WO2012034991A1 - Procédé de préparation de formamides - Google Patents
Procédé de préparation de formamides Download PDFInfo
- Publication number
- WO2012034991A1 WO2012034991A1 PCT/EP2011/065810 EP2011065810W WO2012034991A1 WO 2012034991 A1 WO2012034991 A1 WO 2012034991A1 EP 2011065810 W EP2011065810 W EP 2011065810W WO 2012034991 A1 WO2012034991 A1 WO 2012034991A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- phase
- formula
- amine
- formic acid
- stream
- Prior art date
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- 150000003948 formamides Chemical class 0.000 title claims abstract description 21
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 8
- BDAGIHXWWSANSR-UHFFFAOYSA-N Formic acid Chemical class OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims abstract description 149
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 115
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 102
- 239000012071 phase Substances 0.000 claims abstract description 91
- 239000002798 polar solvent Substances 0.000 claims abstract description 86
- 150000001412 amines Chemical class 0.000 claims abstract description 71
- 150000003512 tertiary amines Chemical class 0.000 claims abstract description 69
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims abstract description 64
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 58
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 56
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 56
- 239000007791 liquid phase Substances 0.000 claims abstract description 55
- 239000003054 catalyst Substances 0.000 claims abstract description 36
- 238000004821 distillation Methods 0.000 claims abstract description 31
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 29
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 26
- 239000001257 hydrogen Substances 0.000 claims abstract description 26
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 23
- 239000007788 liquid Substances 0.000 claims abstract description 16
- 230000000737 periodic effect Effects 0.000 claims abstract description 7
- 239000000543 intermediate Substances 0.000 claims abstract description 6
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims abstract 3
- 235000019253 formic acid Nutrition 0.000 claims description 87
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 69
- 238000000034 method Methods 0.000 claims description 58
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 51
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 44
- 230000008569 process Effects 0.000 claims description 43
- 238000006243 chemical reaction Methods 0.000 claims description 39
- 238000005191 phase separation Methods 0.000 claims description 32
- 238000000605 extraction Methods 0.000 claims description 31
- 239000002815 homogeneous catalyst Substances 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 24
- 238000000926 separation method Methods 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 14
- 125000002015 acyclic group Chemical group 0.000 claims description 10
- 125000004122 cyclic group Chemical group 0.000 claims description 10
- 230000015572 biosynthetic process Effects 0.000 claims description 8
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical class CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 8
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 7
- 150000001298 alcohols Chemical class 0.000 claims description 6
- 125000001931 aliphatic group Chemical group 0.000 claims description 6
- 150000002009 diols Chemical class 0.000 claims description 6
- 238000004064 recycling Methods 0.000 claims description 6
- 150000003462 sulfoxides Chemical class 0.000 claims description 6
- 150000003950 cyclic amides Chemical class 0.000 claims description 4
- 150000003457 sulfones Chemical class 0.000 claims description 4
- 125000004429 atom Chemical group 0.000 claims description 3
- 125000005842 heteroatom Chemical group 0.000 claims description 3
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 claims description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 2
- QWGRWMMWNDWRQN-UHFFFAOYSA-N 2-methylpropane-1,3-diol Chemical compound OCC(C)CO QWGRWMMWNDWRQN-UHFFFAOYSA-N 0.000 claims description 2
- CIUQDSCDWFSTQR-UHFFFAOYSA-N [C]1=CC=CC=C1 Chemical class [C]1=CC=CC=C1 CIUQDSCDWFSTQR-UHFFFAOYSA-N 0.000 claims description 2
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 2
- 229920000166 polytrimethylene carbonate Polymers 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 abstract description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 47
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 45
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 30
- -1 aliphatic aldehydes Chemical class 0.000 description 26
- 239000002904 solvent Substances 0.000 description 22
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 19
- 239000000047 product Substances 0.000 description 17
- 238000002360 preparation method Methods 0.000 description 15
- DIAIBWNEUYXDNL-UHFFFAOYSA-N n,n-dihexylhexan-1-amine Chemical compound CCCCCCN(CCCCCC)CCCCCC DIAIBWNEUYXDNL-UHFFFAOYSA-N 0.000 description 14
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 13
- 229910052707 ruthenium Inorganic materials 0.000 description 11
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 8
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 8
- 229910002091 carbon monoxide Inorganic materials 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 8
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 7
- 230000009435 amidation Effects 0.000 description 7
- 238000007112 amidation reaction Methods 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 7
- 150000003141 primary amines Chemical class 0.000 description 7
- 239000011541 reaction mixture Substances 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- 150000003335 secondary amines Chemical class 0.000 description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- 239000003446 ligand Substances 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 5
- 150000001408 amides Chemical class 0.000 description 5
- VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical class [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 0.000 description 5
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 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
- 125000002524 organometallic group Chemical group 0.000 description 5
- 238000012856 packing Methods 0.000 description 5
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 230000007306 turnover Effects 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
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 230000002051 biphasic effect Effects 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 4
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 4
- 238000003825 pressing Methods 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 229910052703 rhodium Inorganic materials 0.000 description 4
- 239000010948 rhodium Substances 0.000 description 4
- 238000010626 work up procedure Methods 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
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- QQGNLKJAIVSNCO-UHFFFAOYSA-N N-butylformamide Chemical compound CCCCNC=O QQGNLKJAIVSNCO-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- BOUYBUIVMHNXQB-UHFFFAOYSA-N dicyclohexyl(2-dicyclohexylphosphanylethyl)phosphane Chemical compound C1CCCCC1P(C1CCCCC1)CCP(C1CCCCC1)C1CCCCC1 BOUYBUIVMHNXQB-UHFFFAOYSA-N 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 150000004675 formic acid derivatives Chemical class 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 239000012454 non-polar solvent Substances 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 150000003138 primary alcohols Chemical class 0.000 description 3
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 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
- 125000005270 trialkylamine group Chemical group 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
- IVSZLXZYQVIEFR-UHFFFAOYSA-N 1,3-Dimethylbenzene Natural products CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 2
- FEWLNYSYJNLUOO-UHFFFAOYSA-N 1-Piperidinecarboxaldehyde Chemical compound O=CN1CCCCC1 FEWLNYSYJNLUOO-UHFFFAOYSA-N 0.000 description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-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
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- WAIPAZQMEIHHTJ-UHFFFAOYSA-N [Cr].[Co] Chemical compound [Cr].[Co] WAIPAZQMEIHHTJ-UHFFFAOYSA-N 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 2
- BVCZEBOGSOYJJT-UHFFFAOYSA-N ammonium carbamate Chemical class [NH4+].NC([O-])=O BVCZEBOGSOYJJT-UHFFFAOYSA-N 0.000 description 2
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 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
- 238000010586 diagram Methods 0.000 description 2
- GGSUCNLOZRCGPQ-UHFFFAOYSA-N diethylaniline Chemical compound CCN(CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-N 0.000 description 2
- 238000007700 distillative separation Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000002638 heterogeneous catalyst Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 238000000622 liquid--liquid extraction Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-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
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N o-dimethylbenzene Natural products CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 229910052762 osmium Inorganic materials 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
- 150000003003 phosphines Chemical class 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
- 230000003134 recirculating effect Effects 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
- 238000000638 solvent extraction Methods 0.000 description 2
- 239000011877 solvent mixture Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000010561 standard procedure Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- 125000005208 trialkylammonium group Chemical group 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-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
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- IUQJDHJVPLLKFL-UHFFFAOYSA-N 2-(2,4-dichlorophenoxy)acetate;dimethylazanium Chemical compound CNC.OC(=O)COC1=CC=C(Cl)C=C1Cl IUQJDHJVPLLKFL-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-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
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- ODWVFJUVKLPMDM-UHFFFAOYSA-N 9-methyl-9-azabicyclo[3.3.1]nonane Chemical compound C1CCC2CCCC1N2C ODWVFJUVKLPMDM-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- CPOAGAODWFRKCH-UHFFFAOYSA-N CCCC(O)O.CCCC(O)O.CCCC(O)O Chemical compound CCCC(O)O.CCCC(O)O.CCCC(O)O CPOAGAODWFRKCH-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 241000257303 Hymenoptera Species 0.000 description 1
- YFTOYIUGWUPGAC-UHFFFAOYSA-N NC=O.CCCCNC=O Chemical compound NC=O.CCCCNC=O YFTOYIUGWUPGAC-UHFFFAOYSA-N 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 239000012327 Ruthenium complex Substances 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
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- 238000004458 analytical method Methods 0.000 description 1
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- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 238000010533 azeotropic distillation Methods 0.000 description 1
- 235000012216 bentonite Nutrition 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 239000012455 biphasic mixture Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
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- 150000007942 carboxylates Chemical class 0.000 description 1
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- 125000000753 cycloalkyl group Chemical group 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
- 230000007423 decrease Effects 0.000 description 1
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- 238000011161 development Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
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- VFFDVELHRCMPLY-UHFFFAOYSA-N dimethyldodecyl amine Natural products CC(C)CCCCCCCCCCCN VFFDVELHRCMPLY-UHFFFAOYSA-N 0.000 description 1
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- 238000007599 discharging Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- 239000007792 gaseous phase Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 238000009905 homogeneous catalytic hydrogenation 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 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
- 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
- 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
- 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
- 229910052756 noble gas Inorganic materials 0.000 description 1
- 150000002835 noble gases Chemical class 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 125000002868 norbornyl group Chemical group C12(CCC(CC1)C2)* 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 description 1
- WJIBZZVTNMAURL-UHFFFAOYSA-N phosphane;rhodium Chemical class P.[Rh] WJIBZZVTNMAURL-UHFFFAOYSA-N 0.000 description 1
- GTBPUYSGSDIIMM-UHFFFAOYSA-N phosphane;ruthenium Chemical class P.[Ru] GTBPUYSGSDIIMM-UHFFFAOYSA-N 0.000 description 1
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 150000003303 ruthenium Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- RWRDLPDLKQPQOW-UHFFFAOYSA-N tetrahydropyrrole Substances C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 1
- YTWOHSWDLJUCRK-UHFFFAOYSA-N thiolane 1,1-dioxide Chemical compound O=S1(=O)CCCC1.O=S1(=O)CCCC1 YTWOHSWDLJUCRK-UHFFFAOYSA-N 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003623 transition metal compounds Chemical class 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
- PTMFUWGXPRYYMC-UHFFFAOYSA-N triethylazanium;formate Chemical compound OC=O.CCN(CC)CC PTMFUWGXPRYYMC-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- RMZAYIKUYWXQPB-UHFFFAOYSA-N trioctylphosphane Chemical compound CCCCCCCCP(CCCCCCCC)CCCCCCCC RMZAYIKUYWXQPB-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
- 239000008096 xylene Substances 0.000 description 1
- 150000003738 xylenes Chemical class 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229940102001 zinc bromide Drugs 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/02—Preparation of carboxylic acid amides from carboxylic acids or from esters, anhydrides, or halides thereof by reaction with ammonia or amines
Definitions
- the present invention relates to a process for the preparation of formamides, i. of formamide and its / V-substituted derivatives starting from carbon dioxide.
- Formamide and its derivatives are important selective solvents and extractants because of their polarity. They are z. B. for the extraction of butadiene from C 4 cuts, acetylene from C 2 cracker fractions and aromatics used from aliphatic.
- Formamide, / V-Alkylformamide and A / ./V-dialkylformamide are prepared by reacting methyl formate with ammonia, / V-alkylamines or A /, / V-dialkylamines.
- the liberated methanol can be recycled to the Methylformiatsynthese from carbon monoxide and methanol.
- ammonia or the abovementioned amines are reacted at 20 to 100 ° C. and 2 to 10 MPa directly with carbon monoxide instead of methyl formate.
- Work is carried out in methanol as a solvent with alkoxides as catalysts (Hans-Jürgen Arpe, Industrial Organic Chemistry, 6th edition, 2007, pages 48 to 49).
- the TOF value (Turn Over Frequency) is a measure of the efficiency of the catalyst and indicates how many moles of product per mole of catalyst and hour are formed, cf. J.F. Hartwig: Organotransition Metal Chemistry, 1st Edition, 2010, University Science Books, Sausalito, California, p. 545).
- Carbon dioxide can also be hydrogenated in the presence of dimethylamine and homogeneously dissolved platinum complex compounds of the formula ⁇ -Pt 2 (Ph 2 P-CH 2 -PPh 2 ) 3 ) to dimethylformamide.
- platinum complex compounds of the formula ⁇ -Pt 2 (Ph 2 P-CH 2 -PPh 2 ) 3
- TOF values 57.3 are achieved (Schreiner, S., et al., J. Chem. Soc., Chem. Commun., 1988, pages 602-603).
- An enormous increase in TOF was achieved by the use of homogeneously dissolved ruthenium complex compounds containing trialkyl phosphine ligands.
- the highest TOF value was achieved after 70 hours with 6,000 in the hydrogenation of carbon dioxide at 100 ° C, 13 MPa carbon dioxide and 8 MPa hydrogen in the presence of dimethylamine in the form of ammonium carbamate.
- the catalyst used was RuCl 2 [P (CH 3 ) 3 ] 4 (JACS, Table 7).
- EP 0 095 321 A, EP 0 151 510 A and EP 0 181 078 A describe the hydrogenation of carbon dioxide in the presence of a homogeneous catalyst comprising a transition metal of subgroup VIII (group 8, 9, 10), a tertiary amine and a polar solvent to an adduct of formic acid and the tertiary amine known.
- Ruthenium-based carbonyl, halide and / or triphenylphosphine-containing complex catalysts and rhodium-phosphine complexes are mentioned as preferred homogeneous catalysts.
- the hydrogenation is carried out at a carbon dioxide partial pressure of up to 6 MPa, a hydrogen partial pressure of up to 25 MPa and a temperature of about room temperature to 200 ° C.
- JP 1 1322687 shows that salts of formic acid and tertiary amines are obtained in the reaction of aliphatic aldehydes with formaldehyde in the presence of tertiary amines to give polyalcohols. These salts are previously unrecognizable by-products.
- the application teaches the salts at 20 to 130 ° C with primary or secondary amines to formamides, tertiary amines and water to implement.
- the water of reaction is preferably after addition of a solvent such as. B. toluene separated by azeotropic distillation.
- FIG. 7 shows an integrated process concept for the synthesis and work-up of dimethylformamide:
- the reaction effluent consists of two liquid phases, which are separated from each other.
- the upper, toluene and catalyst-containing phase is concentrated and then returned to the synthesis stage.
- the lower aqueous phase containing the target product dimethylformamide is back-extracted with toluene and worked up by distillation.
- the target products formamide and its derivatives should be made accessible with high yields and selectivities.
- the work-up of the reaction effluent from the reactor should be technically simple, require little energy, and be carried out exclusively with substances already present in the process, without additional auxiliaries.
- the separation and recycling of the homogeneous hydrogenation catalysts in the synthesis step should be as efficient as possible.
- This object is achieved by a process for the preparation of formamides of Formal la in the F and R 2 are independently hydrogen, linear or branched radicals having 1 to 15 carbon atoms, cycloaliphatic radicals having 5 to 10 carbon atoms, a substituted or unsubstituted phenyl radical and a
- Phenyl, and R 1 and R 2 may be closed to a five- or six-membered ring which contains an oxygen atom, a ⁇ / - ⁇ - or N-R radical, where R 1 has the abovementioned meaning,
- N-substituted and two or all three radicals can also be linked together to form a chain comprising at least four atoms, with the proviso that the total number of C atoms per molecule is at least 6,
- the partial stream not recycled to the extraction unit III is returned to the tertiary amine-enriched liquid phase in the hydrogenation reactor I.
- the catalyst to be used in the hydrogenation of carbon dioxide in the process according to the invention is preferably a homogeneous catalyst.
- This contains an element from the 8th, 9th or 10th group of the periodic table, ie Fe, Co, Ni, Ru, Rh, Pd, Os, Ir and / or Pt.
- the catalyst contains Ru, Rh, Pd, Os, Ir and / or Pt, more preferably Ru, Rh and / or Pd, and most preferably Ru.
- the elements mentioned above are homogeneously dissolved in the form of complex-like compounds in the reaction mixture.
- the homogeneous catalyst is to be selected so that it is enriched together with the tertiary amine in the liquid phase (B). Under "enriched” is a distribution coefficient of the homogeneous catalyst
- the liquid phase (A) is the phase containing the solvent enriched with the formic acid / amine adducts.
- this also includes radicals such as -CH 2 -C 6 Hn.
- Suitable radicals are, for example, be mentioned methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2-butyl, 1- (2-methyl) propyl, 2- (2, "- 3nty
- 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 three of the above-mentioned unbranched or branched, acyclic or cyclic, aliphatic radicals, with particular preference, all three radicals are the same.
- Preferred phosphines are P (A7-C n H 2 n + i) 3 where n is 1 to 10, more preferably tri-n-butylphosphine, tri-n-octylphosphine and 1, 2-bis (dicyclohexylphosphino) ethane.
- acyclic or cyclic, aliphatic radicals individual carbon atoms may also be substituted by> P-.
- multidentate for example, bidentate or tridentate phosphine ligands are also included. These preferably contain the
- 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. Examples include phenyl, tolyl and xylyl.
- the organometallic complex compound may contain one or more, for example two, three or four, of the abovementioned phosphine groups having at least one unbranched or branched, acyclic or cyclic, aliphatic radical. The remaining ligands of the organometallic complex may be of different nature.
- Examples which may be mentioned are hydride, fluoride, chloride, bromide, iodide, formate, acetate, propionate, carboxylate, acetylacetonate, carbonyl, DMSO, hydroxide, trialkylamine, alkoxide.
- 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 x H 2 O], [M (acetylacetonate) 3 ], [M (COD) Cl 2 ] 2 , [M ( DMSO) 4 CI 2 ] with M equal to element from the 8th, 9th or 10th group of the periodic table with the addition of the corresponding phosphine ligand or 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 x H 2 O], [M (acetylacetonate) 3 ], [M (COD) Cl 2 ] 2 , [M ( DMSO)
- Preferred homogeneous catalysts in the process according to the invention are [Ru (Pn-Bu 3 ) 4 (H) 2 ], [Ru (Pn-octyl 3 ) 4 (H) 2 ], [Ru (Pn-Bu 3 ) 2 (1, 2 bis (dicyclohexylphosphino) ethane) (H) 2 ], [Ru (Pn-Octyl 3 ) 2 (1, 2-bis (dicyclohexylphosphino) ethane) (H) 2 ], [Ru (PEt 3 ) 4 (H) 2 .
- TOF values turn-over frequency
- the amount of said metal component in the organometallic complex is generally from 0.1 to 5000 ppm by weight, preferably from 1 to 800 ppm by weight, and more preferably from 5 to 800 ppm by weight, based in each case on entire liquid reaction mixture in the hydrogenation reactor.
- the distribution coefficient of the homogeneous catalyst based on the amount of ruthenium in the amine phase and the product phase containing the formic acid / amine adduct after hydrogenation in the range of P is greater than 0.5, more preferably greater than 1.0, and most preferably greater than 4.
- the tertiary amine is selected and matched with the polar solvent such that the hydrogenation product forms two liquid phases and the tertiary amine in the upper phase is enriched in the hydrogenation reactor.
- enriched is meant a weight fraction of> 50% of the free, that is not bound in the form of the formic acid / amine adduct, tertiary amine in the upper phase based on the total amount of free, tertiary amine in both liquid phases.
- the proportion by weight is preferably> 90%.
- the choice of tertiary amine is generally made by a simple experiment in which the solubility of the desired tertiary amine in both liquid phases is determined experimentally under the intended process conditions.
- the upper phase may also contain parts of the polar solvent and a non-polar inert solvent.
- the preferred tertiary amine to be used in the process according to the invention is an amine of the general formula (IVa)
- NR 3 R 4 R 5 in which the radicals R 3 to R 5 are identical or different and independently of one another _ : - : __ 3n QC
- Suitable amines of the formula (IVa) include: triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, tri-n-octylamine , Tri-n-nonylamine, tri-n-decylamine, tri-n-undecylamine, tri-n-dodecylamine, tri-n-tridecylamine, tri-n-tetradecylamine, tri-n-pentadecylamine, tri-n hexadecylamine, tri- (2-ethylhexyl) amine. Dimethyldecylamine, dimethyldodecylamine, dimethyl-tetradecylamine, ethyl-di (2-propyl) amine, dioctylmethylamine, dihexylmethylamine.
- Triphenylamine methyldiphenylamine, ethyldiphenylamine, propyldiphenylamine, butyldiphenylamine, 2-ethylhexyldiphenylamine, dimethylphenylamine, diethylphenylamine, dipropylphenylamine, dibutylphenylamine, bis (2-ethylhexyl) phenylamine, tribenzylamine, methyldibenzylamine, ethyldibenzylamine and theirs by a or a plurality of methyl, ethyl, 1-propy, 2-propyl, 1-butyl, 2-butyl or 2-methyl-2-propyl groups substituted derivatives.
- 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
- the tertiary amine is an amine of general formula (IVa), in which the radicals R 1 to R 3 are independently selected from the group d- to C 2 alkyl, C 5 - to C 8 - Cycloalkyl, benzyl and phenyl.
- a saturated amine i. containing only single bonds of the general formula (IVa).
- a tertiary amine is an amine of the general formula (IVa) in which the radicals R 3 to R 5 are independently selected from the group C 5 - to C 8 -alkyl, in particular tri-n - pentylamine, tri-n-hexylamine, tri-n-heptylamine, tri-n-octylamine, dimethylcyclohexylamine, methyldicyclohexylamine, dioctylmethylamine and dimethyldecylamine.
- the radicals R 3 to R 5 are independently selected from the group C 5 - to C 8 -alkyl, in particular tri-n - pentylamine, tri-n-hexylamine, tri-n-heptylamine, tri-n-octylamine, dimethylcyclohexylamine, methyldicyclohexylamine, dioctylmethylamine and dimethyldecylamine.
- the tertiary amine used is an amine of the general formula (IVa) in which the radicals R 1 to R 3 are selected independently of one another from C 5 - and C 6 -alkyl.
- the tertiary amine is preferably liquid in all process stages. However, this is not a mandatory requirement. It would also be sufficient if the tertiary amine were at least dissolved in suitable solvents. Suitable solvents are in principle those which are chemically inert with regard to the hydrogenation of carbon dioxide and the thermal cleavage of the adduct, in which the tertiary amine and, in the case of the use of a homogeneous catalyst, these also dissolve well, inversely polar solvent and formic acid / Dissolve amine adducts poorly.
- polar solvents such as aliphatic, aromatic or araliphatic hydrocarbons, such as octane and higher alkanes, toluene, xylenes.
- the polar solvent to be used in the hydrogenation of carbon dioxide in the process according to the invention is to be selected or matched with the tertiary amine in such a way that the polar solvent is enriched in the lower phase.
- enriched is meant a weight fraction of> 50% of the polar solvent in the lower phase based on the total amount of polar solvent in both liquid phases.
- the proportion by weight of the polar solvent is generally given by a A simple experiment in which the solubility of the desired polar solvent in both liquid phases under the intended process conditions is determined experimentally.
- the polar solvent may be a pure polar solvent as well as a mixture of various polar solvents as long as the solvent, above-mentioned conditions, boiling point and phase behavior apply.
- Suitable classes of substances which are suitable as polar solvents are preferably alcohols and diols and also their formic esters and water.
- Suitable alcohols include alcohols in which the trialkylammonium formates preferably dissolve in a mixture with water and this product phase has a mixture gap with the free trialkylamine.
- suitable alcohols are methanol, ethanol, 2-methoxyethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol.
- the ratio of alcohol to water should be selected such that, together with the trialkylammonium formate and the trialkylamine, a biphasic mixture is formed in which most of the trialkylammonium formate, water and polar solvent are in the lower phase, generally by a simple Experiment is determined by experimentally determining the solubility of the desired polar solvent mixture in both liquid phases under the intended process conditions.
- Suitable classes of compounds which are suitable as polar solvents are preferably diols and also their formic acid esters, polyols and also their formic acid esters, sulfones, sulfoxides, open-chain or cyclic amides and mixtures of the mentioned classes of substances.
- diols and polyols examples include 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 called glycerin.
- sulfone especially tetramethylene sulfone (sulfolane) is called.
- Suitable sulfoxides are dialkyl sulfoxides, preferably C 1 - to C 6 -dialkyl sulfoxides, in particular dimethylsulfoxide.
- suitable open-chain or cyclic amides are formamide, N-methylformamide, A / ./V-dimethylformamide, / V-methylpyrrolidone, acetamide and / V-methylcaprolactam.
- the molar ratio of the polar solvent or solvent mixture to be used in the process according to the invention to the tertiary amine used is generally 0.5 to 30 and preferably 1 to 20.
- the carbon dioxide to be used in the hydrogenation of carbon dioxide 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 to be used in the hydrogenation of carbon dioxide is generally gaseous. Carbon dioxide and hydrogen may also contain inert gases, such as nitrogen or noble gases. Advantageously, however, their content is below 10 mol% based on the total amount of carbon dioxide and hydrogen in the hydrogenation reactor. While larger amounts may also be tolerable, they generally require the use of a higher pressure in the reactor, requiring further compression energy.
- the hydrogenation of carbon dioxide takes place in the liquid phase preferably at a temperature of 20 to 200 ° C and a total pressure 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 15 MPa abs.
- the partial pressure of the carbon dioxide is generally at least 0.5 MPa and preferably at least 2 MPa and generally at most 8 MPa.
- the partial pressure of hydrogen is generally at least 0.5 MPa and preferably at least 1 MPa and generally at most 25 MPa and preferably at most 10 MPa.
- the molar ratio of hydrogen to carbon dioxide in the feed of the hydrogenation reactor is preferably 0, 1 to 10 and particularly preferably 1 to 3.
- the molar ratio of carbon dioxide to tertiary amine in the feed of the hydrogenation reactor is generally 0, 1 to 10 and preferably 0.5 to 3.
- all reactors which are fundamentally suitable for gas / liquid reactions under the given temperature and the given pressure can be used as hydrogenation reactors.
- Suitable standard reactors for liquid-liquid reaction systems are described, for example, in KD Henkel, "Reactor Types and Their Industrial Applications", in Ullmann's Encyclopedia of Industrial Chemistry, 2005, Wiley-VCH Verlag GmbH & Co. KGaA, DOI: 10.1002 / 14356007.
- b04_087 chapter 3.3 "Reactors for gas-liquid reactions”. Examples which may be mentioned stirred tank reactors, tubular reactors or bubble column reactors.
- the hydrogenation of carbon dioxide can be carried out batchwise or continuously in the process according to the invention.
- the reactor is equipped with the desired liquid and optionally solid feedstocks and auxiliaries, and then carbon dioxide and hydrogen are pressed to the desired pressure at the desired temperature.
- the reactor is generally depressurized and the two liquid phases formed are separated from one another.
- the feedstocks and auxiliaries, including carbon dioxide and hydrogen are added continuously. Accordingly, the liquid phase is continuously removed 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 in the hydrogenation reactor is generally 10 minutes to 5 hours.
- the formic acid / amine adducts formed in the hydrogenation of carbon dioxide in the presence of the catalyst to be used, the polar solvent and the tertiary amine generally have the general formula (IIa)
- the respective average compositions of the amine-formic acid ratios in the product phases in the respective process steps, ie the factor x can be determined, for example, by determining the formic acid content by titration with an alcoholic KOH solution against phenolphthalein and the amine content by gas chromatography.
- the composition of the formic acid / amine adducts, ie the factor x can change during the different process steps. For example, adducts are generally formed after removal of the polar solvent a higher formic acid content with x 2 > Xi with x 2 1 to 4, wherein the excess, free amine can form a second phase.
- the lower phase is enriched with the formic acid / amine adducts as well as the polar solvent.
- a distribution coefficient of the formic acid / amine adducts P [concentration of formic acid / amine adduct (II) in liquid phase (A)] / [concentration of formic acid / amine adduct (II) in Liquid phase (B)] of> 1, where A and B have the meaning given above.
- the distribution coefficient is> 2 and more preferably> 5.
- the upper phase is enriched with the tertiary amine. In the case of the use of a homogeneous catalyst this is also enriched in the upper phase.
- the two liquid phases formed are separated from one another in the process according to the invention and the upper phase is recycled to the hydrogenation reactor.
- a further liquid phase comprising both liquid phases containing unconverted carbon dioxide and a gas phase containing unconverted carbon dioxide and / or unreacted hydrogen to the hydrogenation reactor.
- phase separation vessels are, for example, standard apparatuses and standard methods, which are described, for example, in E. Müller et al. , "Liquid Liquid Extraction", in Ullmann's Encyclopaedia of Industrial Chemistry, 2005, Wiley-VCH Verlag GmbH & Co. KGaA, DOI: 10.1002 / 14356007.b03_06, Chapter 3 "Apparatus".
- the liquid phase enriched with the formic acid / amine adducts as well as the polar solvent is heavier and forms the lower phase.
- the phase separation can be carried out, for example, after relaxation, for example to about or near atmospheric pressure, and cooling of the liquid reaction mixture, for example to about or near ambient temperature.
- relaxation for example to about or near atmospheric pressure
- cooling of the liquid reaction mixture for example to about or near ambient temperature.
- at least part of the at the higher reaction pressure in the Liquid phases of dissolved gas, in particular carbon dioxide degassed in the relaxation and to compress separately as a gas stream and is recirculated to the hydrogenation reactor.
- the lower phase before being returned to the hydrogenation reactor separately to bring to reaction pressure.
- a suitable, designed according to the pressure difference to be overcome designed compressor or a pump, which also consumes additional energy during operation for the recirculating gas and liquid phase.
- the solvent and the amine are preferably to be selected so that the separation of the one, enriched with the formic acid / amine adducts and the polar solvent lower phase of the other, enriched with the tertiary amine upper phase, and the return of the upper phase to Hydrogenating reactor can be carried out at a pressure of 1 to 30 MPa abs.
- the pressure is preferably at most 15 MPa abs.
- the process according to the invention can thus preferably be carried out in such a way that the pressure in the hydrogenation reactor and in the phase separation vessel is the same or approximately the same.
- the process according to the invention can thus preferably be carried out in such a way that the pressure and the temperature in the hydrogenation reactor and in the phase separation vessel are the same or approximately the same, whereby a pressure difference of up to +/- 0.5 MPa or approximately a temperature difference of up to +/- 5 ° C is understood.
- the phase separation takes place at a pressure of at least 50%, very particularly preferably of at least 90% and in particular of at least "-gpression pressure.
- the pressure during the phase separation is particularly high preferably at most 105% and most preferably at most 100% of the reaction pressure.
- both liquid phases can separate very well even at an elevated temperature which corresponds to the reaction temperature.
- the phase separation also no cooling and subsequent heating of the recirculating upper phase is required, which also saves energy.
- the findings for the phase separation under elevated pressure and elevated temperature are exceeded even more that just the upper phase according to the inventive system under pressure by suitable choice of the amine and the polar solvent can have a particularly high absorption capacity for carbon dioxide. This means that any excess carbon dioxide which is not reacted in the hydrogenation reaction is very preferably present in the upper phase and can thus be recycled without problems as a liquid to the reactor.
- the majority of the polar solvent of the separated lower phase is thermally separated from the formic acid / amine adducts in a distillation unit, whereby the polar solvent removed by distillation is recycled to the hydrogenation reactor.
- the pure formic acid / amine adducts and free amine are obtained in the bottom of the distillation unit, since formic acid / amine adducts with a lower amine content are formed during the removal of the polar solvent, resulting in a two-phase bottom mixture consisting of an amine and a formic acid / amine Adduct phase forms ( Figure 2).
- the thermal separation of the polar solvent or mixture is preferably carried out at a bottom temperature at which no free formic acid forms from the formic acid / amine adduct having the higher (x1) or lower (x2) amine content at a given pressure
- the bottom temperature of the thermal separation unit is at least 20 ° C, preferably at least 50 ° C and more preferably at least 70 ° C, and generally at most 210 ° C, more preferably at most 190 ° C.
- the pressure is generally at least 0.0001 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 0, 1 MPa abs.
- the thermal separation of the polar solvent or mixture takes place either in an evaporator or in a distillation unit, consisting of evaporator and column, filled with packing, packing and / or trays.
- ien- r rennun g be condensed, again with the liberated condensation enthalpy can be used, for example, to preheat the solvent coming from the extraction with amine / formic acid adduct mixture to the evaporation temperature (FIG. 1). Alternatively, only parts of the solvent mixture can be separated. It is also possible to separate the polar solvent only in substep VI and to return it to the hydrogenation stage I.
- the solution of tertiary amine adduct and formic acid is extracted with free tertiary amine streams from the appropriate phase separation vessels and recycled to the hydrogenation reactor. This is done to separate residual amounts of hydrogenation catalyst from the product stream. This extraction allows efficient recovery of the expensive, active noble metal catalyst for the hydrogenation reaction.
- the extraction takes place at temperatures of 30 to 100 ° C and pressures of 0, 1 to 8 MPa.
- the extraction can also be carried out under hydrogen pressure.
- the extraction of the hydrogenation 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-settlers.
- a device for adsorbing traces of hydrogenation catalyst may be advantageous to integrate a device for adsorbing traces of hydrogenation catalyst between the extraction apparatus and the thermal separation device.
- Many adsorbents are suitable for adsorption. Examples include polyacrylic acid and its salts, sulfonated polystyrenes and their salts, activated carbons, montmorillonites, bentonites, silica gels and zeolites. If the amount of hydrogenation catalyst in the product stream of the phase separation vessel II is less than 1 ppm, in particular less than 0.1 ppm, the adsorption device is sufficient for the separation of the hydrogenation catalyst and its recovery. Then, the extraction step can be omitted and the tertiary amine can be recycled together with the organic solvent in the hydrogenation.
- the reaction is carried out in the presence of the polar solvent used in the hydrogenation reactor.
- the entire amount of polar solvent arriving in the reactor is preferably used.
- the reaction is preferably carried out at temperatures of 80 to 200 ° C, preferably 100 to 180 ° C, particularly preferably 120 to 170 ° C.
- the pressure is 0.01 to 10 MPa, preferably 0.1 to 7 MPa, particularly preferably 0.2 to 5 MPa.
- reaction effluents in addition to formamides of the formula Ia, predominantly as intermediate formates of the formula Va, i.
- the molar ratio of formic acid in adduct IIa to ammonia or amine III is 1 to 5, preferably 1 to 2, particularly preferably 1 to 1.
- the reaction can be carried out batchwise, but preferably continuously.
- formamides 1a can be carried out in standard reactors, as described, for example, in KD Henkel, "Reactor Types and their Industrial Applications” in Ullmann's Encyclopedia of Industrial Chemistry, 2005, Wiley-VCH Verlag, Chapter 3.3 are indicated. Examples which may be mentioned stirred tank reactors, tubular reactors or bubble column reactors.
- part or all of the polar solvent is removed by distillation before being fed to the formamide reactor and recycled to the hydrogenation reactor (I).
- the amount of polar solvent removed can be from 25 to 99%, preferably from 35 to 97%, particularly preferably from 50 to 95%, of the amount of polar solvent present in the stream before being fed to the reactor.
- This process variant is advantageous, for example, when used as the polar solvent in the hydrogenation of carbon dioxide primary alcohols such as methanol together with water. It is also possible in principle and may be advantageous to use a polar solvent other than the amidation step, in the reactor IV, in the hydrogenation step in the hydrogenation reactor I. For this purpose, the polar solvent is separated from the hydrogenation and recycled to the hydrogenation reactor I. In the amidation stage, a different polar solvent used in the hydrogenation step is used in reactor IV, which is separated again after amidation and in the reactor IV, in which the amidation is carried out, is recycled.
- the carbon dioxide hydrogenation in the presence of methanol and water and the reaction of the adduct (IIa) can be carried out with ammonia in the presence of sulfolane.
- Suitable polar solvents for the amidation are, for example, sulfones, sulfoxides or open-chain or cyclic amides.
- the distillation can be carried out in the separation of low-boiling polar solvents such as the monohydric alcohols methanol, ethanol, propanols and butanols at atmospheric pressure or in vacuo.
- low-boiling polar solvents such as the monohydric alcohols methanol, ethanol, propanols and butanols
- diols working in a vacuum is preferred.
- distillation units can be used as distillation units. At far apart boiling points of the adduct IIa and the polar solvent can, for. B. evaporators such as falling film evaporator can be used.
- the distillation unit to be used generally comprises a distillation column containing packing, packing and / or trays.
- the distribution coefficient is> 2, and more preferably> 5.
- the liquid phase D is enriched with the tertiary amine resulting from the adduct II a.
- the two liquid phases C and D formed are separated from one another in the process according to the invention.
- the liquid phase D is returned to the extraction apparatus and serves there for the extraction of residual amounts of homogeneous, dissolved hydrogenation catalyst. If appropriate, it is desirable, for example, for discharging unwanted by-products or impurities, to remove some of the liquid phases C or D from the process.
- the separation of the two liquid phases C and D is generally carried out by gravimetric phase separation. Suitable for this purpose are, for example, standard apparatus and standard methods, which are described, for example, in E. Müller et. Al., "Liquid-Liquid Extraction,” in Ullmann's Encyclopedia of Industrial Chemistry, 2005, Wiley-VCH Verlag GmbH & Co. KGaA, DOI: 10.1002 / 14356007. b03_06, Chapter 3 "Apparatus”.
- the phase separation can be carried out, for example, after relaxation, for example to about or near atmospheric pressure, and cooling of the liquid reaction mixture, for example to about or near ambient temperature.
- the liquid phase C is passed into a distillation unit VI and worked up there by distillation. It contains the target product formamide of the formula (Ia), optionally unreacted ammonia or amine of the formula (IIIa), water of reaction and polar solvents selected from the group of methanol, ethanol, propanols or butanols or from the group of diols.
- the polar solvents are separated before being fed to the formamide reactor and recycled to the hydrogenation stage I.
- the distillation unit VI consists of at least one, preferably two to three distillation columns. These columns contain, depending on the separation problems z. B. packing, packages and / or floors. If the polar solvents have not previously been separated off, the ethanol / water and propanol / water homoazeotrope in the case of ethanol and heteroazeotrope in the case of butanols are to be taken into account.
- the water of reaction is discharged from the process.
- Polar solvents are recycled to the hydrogenation stage, unreacted ammonia and unreacted amines III a to the reactor.
- the target products, the formamides of the formula (Ia) are discharged from the process and, if necessary, fed to a preferably distillative fine purification.
- adducts of the formula (IIa), formates of the formula (Va) or mixtures of adducts of the formula (IIa) and formates of the formula (Va) with amines of the formula (IIIa), preferably with ammonia and polar solvents Implemented distillation conditions.
- the reaction takes place in a distillation apparatus, for example a distillation flask with attached distillation column.
- Aliphatic, cycloaliphatic or aromatic hydrocarbons such as n-heptane, n-hexane, cyclohexane, methylcyclohexane, toluene, ethylbenzene, ortho, meta and para xylene and mixtures of these compounds can be used as nonpolar solvents. These compounds form heteroazeotrope with water.
- the bottom temperatures of this distillation are 80 to 200 ° C, preferably 110 to 200 ° C, particularly preferably 135 to 190 ° C.
- the pressure is 0.01 MPa to 10 MPa, preferably 0.1 MPa to 7 MPa, more preferably 0.2 to 5 MPa.
- the water of reaction is distilled off together with the polar solvent.
- the process according to the invention has particular advantages when constructing a large-scale production plant with "economy of scale" for the preparation of adducts of the formula (IIa) from tertiary amines and formic acid, which is used for the production of formic acid and of formamides I a.
- the total content of formic acid in the formic acid / amine adduct was determined by titration with 0.1 N KOH in methanol potentiometrically using a Mettler Toledo DL50 titrator ®. From this, the turn-over frequency (TOF) and the reaction rate were calculated. The composition of the two phases was determined by gas chromatography. The ruthenium content was determined by atomic absorption spectroscopy (AAS). The parameters and results of the individual experiments are given in Table 1.
- Example B-1 Table 2 shows that in the phase separation of a Wasserstoffrieraustrags 26.2 g of a lower phase were obtained which contained 6.1 wt .-% formic acid in the form of the formic acid / amine adduct and 33 ppm ruthenium.
- This lower phase was stirred at room temperature under inert conditions three times for 10 minutes each with 26.2 g of tri-n-hexylamine. The phases were separated.
- the ruthenium content of the extracted lower phase as determined by AAS analysis was 21 ppm ruthenium.
- Example B-1 shows that the amount of ruthenium in the lower phase can be reduced by about 36% by extraction with the same tertiary amine already used in C0 2 hydrogenation. Additional extraction steps or continuous countercurrent extraction could further reduce the ruthenium content.
- Example C-1 shows the distillative separation of the polar solvents methanol and water from a hydrogenation. At 120 ° C and 0.02 MPa, a distillate was obtained on a rotary evaporator, which contained all the methanol, 0.3 wt .-% formic acid and almost all water.
- the biphasic bottom effluent (upper phase + lower phase) can be used for the amide preparation in reactor IV (FIGS. 1 and 2).
- Hastelloy C autoclave equipped with a magnetic stirrer bar was placed under inert conditions with the formic acid tertiary amine adduct IIa and, optionally, a nominal solvent and water (see Table 4, Examples D-1 through D-19). filled. Subsequently, the autoclave was sealed. At room temperature dimethylamine, n-butylamine, or ammonia were pressed. Subsequently, the reactor was heated with stirring (700 rpm). After the desired reaction time, the autoclave was cooled and the reaction mixture was depressurized.
- a two-phase product mixture was obtained, the upper phase consisting of the tertiary amine and the lower phase consisting of the corresponding amide, water and optionally polar solvent and optionally ammonium formate. Both phases were separated and weighed using a separatory funnel. The composition of the two phases was determined by gas chromatography and proton NMR spectroscopy. The parameters and results of the individual experiments are shown in Tables 4 to 6.
- Example D-1 Example D-2 Example D-3 Example D-4 Example D-5
- Solvent 72 g 4- No LM 72 g 1, 4- No LM 73 g 1, 4- (LM) Butanediol Butanediol Butanediol
- Example D-1 1 Example D-12 Example D- Example D-14 Example D-15
- Experimental result E-1 shows that the reaction of adduct IIa with n-butylamine in the presence of 1,4-butanediol as the polar solvent gives n-butylformamide in quantitative yield.
- Example F-1 Example F-2 Example F-3 Example F-4 Example F-5
- Trihexylamine 57 g Trihexylamine 16 g Trihexylamine
- Figure 2 is a block diagram of a further preferred method for the preparation of
- carbon dioxide, stream 1, and hydrogen, stream 2 are fed into the hydrogenation reactor I. Therein they are reacted 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 to formic acid-amine adducts.
- a supplementary stream of tertiary amine, (stream 4a) may be provided to the hydrogenation reactor I.
- the two-phase discharge from the hydrogenation reactor I (stream 3) is passed into the phase separation vessel II.
- the phase separation vessel II In the phase separation vessel II there is a lower phase which is enriched with formic acid-amine adducts and the polar solvent, and an upper phase 4, which contains predominantly the tertiary amine in which the homogeneous catalyst is enriched enriched, and from the Phase separation vessel II is recycled to the hydrogenation reactor I.
- the lower phase 5 is fed to an extraction apparatus III, wherein catalyst residues are extracted with the tertiary amine from the phase separation vessel V (stream 12).
- the tertiary amine with the catalyst residues (stream 6) from the extraction unit III is recycled to the hydrogenation reactor I, the product phase 7 from the extraction unit III is fed to the reactor IV, wherein the reaction with ammonia or amines, stream IIIa, takes place.
- the biphasic liquid effluent, stream 9, from the reactor IV is separated in a phase separation vessel V into a formamide-enriched liquid phase, stream 10, and a second tertiary amine-enriched liquid phase, stream 12, stream 12 being preferably introduced into the extraction apparatus III is recycled.
- the enriched with the target product formamide liquid phase, stream 10 is separated by distillation in a distillation unit VI to yield the formamide, stream la, discharge of water, H 2 0, and unreacted ammonia or amine, stream 1 1, in the reactor IV and polar solvent (stream 8) which is recycled to the hydrogenation reactor.
- the preferred embodiment shown in Figure 2 differs from the embodiment in Figure 1 only insofar as the extraction unit III is followed by a separation unit 111-1, for separating polar solvent. In the separation unit 111-1, the polar solvent is separated off and recycled as stream 8a into the hydrogenation reactor I.
- a different from the hydrogenation stage solvent can be supplied, which is separated again in the distillation unit VI and as stream 1 1 in the amidation, in the reactor IV, recycled.
- the product stream 7a from the separation unit 111-1 is substantially free of polar solvent, and is passed into the reactor IV.
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Abstract
L'invention concerne un procédé de préparation de formamides par transformation de dioxyde de carbone (1) avec de l'hydrogène (2) dans un réacteur d'hydrogénation I en présence : d'un catalyseur, contenant un élément du 8ème, 9ème ou 10ème groupe du système périodique, d'une amine tertiaire, contenant au moins 6 atomes de carbone par molécule, ainsi que d'un solvant polaire, en formant des produits d'addition d'acide formique/amine comme intermédiaires, qui sont transformés ensuite avec de l'ammoniac ou des amines dans un réacteur, avec obtention d'un produit de réaction liquide à deux phases, dont on sépare par distillation la phase liquide enrichie en formamides, avec obtention du formamide.
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
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US8703994B2 (en) | 2011-07-27 | 2014-04-22 | Basf Se | Process for preparing formamides and formic esters |
US8742171B2 (en) | 2011-06-09 | 2014-06-03 | Basf Se | Process for preparing formic acid |
US8946462B2 (en) | 2011-11-10 | 2015-02-03 | Basf Se | Process for preparing formic acid by reaction of carbon dioxide with hydrogen |
WO2015121357A1 (fr) * | 2014-02-17 | 2015-08-20 | Bayer Technology Services Gmbh | Procédé d'hydrogénation du dioxyde de carbone en formamides |
CN112608240A (zh) * | 2021-01-26 | 2021-04-06 | 张善荣 | 用四聚丙烯和氢氰酸合成n,n-二甲基癸胺的方法 |
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8742171B2 (en) | 2011-06-09 | 2014-06-03 | Basf Se | Process for preparing formic acid |
US8703994B2 (en) | 2011-07-27 | 2014-04-22 | Basf Se | Process for preparing formamides and formic esters |
US8946462B2 (en) | 2011-11-10 | 2015-02-03 | Basf Se | Process for preparing formic acid by reaction of carbon dioxide with hydrogen |
WO2015121357A1 (fr) * | 2014-02-17 | 2015-08-20 | Bayer Technology Services Gmbh | Procédé d'hydrogénation du dioxyde de carbone en formamides |
CN112608240A (zh) * | 2021-01-26 | 2021-04-06 | 张善荣 | 用四聚丙烯和氢氰酸合成n,n-二甲基癸胺的方法 |
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