFFFAOYSA-N n-hexyl-n-methylhexan-1-amine Chemical compound CCCCCCN(C)CCCCCC POMGZMHIXYRARC-UHFFFAOYSA-N 0.000 description 1
- DYFFAVRFJWYYQO-UHFFFAOYSA-N n-methyl-n-phenylaniline Chemical compound C=1C=CC=CC=1N(C)C1=CC=CC=C1 DYFFAVRFJWYYQO-UHFFFAOYSA-N 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- BCFKYKHGGFAUAF-UHFFFAOYSA-N n-phenyl-n-propylaniline Chemical compound C=1C=CC=CC=1N(CCC)C1=CC=CC=C1 BCFKYKHGGFAUAF-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229910052756 noble gas Inorganic materials 0.000 description 1
- 150000002835 noble gases Chemical class 0.000 description 1
- 125000002868 norbornyl group Chemical group C12(CCC(CC1)C2)* 0.000 description 1
- 229940078552 o-xylene Drugs 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 230000006965 reversible inhibition Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
- SWZDQOUHBYYPJD-UHFFFAOYSA-N tridodecylamine Chemical compound CCCCCCCCCCCCN(CCCCCCCCCCCC)CCCCCCCCCCCC SWZDQOUHBYYPJD-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- 229930004006 tropane Natural products 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
-
- 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
- B01J31/0202—Alcohols or phenols
-
- 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
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0237—Amines
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
- B01J31/2409—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom
- B01J31/2414—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom comprising aliphatic or saturated rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/02—Preparation of carboxylic acids or their salts, halides or anhydrides from salts of carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/41—Preparation of salts of carboxylic acids
-
- 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
-
- 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
- C07C51/48—Separation; Purification; Stabilisation; Use of additives by liquid-liquid treatment
-
- 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
- B01J2231/60—Reduction reactions, e.g. hydrogenation
- B01J2231/62—Reductions in general of inorganic substrates, e.g. formal hydrogenation, e.g. of N2
- B01J2231/625—Reductions in general of inorganic substrates, e.g. formal hydrogenation, e.g. of N2 of CO2
-
- 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
- B01J2531/821—Ruthenium
-
- 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
- B01J2531/90—Catalytic systems characterized by the solvent or solvent system used
- B01J2531/98—Phase-transfer catalysis in a mixed solvent system containing at least 2 immiscible solvents or solvent phases
Definitions
- the invention relates to a process for the preparation of formic acid by reacting carbon dioxide with hydrogen in a hydrogenation reactor in the presence of a catalyst containing an element from the 8th, 9th or 10th group of the periodic table, a tertiary amine and a polar solvent, with formation of formic acid-amine adducts, which are then thermally cleaved to formic acid and tertiary amine.
- Adducts of formic acid and tertiary amines can be thermally cleaved into free formic acid and tertiary amine and therefore serve as intermediates in the preparation of formic acid.
- Formic acid is an important and versatile product. It is used, for example, for acidification in the production of animal feed, as a preservative, as a disinfectant, as an adjuvant in the textile and leather industry, as a mixture with their salts for de-icing of airplanes and runways and as a synthesis component in the chemical industry.
- the said adducts of formic acid and tertiary amines can be prepared in various ways, for example (i) by direct reaction of the tertiary amine with formic acid, (ii) by hydrolysis of methyl formate to formic acid in the presence of the tertiary amine, (iii) by catalytic Hydration of carbon monoxide in the presence of the teriary amine or (iv) by hydrogenation of carbon dioxide to formic acid in the presence of the tertiary amine.
- the latter method of catalytic hydrogenation of carbon dioxide has the particular advantage that carbon dioxide is available in large quantities and is flexible in its source.
- EP 0 181 078 describes a process for the preparation of formic acid by thermal cleavage of adducts of formic acid and a teriary amine.
- the process for the preparation of formic acid comprises the following steps: i) reacting carbon dioxide and hydrogen in the presence of a volatile tertiary amine and a catalyst to obtain the adduct of formic acid and the volatile tertiary amine, ii) separation of the adduct of formic acid and volatile tertiary amine from the catalyst and the gaseous components in an evaporator, iii) separation of the unreacted volatile tertiary amine in a distillation column or in a phase separation device from the adduct
- Formic acid and the volatile tertiary amine iv) base exchange of the volatile tertiary amine in the adduct of formic acid and the volatile tertiary amine by a less volatile and weaker nitrogen base, such as 1 -n-butylimidazole, v) thermal cleavage of the adduct of formic acid and the less volatile and weaker nitrogen base to yield formic acid and the less volatile and weaker nitrogenous base.
- a less volatile and weaker nitrogen base such as 1 -n-butylimidazole
- EP 0 181 078 the volatile tertiary amine in the formic acid adduct must be replaced by a less volatile and weaker nitrogen base, such as, for example, 1-n-butylimidazole, before the thermal cleavage.
- a less volatile and weaker nitrogen base such as, for example, 1-n-butylimidazole
- EP 0 181 078 A further significant disadvantage of the process according to EP 0 181 078 is the fact that the separation of the adduct of formic acid and volatile tertiary amine according to the above-described step ii) EP 0 181 078 takes place in an evaporator in the presence of the catalyst.
- the cleavage leads to a significant reduction in the yield of adduct of formic acid and volatile tertiary amine and thus to a reduction in the yield of the target product formic acid.
- EP 0 329 337 proposes the addition of an inhibitor which inhibits the catalyst in order to solve this problem.
- Preferred inhibitors include carboxylic acids, carbon monoxide and oxidizing agents.
- the preparation of formic acid therefore comprises the steps described above in EP 0 181 078 i) to v), wherein the addition of the inhibitor takes place after step i) and before or during step ii).
- the catalyst can be recycled to the reaction.
- a fundamental disadvantage of EP 0 329 337 is that a large part of the catalyst in the process is inhibited.
- WO 2010/149507 describes a process for the preparation of formic acid by hydrogenation of carbon dioxide in the presence of a tertiary amine, a transition metal catalyst and a high-boiling polar solvent having an electrostatic factor> 200 * 10 -30 cm, such as ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, 1, 3-propanediol, 2-methyl-1, 3-propanediol, 1, 4-butanediol, dipropylene glycol, 1, 5-pentanediol, 1, 6-hexanediol and glycerol.
- a disadvantage of the process of WO 2010/149507 is that the separation of the catalyst despite phase separation (step 1)) and extraction (step 2)) is not always completely successful, so that traces of catalyst contained in the raffinate in the thermal cracking in the distillation column in Step 3) can catalyze the cleavage of the formic acid-amine adduct to carbon dioxide and hydrogen and the tertiary amine. It is also disadvantageous that esterification of the formic acid formed with the high-boiling polar solvents (diols and polyols) occurs in the thermal cleavage of the formic acid-amine adduct in the distillation column. This leads to a reduction in the yield of the target product formic acid.
- Solvent selected from the group consisting of methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol and water and at least one tertiary amine of the general formula (A1)
- R 1 , R 2 , R 3 independently represent an unbranched or branched, acyclic or cyclic, aliphatic, araliphatic or aromatic radical each having 1 to 16 carbon atoms, wherein individual carbon atoms independently of one another by a hetero group selected from the groups -O- and > N-substituted and two or all three radicals can also be linked together to form a chain comprising at least four atoms, in the presence of at least one complex catalyst which contains at least one element selected from groups 8, 9 and 10 of the Periodic Table, in a hydrogenation reactor to obtain, optionally after addition of water, a biphasic hydrogenation mixture (H) comprising an upper phase (01) containing the at least one complex catalyst and the at least one tertiary amine (A1), and a lower phase (U 1) the at least one polar solvent,
- H biphasic hydrogenation mixture
- step (b1) phase separation of the hydrogenation mixture (H) obtained in step (a) in a first phase separation device into the upper phase (01) and the lower phase (U 1), or
- step (b2) extraction of the at least one complex catalyst from the hydrogen mixture (H) obtained in step (a) in an extraction unit with an extractant containing the at least one tertiary amine (A1) to obtain a raffinate (R1) containing the at least one formic acid amine Adduct (A2) and the at least one polar solvent and an extract (E1) containing the at least one tertiary amine (A1) and the at least one complex catalyst or
- step (b3) phase separation of the hydrogenation mixture (H) obtained in step (a) in a first phase separation device into the upper phase (01) and the lower phase (U 1) and extraction of the residues of the at least one complex catalyst from the lower phase (U 1) in one
- Extraction unit comprising an extractant containing the at least one tertiary amine (A1) to obtain a raffinate (R2) containing the at least one formic acid-amine adduct (A2) and the at least one polar solvent and an extract (E2) containing the at least one tertiary amine (A1) and the radicals of the at least one complex catalyst, (c) separating the at least one polar solvent from the lower phase (U 1), from the raffinate (R1) or from the raffinate (R2) in a first distillation apparatus to obtain a distillate (D1) containing the at least one polar solvent which is present in the hydrogenation reactor is recycled in step (a), and a biphasic bottom mixture (S1) comprising an upper phase (02) containing the at least one tertiary amine (A1), and a lower phase (U2) containing the at least one formic acid amine Contains adduct (A2),
- step (D) optionally working up of the bottom mixture (S1) obtained in step (c) by phase separation in a second phase separation device in the
- step (e) cleavage of the at least one formic acid-amine adduct (A2) contained in the bottom mixture (S1) or, if appropriate, in the bottom phase (U2) in a thermal splitting unit to give the at least one tertiary amine (A1) which is the hydrogenation reactor in step (a) and formic acid discharged from the thermal cleavage unit, immediately before and / or during step (c) of the lower phase (U 1), the
- Raffinate (R1) or the raffinate (R2) carbon monoxide is added and / or immediately before and / or during step (e) the bottom mixture (S1) or optionally the lower phase (U2) carbon monoxide is added.
- the process according to the invention makes it possible to recycle a large part of the complex catalyst into the hydrogenation in its active form, so that only small amounts of inhibitor have to be added and thus only a small part of the complex catalyst has to be reactivated after its inhibition.
- the complex catalyst inhibited by thermal decomposition by carbon monoxide can be recycled back into the hydrogenation in step (a) via the amine phase from the thermal splitting unit in step (e), where it is reactivated under the reaction conditions.
- the entire bottom of the thermal cleavage need not be recycled in step (a) in order to avoid catalyst losses.
- the separation of the polar solvent used according to the invention also prevents esterification of the formic acid obtained in the thermal splitting unit in step (e), which likewise leads to an increase in the yield of formic acid.
- the use of the polar solvents according to the invention leads to an increase in the concentration of the formic acid-amine adduct (A2) in the hydrogenation mixture (H) obtained in step (a) compared to the high-boiling polar solvents used in WO2010 / 149507. leads. This allows the use of smaller reactors, which in turn leads to a cost savings.
- a reaction mixture (Rg) is reacted in process step (a), the carbon dioxide, hydrogen, at least one complex catalyst containing at least one element selected from groups 8, 9 and 10 of the periodic table, at least one polar solvent selected from Group consisting of methanol, ethanol, 1-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol and water and at least one tertiary amine of the general formula (A1).
- the carbon dioxide used in process step (a) can be solid, liquid or gaseous. It is also possible to use gas mixtures containing large quantities of carbon dioxide, provided they are substantially free of carbon monoxide (volume fraction of ⁇ 1% CO).
- the hydrogen used in the hydrogenation of carbon dioxide in process step (a) is generally gaseous.
- Carbon dioxide and hydrogen may also contain inert gases, such as nitrogen or noble gases.
- inert gases such as nitrogen or noble gases.
- their content is advantageously below 10 mol% based on the total amount of carbon dioxide and hydrogen in the hydrogenation reactor.
- quantities may also be tolerable, they generally require the use of a higher pressure in the reactor, requiring further compression energy.
- Carbon dioxide and hydrogen can be fed to process stage (a) as separate streams. It is also possible to use a mixture containing carbon dioxide and hydrogen in process step (a).
- tertiary amine (A1) is used in process step (a) in the hydrogenation of carbon dioxide.
- tertiary amine (A1) is understood as meaning both one (1) tertiary amine (A1) and mixtures of two or more tertiary amines (A1).
- the tertiary amine (A1) used in the process according to the invention is preferably selected or matched with the polar solvent such that the hydrogenation mixture (H) obtained in process step (a) is at least biphasic, if appropriate after the addition of water.
- the hydrogenation mixture (H) contains an upper phase (01) containing the at least one complex catalyst and the at least one tertiary amine (A1), and a lower phase (U 1) containing the at least one polar solvent, residues of the complex catalyst and at least one formic acid Amine adduct (A2).
- the tertiary amine (A1) should be enriched in the upper phase (01), i. the upper phase (01) should contain the main part of the tertiary amine (A1).
- enriched or "main part” with respect to the tertiary amine (A1) is a weight fraction of the free tertiary amine (A1) in the upper phase (01) of> 50% based on the total weight of the free tertiary Amine (A1) in the liquid phases, ie the upper phase (01) and the lower phase (U 1) in the hydrogenation mixture (H) to understand.
- free tertiary amine (A1) is meant the tertiary amine (A1) which is not bound in the form of the formic acid-amine adduct (A2).
- the weight fraction of the free tertiary amine (A1) in the upper phase (01) is preferably> 70%, in particular> 90%, in each case based on the total weight of the free tertiary amine (A1) in the upper phase (01) and the lower phase ( U 1) in the hydrogenation mixture (H).
- the selection of the tertiary amine (A1) is generally carried out by a simple experiment in which the phase behavior and the solubility of the tertiary amine (A1) in the liquid phases (upper phase (01) and lower phase (U1)) under the process conditions in the process stage (a) be determined experimentally.
- non-polar solvents such as aliphatic, aromatic or araliphatic solvents may be added to the tertiary amine (A1).
- Preferred non-polar solvents are, for example, octane, toluene and / or xylenes (o-xylene, m-xylene, p-xylene).
- the preferred tertiary amine to be used in the process according to the invention is an amine of the general formula
- NR 1 R 2 R 3 in which the radicals R 1 , R 2 , R 3 are identical or different and independently of one another are an unbranched or branched, acyclic or cyclic, aliphatic, araliphatic or aromatic radical having in each case 1 to 16 carbon atoms, preferably 1 to 12 carbon atoms, wherein individual carbon atoms can be substituted independently of one another by a hetero group selected from the groups -O- and> N- and two or all three radicals to form a chain comprising at least four atoms in each case also connected to each other can.
- a tertiary amine of the general formula (A1) is used, with the proviso that the total number of carbon atoms is at least 9.
- Suitable tertiary amines (A1) include:
- triphenylamine methyldiphenylamine, ethyldiphenylamine, propyldiphenylamine, butyldiphenylamine, 2-ethylhexyldiphenylamine, dimethylphenylamine, diethylphenylamine, dipropylphenylamine, dibutylphenylamine, bis (2-ethylhexyl ) - phenylamine, tribenzylamine, methyl-dibenzylamine, ethyl-dibenzylamine and theirs by one or more methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2-butyl or 2-methyl-2- propyl groups substituted derivatives.
- Nd-bis-C 1-4 -alkyl-piperidines N, N-di-d-bis-C 1-4 -alkyl-piperazines, N-crib-C 12 -alkyl-pyrrolidones, NC-bis-C 1-4 -alkyl-imidazoles and theirs one or more methyl.
- DBU 1, 8-diazabicyclo [5.4.0] undec-7-ene
- DABCO 1, 4-diazabicyclo [2.2.2] octane
- tropane N-methyl-8-azabicyclo [3.2 .1] octane
- garnetane N-methyl-9-azabicyclo [3.3.1] nonane
- 1-azabicyclo [2.2.2] octane quinuclidine
- mixtures of two or more different tertiary amines (A1) can also be used.
- the unbranched or branched, acyclic or cyclic, aliphatic radical preferably contains at least 1 and preferably not more than 10 carbon atoms. In the case of an exclusively cyclic radical in the above-mentioned sense, the number of carbon atoms is 3 to 12 and preferably at least 4 and preferably at most 8 carbon atoms.
- Preferred radicals are ethyl, 1-butyl, sec-butyl, 1-octyl and cyclohexyl.
- the phosphine group can contain one, two or three of the above-mentioned unbranched or branched, acyclic or cyclic, aliphatic radicals. These can be the same or different.
- the phosphine group contains radicals other than the abovementioned unbranched or branched, acyclic or cyclic, aliphatic radicals, these generally correspond to those which are customarily used in the case of phosphine ligands for organometallic complex catalysts.
- acyclic or cyclic, aliphatic radicals these generally correspond to those which are customarily used in the case of phosphine ligands for organometallic complex catalysts.
- phenyl, tolyl and xylyl examples of its called phenyl, tolyl and xylyl.
- the homogeneous catalysts can be used both directly in their active form and starting from customary standard complexes such as [M (p-cymene) Cl 2 ] 2 , [M (benzene) Cl 2 ] n , [M (COD) (allyl)], [MCI 3 ⁇ H 2 O], [M (acetylacetonate) 3 ], [M (COD) Cl 2 ] 2 , [M (DMSO) 4 Cl 2 ] with M being the same element from the 8th, 9th or 10th Group of the periodic table with the addition of the corresponding or the corresponding phosphine ligands are produced only under reaction conditions.
- customary standard complexes such as [M (p-cymene) Cl 2 ] 2 , [M (benzene) Cl 2 ] n , [M (COD) (allyl)], [MCI 3 ⁇ H 2 O], [M (acetylacetonate) 3 ], [M (COD) Cl 2 ] 2
- Homogeneous complex catalysts which are preferred in the process according to the invention are selected from the group consisting of [Ru (P n Bu 3 ) 4 (H) 2 ], [Ru (P n octyl 3 ) 4 (H) 2 ], [Ru (P n Bu 3 ) 2 (1, 2-bis (dicyclohexylphosphino) ethane) (H) 2], [Ru (P n-octyl 3) 2 (1, 2-bis (dicyclohexylphosphino) ethane) (H) 2], [Ru (PEt 3 ) 4 (H) 2 ]
- TOF values (turn-over-frequency) of greater than 1000 r.sup.- 1 can be achieved.
- the hydrogenation of carbon dioxide in process step (a) is preferably carried out in the liquid phase at a temperature in the range of 20 to 200 ° C and a total pressure in the range of 0.2 to 30 MPa abs.
- the temperature is at least 30 ° C and more preferably at least 40 ° C and preferably at most 150 ° C, more preferably at most 120 ° C and most preferably at most 80 ° C.
- the total pressure is preferably at least 1 MPa abs and more preferably at least 5 MPa abs and preferably at most 20 MPa abs.
- the hydrogenation is carried out in process step (a) at a temperature in the range of 40 to 80 ° C and a pressure in the range of 5 to 20 MPa abs.
- the partial pressure of the carbon dioxide in process step (a) is generally at least 0.5 MPa and preferably at least 2 MPa and generally at most 8 MPa.
- the hydrogenation is carried out in Process step (a) at a partial pressure of carbon dioxide in the range of 2 to 7.3 MPa.
- the partial pressure of the hydrogen in process step (a) is generally at least 0.5 MPa and preferably at least 1 MPa and generally at most 25 MPa and preferably at most 15 MPa.
- the hydrogenation in process step (a) is carried out at a partial pressure of the hydrogen in the range of 1 to 15 MPa.
- the molar ratio of hydrogen to carbon dioxide in the reaction mixture (Rg) in the hydrogenation reactor is preferably 0, 1 to 10 and more preferably 1 to 3.
- the molar ratio of carbon dioxide to tertiary amine (A1) in the reaction mixture (Rg) in the hydrogenation reactor is preferably 0, 1 to 10 and more preferably 0.5 to 3.
- the reactor In the batchwise procedure, the reactor is equipped with the desired liquid and optionally solid feedstocks and auxiliaries, and then carbon dioxide and the polar solvent are pressed to the desired pressure at the desired temperature. After the end of the reaction, the reactor is normally depressurized and the two liquid phases formed are separated from one another. In the continuous mode of operation, the feedstocks and auxiliaries, including carbon dioxide and hydrogen, are added continuously. Accordingly, the liquid phases are continuously discharged from the reactor, so that the liquid level in the reactor remains the same on average. Preference is given to the continuous hydrogenation of carbon dioxide.
- the average residence time of the components in the hydrogenation reactor contained in the reaction mixture (Rg) is generally from 5 minutes to 5 hours.
- a hydrogenation mixture (H) is obtained in process step (a) which contains the complex catalyst, the polar solvent, the tertiary amine (A1) and the at least one formic acid-amine adduct (A2).
- formic acid-amine adduct (A2) is understood as meaning both one (1) formic acid-amine adduct (A2) and mixtures of two or more formic acid-amine adducts (A2) or more formic acid-amine adducts (A2) are obtained in process step (a), if in the reaction mixture used (Rg) two or more tertiary amines (A1) are used.
- a reaction mixture (Rg) is used in process step (a) which comprises a (1) tertiary amine (A1), a hydrogenation mixture (H) being obtained which comprises one (1) formic acid amine.
- Adduct (A2) contains.
- a reaction mixture (Rg) is used in process step (a) which comprises tri-n-hexylamine as the tertiary amine (A1) to give a hydrogenation mixture (H) which comprises the formic acid amine.
- Adduct of tri-n-hexylamine and formic acid corresponds to the following formula (A3)
- x is in the range of 0.4 to 5.
- the factor X indicates the average composition of the formic acid-amine adduct (A2) and (A3), respectively. the ratio of bound tertiary amine (A1) to bound formic acid in the formic acid-amine adduct (A2) or (A3).
- the factor x can be determined, for example, by determining the formic acid content by acid-base titration with an alcoholic KOH solution against phenolphthalein. In addition, a determination of the factor x, by determining the amine content by gas chromatography is possible.
- the exact composition of the formic acid-amine adduct (A2) or (A3) depends on many parameters, such as the concentrations of formic acid and tertiary amine (A1), the pressure, the temperature and the presence and nature of other components, in particular of the polar solvent. Therefore, the composition of the formic acid amine adduct (A2) or (A3), ie the factor x ,, can also change over the individual process stages.
- a formic acid-amine adduct (A2) or (A3) with a higher formic acid content generally forms, the excess bound tertiary amine (A1) being formed from the formic acid-amine adduct (A2 ) is split off and forms a second phase.
- a formic acid-amine adduct (A2) or (A3) is generally obtained in which x is in the range from 0.4 to 5, preferably in the range from 0.7 to 1.6 ,
- the formic acid-amine adduct (A2) is enriched in the lower phase (U 1), i. the lower phase (U 1) contains the major part of the formic acid-amine adduct.
- the term "enriched" or "main part" with respect to the formic acid-amine adduct (A2) refers to a weight proportion of the formic acid-amine adduct (A2) in the lower phase (U 1) of> 50% to understand the total weight of the formic acid-amine adduct (A2) in the liquid phases (upper phase (01) and lower phase (U 1)) in the hydrogenation reactor.
- the weight fraction of the formic acid-amine adduct (A2) in the lower phase (U 1) is preferably> 70%, in particular> 90%, in each case based on the total weight of the formic acid-amine adduct (A2) in the upper phase (01 ) and the lower phase (U 1).
- the hydrogenation mixture (H) obtained in the hydrogenation of carbon dioxide in process step (a) preferably has two liquid phases and is further worked up in process step (b) according to one of the steps (b1), (b2) or (b3).
- the hydrogenation mixture (H) according to step (b1) is further worked up.
- the invention therefore also provides a process for the preparation of formic acid, comprising the steps
- reaction mixture comprising carbon dioxide, hydrogen, at least one polar solvent selected from the group consisting of methanol,
- R 1 , R 2 , R 3 have the abovementioned meanings, phase separation of the hydrogenation mixture (H) obtained in step (a) in a first phase separation device into the upper phase (01) and the lower phase (U 1), (c) separating the at least one polar solvent from the lower phase (U 1) in a first distillation apparatus to obtain a distillate (D1) containing the at least one polar solvent which is recycled to the hydrogenation reactor in step (a) and a biphasic mixed slurry (S1) comprising an upper phase (02) containing the at least one tertiary amine (A1), and a lower phase (U2) containing the at least one formic acid-amine adduct (A2),
- step (e) cleavage of the at least one formic acid-amine adduct (A2) contained in the bottom mixture (S1) or, if appropriate, in the bottom phase (U2) in a thermal splitting unit to give the at least one tertiary amine (A1) which is the hydrogenation reactor in step (a) and formic acid discharged from the thermal cleavage unit, carbon monoxide being added immediately before and / or during step (c) to the lower phase (U 1) and / or immediately before and / or during step (e ) is added to the bottom mixture (S1) or optionally the lower phase (U2) carbon monoxide.
- the polar solvent and the tertiary amine (A1) can be selected such that the separation of the lower phase (U 1) enriched with the formic acid-amine adducts (A2) and the polar solvent from the tertiary amine (A1 ) and complex catalyst-enriched upper phase (01) and the return of the upper phase (01) to the hydrogenation reactor at a pressure of 1 to 30 MPa abs can be carried out.
- the pressure is preferably at most 15 MPa abs. It is thus possible, without prior relaxation, to separate both liquid phases (upper phase (01) and lower phase (U 1)) in the first phase separation device and to recirculate the upper phase (01) to the hydrogenation reactor without appreciable pressure increase.
- R 1 , R 2 , R 3 have the meanings given above,
- step (b3) Phase separation of the hydrogenation mixture (H) obtained in step (a) in a first phase separation apparatus into the upper phase (01) and the lower phase (U 1) and extraction of the residues of the at least one complex catalyst from the lower phase (U 1) in an extraction unit with an extractant containing the at least one tertiary amine (A1) to obtain a raffinate (R2) containing the at least one formic acid amine
- step (c) separating the at least one polar solvent from the raffinate (R2) in a first distillation apparatus to obtain a distillate (D1) containing the at least one polar solvent which is recycled to the hydrogenation reactor in step (a) and a biphasic mixture of bottoms ( S1) an upper phase (02) containing the at least one tertiary amine (A1) and a lower phase (U2) containing the at least one formic acid-amine adduct (A2),
- A2 formic acid-amine adduct
- the hydrogenation mixture (H) obtained in process step (a) is separated into the lower phase (U 1) and the upper phase (01), which is recycled to the hydrogenation reactor, as described above for process step (b1) in the first phase separation device.
- the statements and preferences made for process step (b1) apply correspondingly to process step (b3).
- the hydrogenation reactor simultaneously acts as the first phase separation device. The upper phase (01) then remains in the hydrogenation reactor and the lower phase (U 1) is fed to the extraction unit.
- the lower phase (U 1) obtained after phase separation is subsequently subjected in an extraction unit to extraction with at least one tertiary amine (A1) as extractant to remove the residues of the complex catalyst to obtain a raffinate (R2) containing the at least one formic acid-amine adduct (A2) and the at least one polar solvent and an extract (E2) containing the at least one tertiary amine (A1) and the radicals of the complex catalyst.
- the same tertiary amine (A1) used in process step (a) in the reaction mixture (Rg) is used as extractant, so that the statements and preferences with respect to the tertiary amine (A) for the process step (a) A1) apply correspondingly to process step (b3).
- the extract (E2) obtained in process step (b3) is recycled in a preferred embodiment to the hydrogenation reactor in process step (a). This allows efficient recovery of the expensive complex catalyst.
- the raffinate (R2) is supplied in a preferred embodiment of the first distillation apparatus in process step (c).
- the extractant used in process step (b3) is preferably the tertiary amine (A1) which is obtained in the thermal splitting unit in process step (e).
- the tertiary amine (A1) obtained in the thermal splitting unit in process step (e) is recycled to the extraction unit in process step (b3).
- the extraction is carried out in process step (b3) generally at temperatures in the range of 30 to 100 ° C and pressures in the range of 0, 1 to 8 MPa.
- the extraction can also be carried out under hydrogen pressure.
- the extraction of the complex catalyst can be carried out in any suitable apparatus known to the person skilled in the art, preferably in countercurrent extraction columns, mixer-settler cascades or combinations of mixer-settler cascades and countercurrent extraction columns.
- fractions of individual components of the polar solvent from the subphase (U 1) to be extracted in the extraction agent, the tertiary amine (A1), are dissolved in addition to the complex catalyst. This is not a disadvantage for the process, since the already extracted amount of polar solvent does not have to be supplied to the solvent removal and thus may save evaporation energy.
- the hydrogenation mixture (H) is further worked up according to step (b2).
- the invention therefore also provides a process for the preparation of formic acid, comprising the steps (A) homogeneously catalyzed reaction of a reaction mixture (Rg) containing carbon dioxide, hydrogen, at least one polar solvent selected from the group consisting of methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl 1-propanol and water and at least one tertiary amine of the general formula
- step (c) separating the at least one polar solvent from the raffinate (R1) in a first distillation apparatus to obtain a distillate (D1) containing the at least one polar solvent which is recycled to the hydrogenation reactor in step (a) and a biphasic mixture ( S1) comprising an upper phase (02) containing the at least one tertiary amine (A1) and a lower phase (U2) containing the at least one formic acid-amine adduct (A2),
- step (D) optionally working up of the bottom mixture (S1) obtained in step (c) by phase separation in a second phase separation device in the
- the hydrogenation mixture (H) is in this case subjected in an extraction unit to extraction with at least one tertiary amine (A1) as extractant to remove the catalyst to obtain a raffinate (R1) containing the at least one formic acid-amine adduct (A2) and the at least a polar solvent and an extract (E1) containing the at least one tertiary amine (A1) and the at least one complex catalyst.
- the same tertiary amine (A1) used in process step (a) in the reaction mixture (Rg) is used as extractant, so that the statements and preferences with respect to the tertiary amine (A) for the process step (a) A1) apply correspondingly to process step (b2).
- the extract (E1) obtained in process step (b2) is recycled in a preferred embodiment to the hydrogenation reactor in process step (a). This allows efficient recovery of the expensive complex catalyst.
- the raffinate (R1) is supplied in a preferred embodiment of the first distillation apparatus in process step (c).
- the extraction of the complex catalyst can be carried out in any suitable apparatus known to the person skilled in the art, preferably in countercurrent extraction columns, mixer-settler cascades or combinations of mixer-settler cascades and countercurrent extraction columns.
- the complex catalyst in addition to the complex catalyst also shares of individual components of the polar solvent from the hydrogenation mixture to be extracted (H) in the extractant, the tertiary amine (A1), dissolved.
- H hydrogenation mixture
- A1 tertiary amine
- the inhibition of the complex catalyst with carbon monoxide may occur immediately before and / or during step (c) and / or immediately before and / or during step (e).
- inhibition occurs exclusively immediately before and / or during step (c). In one embodiment, inhibition occurs exclusively immediately before and / or during step (e).
- the raffinate (R2) obtained according to process step (b3) contains traces of the complex catalyst in amounts of ⁇ 30 ppm, preferably ⁇ 20 ppm and in particular ⁇ 10 ppm, in each case based on the total weight of the raffinate (R2).
- the inhibitor converts the complex catalyst into an inactive form (inhibited complex catalyst).
- at least one ligand of the complex catalyst is replaced by carbon monoxide.
- Part of the ligands originally contained in the active complex catalyst is split off.
- the cleaved ligands are after the inhibition in their free, ie not bound to the metal component of the complex catalyst form before (free ligands).
- the cleavage of the formic acid-amine adduct (A2) or the free formic acid is prevented, since the complex catalyst in the presence of carbon monoxide (in its inhibited form) the cleavage of the formic acid-amine adduct (A2) or the free formic acid not can catalyze more.
- enriched for process step (e) is a distribution coefficient
- the inhibited complex catalyst contained in the upper phase (03) is reactivated before recycling in step (a).
- the inhibited complex catalyst is subjected to a thermal treatment in the absence of free carbon monoxide to convert the inhibited complex catalyst to the active form prior to recycling in step (a), thereby increasing the space-time yield in the hydrogenation.
- the upper phase (03) is heated to a pressure of 10 mbar to 10 bar to 100 to 200 ° C. Separation of the polar solvent; Process step (c)
- the polar solvent is separated off from the lower phase (U 1), from the raffinate (R 1) or from the raffinate (R 2) in a first distillation apparatus.
- a distillate (D1) and a two-phase bottoms mixture (S1) are obtained.
- the distillate (D1) contains the separated polar solvent and is recycled to the hydrogenation reactor in step (a).
- the bottoms mixture (S1) contains the upper phase (02) containing the tertiary amine (A1) and a lower phase (U2) containing the formic acid-amine adduct (A2).
- the polar solvent in the first distillation apparatus in process stage (c), the polar solvent is partly removed, so that the bottom mixture (S1) contains not yet separated polar solvent.
- process step (c) for example, from 5 to 98% by weight of the polar solvent contained in the lower phase (U 1), in the raffinate (R 1) or in the raffinate (R 2), preferably 50 to 98% by weight, more preferably 80 to 98 wt .-% and particularly preferably 80 to 90 wt .-% are separated, in each case based on the total weight of the in the lower phase (U 1) in the raffinate (R1) or in the raffinate (R2) polar solvent.
- the carbon monoxide serving as a decomposition inhibitor can be added in gaseous form either into the feed or directly into the first distillation apparatus.
- the polar solvent is used in the first distillation apparatus in process stage (c) completely detached.
- “completely separated off” is a separation of more than 98% by weight of the polar solvent present in the lower phase (U 1), in the raffinate (R 1) or in the raffinate (R 2), preferably more than 98.5 wt .-%, particularly preferably more than 99 wt .-%, in particular more than 99.5 wt .-%, understood, in each case based on the total weight of the in the lower phase (U 1), in the raffinate (R1) or in the raffinate (R2) contained polar solvent.
- the distillate (D1) separated in the first distillation apparatus is recycled in a preferred embodiment to the hydrogenation reactor in step (a).
- a mixture of one or more alcohols and water is used as the polar solvent, it is also possible to remove from the first distillation apparatus a low-water distillate (D1 wa ) and a water-rich distillate (D1 wr ).
- the water-rich distillate (D1 wr ) contains more than 50 wt .-% of the water contained in the distillate (D1), preferably more than 70 wt .-%, especially more than 80 wt .-%, in particular more than 90 wt .-%
- the low-water distillate (D1 wa ) contains less than 50 wt .-% of the water contained in the distillate D1, preferably less than 30 wt .-%, more preferably less than 20 wt .-%, in particular less than 10 wt .-%.
- the low-water distillate (D1 wa ) is recycled to the hydrogenation reactor in step (a).
- the water-rich distillate (D 1 wr ) is fed to the upper phase (01).
- the separation of the polar solvent from the lower phase (U 1), the raffinate (R 1) or the raffinate (R 2) can be carried out, for example, in an evaporator or in a distillation unit consisting of evaporator and column, the column containing packings, fillers and / or trays filled, done.
- the at least partial removal of the polar solvent preferably takes place at a bottom temperature at which no free formic acid is formed from the formic acid-amine adduct (A2) at a given pressure.
- the factor x, of the formic acid-amine adduct (A2) in the first distillation apparatus is generally in the range of 0.4 to 3, preferably in the range of 0.6 to 1, 8, particularly preferably in the range of 0.7 to 1, 7.
- the bottom temperature in the first distillation apparatus is at least 20 ° C, preferably at least 50 ° C and particularly preferably at least 70 ° C, and generally at most 210 ° C, preferably at most 190 ° C.
- the temperature in the first distillation apparatus is generally in the range of 20 ° C to 210 ° C, preferably in the range of 50 ° C to 190 ° C.
- the pressure in the first distillation apparatus is generally at least 0.001 MPa abs, preferably at least 0.005 MPa abs and more preferably at least 0.01 MPa abs and generally at most 1 MPa abs and preferably at most 0, 1 MPa abs.
- the pressure in the first distillation apparatus is generally in the range of 0.0001 MPa abs to 1 MPa abs, preferably in the range of 0.005 MPa abs to 0.1 MPa abs and more preferably in the range of 0.01 MPa abs to 0.1 MPa abs.
- the formic acid-amine adduct (A2) and free tertiary amine (A1) can be obtained in the bottom of the first distillation apparatus, since the removal of the polar solvent gives formic acid-amine adducts with a lower amine content ,
- the bottom mixture (S1) contains, depending on the separated amount of the polar solvent, the formic acid-amine adduct (A2) and optionally the free tertiary amine (A1) formed in the bottom of the first distillation apparatus.
- the bottoms mixture (S1) is further worked up in process step (d) for further work-up and then fed to process step (e). It is also possible to feed the bottoms mixture (S1) from process step (c) directly to process step (e).
- the bottoms mixture (S1) obtained in step (c) can be separated in a second phase separation device into the upper phase (02) and the lower phase (U2).
- the lower phase (U2) is then further worked up according to process step (e).
- the upper phase (02) is recycled from the second phase separation device to the hydrogenation reactor in step (a).
- the upper phase (02) is recycled from the second phase separation device to the extraction unit.
- the method according to the invention comprises the steps (a), (b3), (c) and (e).
- the method according to the invention consists of the steps (a), (b1), (c), (d) and (e).
- the process according to the invention consists of the steps (a), (b2), (c), (d) and (e).
- the process according to the invention consists of the steps (a), (b3), (c), (d) and (e).
- the process according to the invention consists of the steps (a), (b3), (c), (d) and (e).
- the process according to the invention consists of the steps (a), (b1), (c) and (e).
- the process according to the invention consists of the steps (a), (b2), (c) and (e).
- the process according to the invention consists of the steps (a), (b3), (c) and (e).
- the formic acid-amine adduct (A2) present in the bottom mixture (S1) or optionally in the bottom phase (U2) is cleaved in the thermal splitting unit to give formic acid and tertiary amine (A1).
- the carbon monoxide serving as a decomposition inhibitor can be added in gaseous form either into the feed or directly into the thermal splitting unit.
- the formic acid is discharged from the thermal splitting unit.
- the tertiary amine (A1) is recycled to the hydrogenation reactor in step (a).
- the tertiary amine (A1) from the thermal cleavage unit can be recycled directly to the hydrogenation reactor. It is also possible to initially recycle the tertiary amine (A1) from the thermal splitting unit to the extraction unit in process stage (b2) or process stage (b3) and then to pass it on from the extraction unit to the hydrogenation reactor in step (a); this embodiment is preferred.
- the upper phase (03) contains the inhibited complex catalyst and the free ligands in addition to the tertiary amine (A1).
- thermal cleavage of the formic acid-amine adduct (A2) is generally carried out according to the process parameters known in the prior art with respect to pressure, temperature and apparatus design. These are described, for example, in EP 0 181 078 or WO 2006/021 41 1.
- distillation columns are suitable, which generally contain packing, packings and / or trays.
- the bottom temperature in the second distillation apparatus is at least 130 ° C, preferably at least 140 ° C and more preferably at least 150 ° C, and generally at most 210 ° C, preferably at most 190 ° C, particularly preferably at most 185 ° C.
- the pressure in the second distillation apparatus is generally at least 1 hPa abs, preferably at least 50 hPa abs and more preferably at least 100 hPa abs, and generally at most 500 hPa, more preferably at most 300 hPa abs and more preferably at most 200 hPa abs.
- the feed of the bottom mixture (S1) or optionally the lower phase (U2) takes place both in the second distillation device of the thermal splitting unit, as well as in the third phase separation device of the thermal splitting unit.
- the bottoms mixture (S1) or optionally the lower phase (U2) is divided into two partial streams, wherein a partial stream of the second distillation apparatus and a partial stream of the third phase separator are fed to the thermal splitting unit.
- FIG. 1 a block diagram of a preferred embodiment of the method according to the invention
- FIG. 2 shows a block diagram of a further preferred embodiment of the method according to the invention
- FIG. 5 shows a block diagram of a further preferred embodiment of the method according to the invention.
- FIGS. 7, 8, 9 and 10 are graphical representations of the inhibition experiments H 1, H 2,
- Amine adduct (A2) (lower phase (U2)); Swamp mixture (S1)
- III-3 third phase separation device (the thermal splitting unit)
- the current 3 is added continuously or discontinuously, the inhibitor as stream 4.
- the lower phase (U 1) is separated into a distillate (D 1) containing the polar solvent, which is recycled as stream 5 to the hydrogenation reactor 1-1, and into a biphasic bottom mixture (S1) containing an upper phase (02) containing the tertiary amine (A1) and the inhibited complex catalyst, and the lower phase (U2) containing the formic acid amine adduct (A2).
- the distillate (D2) containing formic acid is discharged as stream 9 from the distillation apparatus IV-1.
- the biphasic bottoms mixture (S2) containing the upper phase (03) containing the tertiary amine (A1) and the lower phase (U3) containing the formic acid-amine adduct (A2) is added as stream 8 to the third phase separation device 111- 1 of the thermal splitting unit recycled.
- the third phase separation device 111-1 the sump mixture (S2) is separated into upper phase (03) and lower phase (U3).
- the upper phase (03) is recycled as stream 10 to the hydrogenation reactor 1-1.
- the lower phase (U3) is recycled as stream 7 to the second distillation device IV-1.
- a tertiary amine (A1) a polar solvent and a complex catalyst containing at least one element from Groups 8, 9 and 10 of the Periodic Table.
- a biphasic hydrogenation mixture (H) which has an upper phase (01) comprising the complex catalyst and the tertiary amine (A1) and a lower phase (U 1) containing the polar solvent, residues of the complex catalyst and the formic acid-amine adduct (A2 ) contains.
- the hydrogenation mixture (H) is fed as stream 13a to a first phase separation device V-2.
- the hydrogenation mixture (H) is separated into the upper phase (01) and the lower phase (U 1).
- the upper phase (01) is recycled as stream 22 to the hydrogenation reactor I-2.
- the lower phase (U 1) is supplied as stream 13b of the extraction unit VI-2.
- the lower phase (U 1) is extracted with the tertiary amine (A1), which is the stream 20 (Upper phase (03)) is recycled from the third phase separation apparatus 111-2 to the extraction apparatus VI-2.
- the sump mixture (S1) is supplied as stream 96 to the third phase separator I I I-6 of the thermal splitting unit.
- Examples E-1 to E-5 show that by varying the catalyst, the amount of water added (both before and after the reaction) and the reaction conditions, the active catalyst can be used again for C0 2 hydrogenation and the ruthenium in deplete the product phase down to 2 ppm with only one extraction.
- Examples F-1 to F-4 show that in the process according to the invention, various polar solvents can be separated under mild conditions from the product phase (lower phase (U1), raffinate (R1) or raffinate (R2)), a lower phase containing lower U2 (U2 ) and an upper phase (02), consisting predominantly of tertiary amine, is obtained.
- product phase lower phase (U1), raffinate (R1) or raffinate (R2)
- U2 lower phase containing lower U2
- an upper phase (02) consisting predominantly of tertiary amine
- the formic acid is then thermally cleaved from the lower phase (U2) from the first step in a vacuum distillation apparatus via a 10 cm Vigreux column from the tertiary amine (A2).
- a single-phase bottom product (S2) is obtained, consisting of the pure tertiary amine (A2), which can be used for extraction of the catalyst and recycling into the hydrogenation.
- the distillate (D2) contains formic acid and residual water.
- composition of the sump (S2) and of the distillate was determined by gas chromatography and by titration of the formic acid with 0.1 N KOH in MeOH potentiometrically using a "Mettler Toledo DL50" titrator
- the parameters and results of the individual experiments are shown in Table 1 .12 reproduced.
- Examples G-1 and G-2 show that in the process according to the invention, various polar solvents can be separated from the product phase under mild conditions, with a lower (U3) formic acid and an upper phase (03) consisting predominantly of tertiary amine (A1).
- U3 formic acid
- U3 the formic acid-rich lower phase
- the formic acid can then be cleaved off at higher temperatures from the tertiary amine (A1), the free tertiary amine (A1) being obtained.
- the formic acid thus obtained still contains some water, which, however, can be separated from the formic acid by a column having a greater separation efficiency.
- the resulting in both the separation of the solvent and in the thermal cleavage tertiary amine (A1) can be used to extract the catalyst.
- the formic acid concentration was determined by titration against 0.1 N KOH in MeOH potentiometrically using a "Mettler Toledo DL50" titrator Synthesis of the catalyst stock solution (KS1) for inhibition experiments: 3.15 g of [Ru (COD) CI 2 ] in air are added to a 1 submitted .2 I Hastelloy autoclave, and 150 g trihexylamine (THA) was added. the autoclave is sealed, checked for leaks with N2 and purged with N 2.
- KS1 catalyst stock solution
- Example H-2 shows that in the process according to the invention the decomposition of the formic acid by residues of the catalyst under the conditions of the solvent separation (step (c)) can be largely suppressed by addition of CO.
- the amine phase which contains most of the inhibited complex catalyst, separated and used in the C0 2 hydrogenation.
- 37.5 g of the amine phase from the experiment for inhibition 12.5 g of methanol and 1 g of water are placed in a 100 ml HC autoclave.
- the autoclave is rendered inert with N 2 and 10 g of CO 2 (22 bar) are pressed on.
- at 70 ° C pressed to 80 bar with H 2 and maintained the pressure over the reaction time by pressing with H 2 to 80 bar.
- the concentration of formic acid in the product phase is 1.6% after 2 hours and 4.3% after 16 hours.
- Example H-3 shows that in the process according to the invention the inhibited complex catalyst can be converted back into the active form under the hydrogenation conditions.
- this reaction mixture is boiled under reflux for a further 10 hours without the addition of CO in order to reactivate the inhibited complex catalyst.
- the formic acid is completely decomposed.
- the amine phase which contains most of the complex catalyst, separated and used again in the C0 2 - hydrogenation.
- 37.5 g of the amine phase from the experiment for inhibition 12.5 g of methanol and 1 g of water are placed in a 100 ml HC autoclave.
- the autoclave is rendered inert with N 2 and 10 g of CO 2 (21 bar) are pressed on.
- Example H-4 shows that in the process according to the invention, the inhibited complex catalyst can be converted back into the active form by thermal treatment without CO under the hydrogenation conditions, and then significantly faster in the hydrogenation and also that the complex catalyst even after inhibition and reactivation preferably present in the amine phase.
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Abstract
Priority Applications (1)
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EP12766684.0A EP2763950A2 (fr) | 2011-10-07 | 2012-10-02 | Procédé de production d'acide formique par réaction de dioxyde de carbone avec de l'hydrogène |
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EP11184297 | 2011-10-07 | ||
PCT/EP2012/069458 WO2013050367A2 (fr) | 2011-10-07 | 2012-10-02 | Procédé de production d'acide formique par réaction de dioxyde de carbone avec de l'hydrogène |
EP12766684.0A EP2763950A2 (fr) | 2011-10-07 | 2012-10-02 | Procédé de production d'acide formique par réaction de dioxyde de carbone avec de l'hydrogène |
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EP2763950A2 true EP2763950A2 (fr) | 2014-08-13 |
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EP12766684.0A Withdrawn EP2763950A2 (fr) | 2011-10-07 | 2012-10-02 | Procédé de production d'acide formique par réaction de dioxyde de carbone avec de l'hydrogène |
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EP (1) | EP2763950A2 (fr) |
JP (1) | JP2014530216A (fr) |
KR (1) | KR20140074373A (fr) |
CN (1) | CN103974927A (fr) |
BR (1) | BR112014008338A2 (fr) |
CA (1) | CA2851175A1 (fr) |
IN (1) | IN2014DN03122A (fr) |
RU (1) | RU2014118032A (fr) |
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WO2016024293A1 (fr) | 2014-08-12 | 2016-02-18 | Council Of Scientific & Industrial Research | Processus catalysé au métal pour la réduction de co2 en formate de sodium et en acide formique |
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GB201112231D0 (en) * | 2011-07-15 | 2011-08-31 | Verdant Bioproducts Ltd | Micro-organism |
US8596013B2 (en) | 2012-04-04 | 2013-12-03 | Valinge Innovation Ab | Building panel with a mechanical locking system |
US9428438B2 (en) | 2012-11-27 | 2016-08-30 | Basf Se | Process for preparing formic acid |
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CA1220222A (fr) * | 1982-05-22 | 1987-04-07 | David J. Drury | Production des sels de formates |
GB8424672D0 (en) | 1984-09-29 | 1984-11-07 | Bp Chem Int Ltd | Production of formic acid |
NZ227890A (en) * | 1988-02-17 | 1992-02-25 | Bp Chemical Ltd | Production of formic acid from a nitrogenous base, carbon dioxide and hydrogen |
DE102004040789A1 (de) | 2004-08-23 | 2006-03-02 | Basf Ag | Verfahren zur Herstellung von Ameisensäure |
US20100063320A1 (en) * | 2007-03-23 | 2010-03-11 | Nina Challand | Method for producing formic acid |
PL2445860T3 (pl) * | 2009-06-26 | 2013-10-31 | Basf Se | Sposób wytwarzania kwasu mrówkowego |
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- 2012-10-02 EP EP12766684.0A patent/EP2763950A2/fr not_active Withdrawn
- 2012-10-02 KR KR1020147011873A patent/KR20140074373A/ko not_active Application Discontinuation
- 2012-10-02 BR BR112014008338A patent/BR112014008338A2/pt not_active IP Right Cessation
- 2012-10-02 CN CN201280059095.3A patent/CN103974927A/zh active Pending
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- 2012-10-02 SG SG11201400997TA patent/SG11201400997TA/en unknown
- 2012-10-02 CA CA2851175A patent/CA2851175A1/fr not_active Abandoned
- 2012-10-02 WO PCT/EP2012/069458 patent/WO2013050367A2/fr active Application Filing
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WO2016024293A1 (fr) | 2014-08-12 | 2016-02-18 | Council Of Scientific & Industrial Research | Processus catalysé au métal pour la réduction de co2 en formate de sodium et en acide formique |
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IN2014DN03122A (fr) | 2015-05-22 |
WO2013050367A2 (fr) | 2013-04-11 |
CN103974927A (zh) | 2014-08-06 |
RU2014118032A (ru) | 2015-11-20 |
WO2013050367A3 (fr) | 2013-10-03 |
SG11201400997TA (en) | 2014-09-26 |
BR112014008338A2 (pt) | 2017-04-18 |
JP2014530216A (ja) | 2014-11-17 |
KR20140074373A (ko) | 2014-06-17 |
CA2851175A1 (fr) | 2013-04-11 |
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