CN114521194B - 醛的制备方法和醛的制备装置 - Google Patents
醛的制备方法和醛的制备装置 Download PDFInfo
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- CN114521194B CN114521194B CN202180005375.5A CN202180005375A CN114521194B CN 114521194 B CN114521194 B CN 114521194B CN 202180005375 A CN202180005375 A CN 202180005375A CN 114521194 B CN114521194 B CN 114521194B
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- collection tank
- boiling point
- evaporator
- aldehyde
- point component
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- 238000000034 method Methods 0.000 title claims description 16
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 title abstract 5
- 238000009835 boiling Methods 0.000 claims abstract description 110
- 238000007037 hydroformylation reaction Methods 0.000 claims abstract description 61
- 239000003054 catalyst Substances 0.000 claims abstract description 32
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 27
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 16
- 150000001875 compounds Chemical class 0.000 claims abstract description 15
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 14
- 238000004064 recycling Methods 0.000 claims abstract description 12
- 239000006200 vaporizer Substances 0.000 claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 claims abstract description 10
- 150000001299 aldehydes Chemical class 0.000 claims description 93
- 239000000126 substance Substances 0.000 claims description 29
- 239000000539 dimer Substances 0.000 claims description 26
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical group CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 claims description 25
- 239000010948 rhodium Substances 0.000 claims description 17
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 16
- 239000007789 gas Substances 0.000 claims description 16
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 16
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 claims description 14
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 10
- 239000000460 chlorine Substances 0.000 claims description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 10
- 239000003446 ligand Substances 0.000 claims description 9
- 229910052703 rhodium Inorganic materials 0.000 claims description 9
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 9
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 7
- 150000003623 transition metal compounds Chemical class 0.000 claims description 7
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 6
- 229910052801 chlorine Inorganic materials 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 6
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 6
- 239000000376 reactant Substances 0.000 claims description 6
- 229910017052 cobalt Inorganic materials 0.000 claims description 5
- 239000010941 cobalt Substances 0.000 claims description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 5
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 4
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- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 4
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 4
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- 125000003118 aryl group Chemical group 0.000 claims description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052794 bromium Inorganic materials 0.000 claims description 4
- -1 ethylene, propylene, 1-butene Chemical class 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 239000011737 fluorine Substances 0.000 claims description 4
- 229910052741 iridium Inorganic materials 0.000 claims description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 4
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 claims description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 3
- 150000001336 alkenes Chemical class 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052762 osmium Inorganic materials 0.000 claims description 3
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- RRKODOZNUZCUBN-CCAGOZQPSA-N (1z,3z)-cycloocta-1,3-diene Chemical compound C1CC\C=C/C=C\C1 RRKODOZNUZCUBN-CCAGOZQPSA-N 0.000 claims description 2
- JCXJVPUVTGWSNB-UHFFFAOYSA-N Nitrogen dioxide Chemical compound O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 2
- 238000006243 chemical reaction Methods 0.000 description 17
- 239000000243 solution Substances 0.000 description 14
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- 239000000203 mixture Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 6
- 238000004817 gas chromatography Methods 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- RKQZLPCYBYUNPD-UHFFFAOYSA-N (triphenyl-$l^{5}-phosphanylidene)methanone Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)(=C=O)C1=CC=CC=C1 RKQZLPCYBYUNPD-UHFFFAOYSA-N 0.000 description 2
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- HSJKGGMUJITCBW-UHFFFAOYSA-N 3-hydroxybutanal Chemical compound CC(O)CC=O HSJKGGMUJITCBW-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- 239000004435 Oxo alcohol Substances 0.000 description 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 125000005595 acetylacetonate group Chemical group 0.000 description 2
- 238000005575 aldol reaction Methods 0.000 description 2
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 2
- 238000005194 fractionation Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 150000003003 phosphines Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
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- DAFHKNAQFPVRKR-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylpropanoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)C DAFHKNAQFPVRKR-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- XYHKNCXZYYTLRG-UHFFFAOYSA-N 1h-imidazole-2-carbaldehyde Chemical compound O=CC1=NC=CN1 XYHKNCXZYYTLRG-UHFFFAOYSA-N 0.000 description 1
- JCTXKRPTIMZBJT-UHFFFAOYSA-N 2,2,4-trimethylpentane-1,3-diol Chemical compound CC(C)C(O)C(C)(C)CO JCTXKRPTIMZBJT-UHFFFAOYSA-N 0.000 description 1
- LGYNIFWIKSEESD-UHFFFAOYSA-N 2-ethylhexanal Chemical compound CCCCC(CC)C=O LGYNIFWIKSEESD-UHFFFAOYSA-N 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-M 3-Methylbutanoic acid Natural products CC(C)CC([O-])=O GWYFCOCPABKNJV-UHFFFAOYSA-M 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
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- 239000002253 acid Substances 0.000 description 1
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- GWYFCOCPABKNJV-UHFFFAOYSA-N beta-methyl-butyric acid Natural products CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
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- 150000002148 esters Chemical class 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- HLYTZTFNIRBLNA-LNTINUHCSA-K iridium(3+);(z)-4-oxopent-2-en-2-olate Chemical compound [Ir+3].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O HLYTZTFNIRBLNA-LNTINUHCSA-K 0.000 description 1
- 150000002527 isonitriles Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 description 1
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- HBYRZSMDBQVSHO-UHFFFAOYSA-N tris(2-tert-butyl-4-methylphenyl) phosphite Chemical compound CC(C)(C)C1=CC(C)=CC=C1OP(OC=1C(=CC(C)=CC=1)C(C)(C)C)OC1=CC=C(C)C=C1C(C)(C)C HBYRZSMDBQVSHO-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
- C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions
- C07C45/505—Asymmetric hydroformylation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
- C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/009—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping in combination with chemical reactions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/14—Fractional distillation or use of a fractionation or rectification column
- B01D3/143—Fractional distillation or use of a fractionation or rectification column by two or more of a fractionation, separation or rectification step
-
- 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
- B01J31/0255—Phosphorus containing compounds
- B01J31/0257—Phosphorus acids or phosphorus acid esters
- B01J31/0259—Phosphorus acids or phosphorus acid esters comprising phosphorous acid (-ester) groups ((RO)P(OR')2) or the isomeric phosphonic acid (-ester) groups (R(R'O)2P=O), i.e. R= C, R'= C, H
-
- 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
- B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
- B01J31/122—Metal aryl or alkyl compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1845—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1845—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
- B01J31/185—Phosphites ((RO)3P), their isomeric phosphonates (R(RO)2P=O) and RO-substitution derivatives thereof
-
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Abstract
根据本申请的一个实施方案的醛的制备方法包括:在加氢甲酰化反应器中,在用于加氢甲酰化反应的催化剂下,通过使烯烃类化合物与合成气反应来形成包含醛的反应产物;将所述包含醛的反应产物引入蒸发器中;将包含在蒸发器中的所述反应产物的低沸点组分分离到蒸发器收集罐的上部,并将所述反应产物的高沸点组分分离到所述蒸发器收集罐的下部;和将至少一部分的分离到所述蒸发器收集罐的上部的低沸点组分再循环到所述蒸发器收集罐中。
Description
技术领域
本申请要求于2020年9月17日在韩国知识产权局提交的韩国专利申请No.10-2020-0119657的优先权和权益,该专利申请的全部内容通过引用并入本说明书中。
本申请涉及一种醛的制备方法,和一种醛的制备装置。
背景技术
在均相有机金属催化剂和配体的存在下,将各种烯烃与通常称为合成气的一氧化碳(CO)和氢气(H2)反应来生成碳原子数增加一的直链(正)和支链(异)醛的加氢甲酰化反应在1938年由德国的Otto Roelen首次发现。
加氢甲酰化反应,通常称为羰基合成反应,是均相催化剂反应中的一个工业上非常重要的反应,包括醇衍生物的各种醛通过羰基合成法生产并在世界范围内消耗。
通过羰基合成反应合成的各种醛有时在缩合反应后被氧化或氢化,例如羟醛,并改变为各种包含长烷基的酸和醇。特别地,通过这种羰基合成反应生成的醛的氢化醇被称为羰基合成醇,羰基合成醇在工业上被广泛用作溶剂、添加剂、各种增塑剂的原料、合成润滑剂等。
目前羰基合成过程中使用的催化剂主要是钴(Co)和铑(Rh)系列,生成的醛的正/异选择性(直链(正)与支链(异)异构体的比例)根据使用的配体的类型和操作条件而不同。目前,世界上70%以上的羰基合成工厂采用使用铑类催化剂的低压羰基合成工艺。
作为羰基合成催化剂的中心金属,除了钴(Co)和铑(Rh)之外,还可以使用铱(Ir)、钌(Ru)、锇(Os)、铂(Pt)、钯(Pd)、铁(Fe)、镍(Ni)等。然而,已知每种金属表现出催化活性的顺序为Rh>>Co>Ir,Ru>Os>Pt>Pd>Fe>Ni等,因此,大多数工艺和研究集中于铑和钴。
作为配体,可以使用膦(PR3,R是C6H5或n-C4H9)、氧化膦(O=P(C6H5)3)、亚磷酸酯、胺、酰胺、异腈等。
加氢甲酰化的代表性实例包括使用铑类催化剂由丙烯制备辛醇(2-乙基己醇)。
辛醇主要用作PVC增塑剂例如DOP(邻苯二甲酸二辛酯)的原料,此外,还用作合成润滑剂、表面活性剂等的中间物质。将丙烯引入羰基合成反应器中,使用催化剂以及合成气(CO/H2)以生产正丁醛和异丁醛。将生成的醛混合物与催化剂混合物送入分离系统中,并且分离成烃和催化剂混合物,然后将催化剂混合物循环到反应器中,并将烃组分输送到汽提器中。汽提器的烃通过新供应的合成气汽提以将未反应的丙烯和合成气回收到羰基合成反应器中,并将丁醛输送到分馏塔并且分离成正丁醛和异丁醛。将分馏塔的底部的正丁醛引入羟醛缩合反应器中以利用缩合和脱水反应生成2-乙基己醛,然后输送到加氢反应器中,并通过加氢生成辛醇(2-乙基己醇)。将加氢反应器的出口处的反应物输送到分馏塔中,并在分离软/硬端后,得到辛醇产品。
加氢甲酰化反应可以连续、半连续或分批来进行,典型的加氢甲酰化反应过程为气体或液体再循环系统。在加氢甲酰化反应中,重要的是通过使在液相和气相中形成的初始材料彼此顺利接触来提高反应效率。为此,本领域中主要使用连续搅拌釜反应器(CSTR)搅拌液相和气相组分以在反应器中彼此均匀接触。
在这方面,本领域对催化剂的大部分研究在增加直链醛衍生物(正醛)的比例的方向进行,因为在通过羰基合成反应生成的醛中,直链醛衍生物具有更高的价值。然而,随着使用支链醛衍生物(异醛)的化合物例如异丁酸、新戊二醇(NPG)、2,2,4-三甲基-1,3-戊二醇、异戊酸等的发展,最近对异醛的需求已经增加,已经不断进行在提高支链醛衍生物的选择性的方向的研究。
发明内容
技术问题
本申请旨在提供一种醛的制备方法,和一种醛的制备装置。
技术方案
本申请的一个实施方案提供一种醛的制备方法,该制备方法包括:
在加氢甲酰化反应器中,在用于加氢甲酰化反应的催化剂下,通过使烯烃类化合物与合成气反应来形成包含醛的反应产物;
将所述包含醛的反应产物引入蒸发器中;
将包含在蒸发器中的所述反应产物的低沸点组分分离到蒸发器收集罐的上部,并将所述反应产物的高沸点组分分离到所述蒸发器收集罐的下部;和
将至少一部分的分离到所述蒸发器收集罐的上部的低沸点组分再循环到所述蒸发器收集罐中,
其中,再循环到所述蒸发器收集罐的低沸点组分的重量是分离到所述蒸发器收集罐的下部的高沸点组分的重量的0.1倍至10倍。
另外,本申请的另一实施方案提供一种醛的分离方法,该分离方法包括:
将包括包含醛的低沸点组分和包含用于加氢甲酰化反应的催化剂溶液的高沸点组分的组合物引入配备有蒸发器收集罐的蒸发器中;
将所述包含醛的低沸点组分分离到所述蒸发器收集罐的上部,并将所述包含用于加氢甲酰化反应的催化剂溶液的高沸点组分分离到所述蒸发器收集罐的下部;和
将至少一部分的分离到所述蒸发器收集罐的上部的低沸点组分再循环到所述蒸发器收集罐中,
其中,再循环到所述蒸发器收集罐的低沸点组分的重量是分离到所述蒸发器收集罐的下部的高沸点组分的重量的0.1倍至10倍。
另外,本申请的另一实施方案提供一种醛的制备装置,该制备装置包括:
加氢甲酰化反应器,其设置有反应物供应管和反应产物输送管;
蒸发器,其与所述加氢甲酰化反应器的反应产物输送管连接并且设置有蒸发器收集罐;
设置在所述蒸发器收集罐的上部的低沸点组分管和设置在所述蒸发器收集罐的下部的高沸点组分管;和
连接所述低沸点组分管与所述蒸发器收集罐的低沸点再循环管。
有益效果
根据本申请的一个实施方案的醛的制备方法包括将至少一部分的分离到蒸发器收集罐的上部的低沸点组分再循环到蒸发器收集罐中。因此,可以降低通过高沸点再循环管,从蒸发器收集罐至加氢甲酰化反应器的部分中存在的高沸点组分的浓度,可以降低溶液的温度,并且可以减少到达加氢甲酰化反应器所花费的停留时间,因此,可以减少在通过高沸点再循环管到达加氢甲酰化反应器的部分中会合成的醛二聚体的含量。
根据本申请的一个实施方案,可以减少醛二聚体的产生量,从而可以提高醛的制备过程的反应收率。
附图说明
图1是示意性地示出根据本申请的一个实施方案的醛的制备装置的图;
图2是示意性地示出现有的醛的制备装置的图;
图3是示意性地示出加氢甲酰化反应的产物丁醛的二聚体形成原理的图;
图4是示出本申请的实施例和比较例的醛二聚体的增加量的图。
[附图标记]
1:反应物供应管
2:加氢甲酰化反应器
3:反应产物输送管
4:蒸发器
5:蒸发器收集罐
6:低沸点组分管
7:高沸点组分管
8:循环泵
9:高沸点组分再循环管
10:低沸点组分再循环管
具体实施方式
下文中,将更详细地描述本申请。
在本说明书中,某个部件位于另一部件“上”的描述不仅包括某个部件与另一部件接触的情况,还包括两个部件之间存在再一部件的情况。
在本说明书中,特定部分“包含”特定组成的描述是指能够进一步包括其它组成,并且不排除其它组成,除非进行相反地具体说明。
如图3中所示,当丙烯、氢气和一氧化碳在催化剂下进行加氢甲酰化时生成丁醛。此处生成的丁醛有正构体和异构体,并且两种丁醛还可以分别进一步进行羟醛反应以生成醛二聚体。特别地,加氢甲酰化反应后没有通过蒸发器的低沸点组分管排出的醛可以通过羟醛反应生成醛二聚体,并且生成的醛二聚体导致降低目标醛的制备过程的反应收率的问题。
另外,在从蒸发器再循环至加氢甲酰化反应器的管道中,高沸点组分被浓缩,因此,为了防止催化剂沉淀,将高沸点组分再循环到在一定温度以上的条件下包含一定量的醛的反应器中。在此过程中,醛二聚体含量增加,造成更大量的醛进行羟醛反应的问题。
为了解决上述问题,本申请尝试减少会降低醛的制备过程的反应收率的醛二聚体的产生量。
根据本申请的一个实施方案的醛的制备方法包括:在加氢甲酰化反应器中,在用于加氢甲酰化反应的催化剂下,通过使烯烃类化合物与合成气反应来形成包含醛的反应产物;将所述包含醛的反应产物引入蒸发器中;将包含在蒸发器中的所述反应产物的低沸点组分分离到蒸发器收集罐的上部,并将所述反应产物的高沸点组分分离到所述蒸发器收集罐的下部;和将至少一部分的分离到所述蒸发器收集罐的上部的低沸点组分再循环到所述蒸发器收集罐中,其中,再循环到所述蒸发器收集罐的低沸点组分的重量是分离到所述蒸发器收集罐的下部的高沸点组分的重量的0.1倍至10倍。
此外,根据本申请的一个实施方案的醛的分离方法包括:将包括包含醛的低沸点组分和包含用于加氢甲酰化反应的催化剂溶液的高沸点组分的组合物引入配备有蒸发器收集罐的蒸发器中;将所述包含醛的低沸点组分分离到所述蒸发器收集罐的上部,并将所述包含用于加氢甲酰化反应的催化剂溶液的高沸点组分分离到所述蒸发器收集罐的下部;和将至少一部分的分离到所述蒸发器收集罐的上部的低沸点组分再循环到所述蒸发器收集罐中,其中,再循环到所述蒸发器收集罐的低沸点组分的重量是分离到所述蒸发器收集罐的下部的高沸点组分的重量的0.1倍至10倍。
在本申请的一个实施方案中,分离到蒸发器收集罐的上部的低沸点组分可以包含醛、未反应的烯烃类化合物和合成气。此处,将至少一部分的分离到蒸发器收集罐的上部的低沸点组分再循环到蒸发器收集罐中。通过如上将至少一部分的分离到蒸发器收集罐的上部的低沸点组分再循环到蒸发器收集罐中,将再循环的低沸点组分与蒸发器收集罐中存在的高沸点组分混合,这可以降低高沸点组分的浓度。因此,可以降低通过高沸点再循环管,从蒸发器收集罐至加氢甲酰化反应器的部分中存在的高沸点组分的浓度,可以降低溶液的温度,并且可以减少到达加氢甲酰化反应器所花费的停留时间,因此,可以减少在通过高沸点再循环管到达加氢甲酰化反应器的部分中会合成的醛二聚体的含量。
在本申请的一个实施方案中,再循环到蒸发器收集罐的低沸点组分的重量可以是分离到蒸发器收集罐的下部的高沸点组分的重量的0.1倍至10倍,并且可以是1倍至8倍。当满足再循环到蒸发器收集罐的低沸点组分的重量范围时,可以减少在通过高沸点再循环管到达加氢甲酰化反应器的部分中会合成的醛二聚体的含量。
另外,当再循环到蒸发器收集罐的低沸点组分的重量小于分离到蒸发器收集罐的下部的高沸点组分的重量的0.1倍时,上述减少醛二聚体的生成量的效果不显著,并且通过消耗作为加氢甲酰化反应的产物的醛,反应收率会降低。此外,当再循环到蒸发器收集罐的低沸点组分的重量大于分离到蒸发器收集罐的下部的高沸点组分的重量的10倍时,通过高沸点再循环管引入加氢甲酰化反应器中的催化剂组分的浓度变得太低,降低加氢甲酰化反应性。
在本申请的一个实施方案中,分离到蒸发器收集罐的下部的高沸点组分可以包含醛二聚体和用于加氢甲酰化反应的催化剂。此处,分离到蒸发器收集罐的下部的高沸点组分可以再循环到加氢甲酰化反应器中。如图3中所示,醛二聚体由两个醛彼此进行羟醛反应来生成。
在本申请的一个实施方案中,通过将至少一部分的分离到蒸发器收集罐的上部的低沸点组分再循环到蒸发器收集罐中,再循环的低沸点组分与蒸发器收集罐中存在的高沸点组分混合,这可以降低高沸点组分的浓度。
在本申请的一个实施方案中,基于分离到蒸发器收集罐的下部的高沸点组分的总重量,醛二聚体的含量可以为10重量%以下,可以为5重量%以下,并且可以为1重量%以上。基于分离到蒸发器收集罐的下部的高沸点组分的总重量,醛二聚体的含量大于10重量%是不优选的,因为在高沸点再循环管中生成的醛的量增加,这会增加加氢甲酰化反应器中的醛二聚体的含量。
在本申请的一个实施方案中,蒸发器收集罐的温度可以为50℃至100℃,以及55℃至90℃。此外,蒸发器收集罐可以具有大气压至5巴和大气压至3巴的压力。此处,大气压是指常压,并且是指没有特别增加或降低时的压力。当满足蒸发器收集罐的温度范围和压力范围时,可以降低醛二聚体的含量。
在本申请的一个实施方案中,用于加氢甲酰化反应的催化剂可以包括由下面化学式1表示的亚磷酸酯配体和由下面化学式2表示的过渡金属化合物。
[化学式1]
[化学式2]
M(L1)x(L2)y(L3)z
在化学式2中,
M是钴(Co)、铑(Rh)、铱(Ir)、钌(Ru)、铁(Fe)、镍(Ni)、钯(Pd)、铂(Pt)或锇(Os),
L1、L2和L3彼此相同或不同,并且各自独立地是氢、羰基(CO)、环辛二烯、降冰片烯、氯、三苯基膦(TPP)或乙酰丙酮(AcAc),并且
x、y和z各自独立地是0至5,并且x、y和z不同时是0。
在本申请的一个实施方案中,基于1摩尔的由化学式1表示的亚磷酸酯配体,由化学式2表示的过渡金属化合物的含量可以为0.003摩尔至0.05摩尔,可以为0.004摩尔至0.045摩尔,并且可以为0.0042摩尔至0.042摩尔。当基于1摩尔由化学式1表示的亚磷酸酯配体,由化学式2表示的过渡金属化合物的含量满足0.003摩尔至0.05摩尔时,用于加氢甲酰化反应的催化剂的活性可以优异,并且含量在上述范围之外会引起降低催化剂的活性和稳定性的问题。
由化学式2表示的过渡金属化合物可以是选自羰基钴(Co2(CO)8)、乙酰丙酮二羰基铑(Rh(AcAc)(CO)2)、乙酰丙酮羰基三苯基膦铑(Rh(AcAc)(CO)(TPP))、氢化羰基三(三苯基膦)铑[HRh(CO)(TPP)3]、乙酰丙酮二羰基铱(Ir(AcAc)(CO)2)和氢化羰基三(三苯基膦)铱(HIr(CO)(TPP)3)中的一种或多种类型。
在本申请的一个实施方案中,烯烃类化合物可以由下面化学式3表示。
[化学式3]
在化学式3中,
R5和R6彼此相同或不同,并且各自独立地是氢、烷基、氟(F)、氯(Cl)、溴(Br)、三氟甲基(-CF3)、或者被取代或未被取代的芳基。
所述芳基可以未被取代或被硝基(-NO2)、氟(F)、氯(Cl)、溴(Br)、甲基、乙基、丙基和丁基中的一种或多种类型的取代基取代。
更具体地,烯烃类化合物可以是选自乙烯、丙烯、1-丁烯、1-戊烯、1-己烯、1-辛烯和苯乙烯中的一种或多种类型。
在本申请的一个实施方案中,烯烃类化合物可以是丙烯,并且醛可以是丁醛。
在本申请的一个实施方案中,加氢甲酰化反应可以使用将由化学式2表示的过渡金属化合物和由化学式1表示的亚磷酸酯配体溶解在溶剂中以制备过渡金属化合物和亚磷酸酯配体的混合溶液,即,催化剂组合物;注入由化学式3表示的烯烃类化合物和合成气以及催化剂组合物;并在升高温度和施加压力的同时搅拌所得物的方法来进行。
溶剂可以是选自丙醛、丁醛、戊醛(pentyl aldehyde)、正戊醛(valeraldehyde)、丙酮、甲乙酮、甲基异丁基酮、苯乙酮、环己酮、乙醇、戊醇、辛醇、酯醇十二(texanol)、苯、甲苯、二甲苯、邻二氯苯、四氢呋喃、二甲氧基乙烷、二氧六环、二氯甲烷和庚烷中的一种或多种类型。
在本申请的一个实施方案中,使烯烃类化合物与合成气在加氢甲酰化反应器中反应的步骤可以在50℃至90℃的温度和5巴至25巴的压力下进行,并且可以在55℃至85℃的温度和8巴至18巴的压力下进行。当加氢甲酰化反应步骤中的温度低于50℃时,反应性会显著降低,而当温度高于90℃时,重组分的含量增加,导致收率下降。此外,当加氢甲酰化反应步骤中的压力小于5巴时,反应性会显著降低,而压力大于25巴在成本和装置的设计方面具有缺点。
在本申请的一个实施方案中,在加氢甲酰化反应步骤中,烯烃类化合物:合成气的摩尔比可以为95:5至5:95,以及75:25至25:75。当在加氢甲酰化反应步骤中,烯烃类化合物:合成气的摩尔比为95:5至5:95时,用于加氢甲酰化反应的催化剂的活性可以优异,并且摩尔比在上述范围之外会引起降低催化剂的活性和稳定性的问题。
此外,根据本申请的一个实施方案的醛的制备装置包括:加氢甲酰化反应器,其设置有反应物供应管和反应产物输送管;蒸发器,其与所述加氢甲酰化反应器的反应产物输送管连接并且设置有蒸发器收集罐;设置在所述蒸发器收集罐的上部的低沸点组分管和设置在所述蒸发器收集罐的下部的高沸点组分管;和连接所述低沸点组分管与所述蒸发器收集罐的低沸点再循环管。
在本申请的一个实施方案中,还可以包括连接高沸点组分管与加氢甲酰化反应器的高沸点再循环管。
图1示意性地示出了根据本申请的一个实施方案的醛的制备装置,图2示意性地示出了现有的醛的制备装置。
如图1中所示,根据本申请的一个实施方案的醛的制备装置包括:加氢甲酰化反应器(2),其设置有反应物供应管(1)和反应产物输送管(3);蒸发器(4),其与加氢甲酰化反应器(2)的反应产物输送管(3)连接并且设置有蒸发器收集罐(5);设置在蒸发器收集罐(5)的上部的低沸点组分管(6)和设置在蒸发器收集罐(5)的下部的高沸点组分管(7);和连接低沸点组分管(6)与蒸发器收集罐(5)的低沸点再循环管(10)。此处,醛的制备装置还可以包括连接高沸点组分管(7)与加氢甲酰化反应器(2)的高沸点再循环管(9)。蒸发器(4)和蒸发器收集罐(5)可以直接彼此连接。例如,蒸发器(4)的出口可以成为蒸发器收集罐(5)的入口。
下文中,为了具体描述本申请,将参照实施例详细描述本申请。然而,根据本申请的实施例可以修改为各种不同的形式,并且本申请的范围不应该理解为限于以下描述的实施例。提供本申请的实施例是为了向本领域普通技术人员更全面地描述本申请。
<实施例>
<实施例1>
作为催化剂,使用乙酰丙酮羰基三苯基膦铑(Rh(AcAc)(CO)(TPP),ROPAC)和三(2-叔丁基-4-甲基苯基)亚磷酸酯(TTBMPP)。
将包含ROPAC和TTBMPP的高沸点组分溶液溶解在低沸点组分丁醛溶液中,以制备具有如下面表1中所示的浓度的醛溶液(100g),并将醛溶液引入到600mL的高压釜反应器中。引入醛溶液后,使用氮气将高压釜反应器内部加压至1.8巴,并在65℃和1,000rpm的搅拌速率下进行反应2小时。每30分钟对反应溶液取样,并通过气相色谱(GC)分析各个有机物的含量。
实施例1设置蒸发器收集罐和高沸点再循环管的条件。换言之,实施例1设定工艺条件,其中,将至少一部分的分离到蒸发器收集罐的上部的低沸点组分再循环到蒸发器收集罐中。此处,将再循环到蒸发器收集罐的低沸点组分的重量设定为分离到蒸发器收集罐的下部的高沸点组分的重量的6.43倍。
<实施例2和实施例3以及比较例1>
除了如下面表1中调节再循环到蒸发器收集罐的低沸点组分的重量之外,以与实施例1相同的方式进行制备。
[表1]
<实验例1>
每30分钟对实施例和比较例的反应溶液取样一次,通过气相色谱分析各个有机物的含量。醛二聚体的含量示于下面表2中,反应前后醛二聚体的增加量示于图4中。
<GC分析的条件>
1)色谱柱:HP-1(L:30m,ID:0.32mm,膜:1.05m)
2)进样量:1μl
3)入口温度:250℃,压力:6.92psi,总流量:64.2ml/min,分流:60ml/min,分流比:50:1
4)柱流速:1.2ml/min
5)烘箱温度:70℃/3min-10℃/min-280℃/35min
6)检测器温度:280℃,H2:35ml/min,空气:300ml/min,He:20ml/min
7)GC型号:Agilent 7890
[表2]
由上面示出的结果可以确定,反应前醛二聚体的含量越低,相同条件下生成的醛二聚体的含量越低。
根据本申请的一个实施方案的醛的制备方法包括将至少一部分的分离到蒸发器收集罐的上部的低沸点组分再循环到蒸发器收集罐中。因此,存在于通过高沸点再循环管,从蒸发器收集罐至加氢甲酰化反应器的部分中的高沸点组分的浓度可以降低,溶液的温度可以降低,并且到达加氢甲酰化反应器所花费的停留时间可以降低,因此,可以减少在通过高沸点再循环管到达加氢甲酰化反应器的部分中会合成的醛二聚体的含量。
根据本申请的一个实施方案,可以减少醛二聚体的生成量,因此,可以提高醛的制备过程的反应收率。
Claims (7)
1.一种醛的制备方法,该制备方法包括:
在加氢甲酰化反应器中,在用于加氢甲酰化反应的催化剂下,通过使烯烃类化合物与合成气反应来形成包含醛的反应产物;
将所述包含醛的反应产物引入蒸发器中,所述蒸发器设置有蒸发器收集罐;
将包含在蒸发器中的所述反应产物的低沸点组分分离到所述蒸发器收集罐的上部,并将所述反应产物的高沸点组分分离到所述蒸发器收集罐的下部;和
将至少一部分的分离到所述蒸发器收集罐的所述上部的低沸点组分再循环到所述蒸发器收集罐中,
其中,再循环到所述蒸发器收集罐的低沸点组分的重量是分离到所述蒸发器收集罐的所述下部的高沸点组分的重量的0.1倍至10倍,
其中,分离到所述蒸发器收集罐的所述上部的低沸点组分包含醛、未反应的烯烃类化合物和合成气,并且
其中,分离到所述蒸发器收集罐的所述下部的高沸点组分包含醛二聚体和所述用于加氢甲酰化反应的催化剂,
其中,将分离到所述蒸发器收集罐的所述下部的高沸点组分再循环到所述加氢甲酰化反应器中。
2.根据权利要求1所述的醛的制备方法,其中,基于分离到所述蒸发器收集罐的所述下部的高沸点组分的总重量,所述醛二聚体的含量为10重量%以下。
3.根据权利要求1所述的醛的制备方法,其中,所述用于加氢甲酰化反应的催化剂包括由下面化学式1表示的亚磷酸酯配体和由下面化学式2表示的过渡金属化合物:
[化学式1]
[化学式2]
M(L1)x(L2)y(L3)z
在化学式2中,
M是钴(Co)、铑(Rh)、铱(Ir)、钌(Ru)、铁(Fe)、镍(Ni)、钯(Pd)、铂(Pt)或锇(Os);
L1、L2和L3彼此相同或不同,并且各自独立地是氢、羰基(CO)、环辛二烯、降冰片烯、氯、三苯基膦(TPP)或乙酰丙酮(AcAc);并且
x、y和z各自独立地是0至5,并且x、y和z不同时是0。
4.根据权利要求1所述的醛的制备方法,其中,所述烯烃类化合物由下面化学式3表示:
[化学式3]
在化学式3中,
R5和R6彼此相同或不同,并且各自独立地是氢、烷基、氟(F)、氯(Cl)、溴(Br)、三氟甲基(-CF3)、被硝基(-NO2)、氟(F)、氯(Cl)、溴(Br)、甲基、乙基、丙基和丁基中的一种或多种类型的取代基取代的芳基或未被取代的芳基。
5.根据权利要求1所述的醛的制备方法,其中,所述烯烃类化合物是选自乙烯、丙烯、1-丁烯、1-戊烯、1-己烯、1-辛烯和苯乙烯中的一种或多种类型。
6.根据权利要求1所述的醛的制备方法,其中,所述烯烃类化合物是丙烯,并且所述醛是丁醛。
7.一种醛的制备装置,所述制备装置使用权利要求1所述的醛的制备方法,该制备装置包括:
加氢甲酰化反应器,其设置有反应物供应管和反应产物输送管;
蒸发器,其与所述加氢甲酰化反应器的反应产物输送管连接并且设置有蒸发器收集罐;
设置在所述蒸发器收集罐的上部的低沸点组分管和设置在所述蒸发器收集罐的下部的高沸点组分管;
连接所述低沸点组分管与所述蒸发器收集罐的低沸点再循环管;和
连接所述高沸点组分管与所述加氢甲酰化反应器的高沸点再循环管,
其中,所述反应产物的包含醛的低沸点组分被分离到所述蒸发器收集罐的上部,并且所述反应产物的高沸点组分被分离到所述蒸发器收集罐的下部,
其中,被分离到所述蒸发器收集罐的上部的低沸点组分的至少一部分再循环到所述蒸发器收集罐。
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CN104001548A (zh) * | 2014-03-28 | 2014-08-27 | 山东华鲁恒升化工股份有限公司 | 羰基合成丁醛的均相催化体系及其制备和应用 |
CN106278844A (zh) * | 2016-09-13 | 2017-01-04 | 天津渤化永利化工股份有限公司 | 一种降低丙烯羰基化过程中原料消耗的装置及方法 |
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US4215077A (en) | 1978-02-09 | 1980-07-29 | Kuraray Co., Ltd. | Hydroformylation of olefins |
DE10006489A1 (de) * | 2000-02-14 | 2001-08-16 | Basf Ag | Verfahren zur Aufarbeitung eines flüssigen Hydroformylierungsaustrages |
EP1249439A1 (en) * | 2001-04-13 | 2002-10-16 | Dsm N.V. | Continuous hydroformylation process |
FR2933974B1 (fr) * | 2008-07-18 | 2010-09-17 | Rhodia Operations | Procede de separation d'un aldehyde aromatique |
KR101457734B1 (ko) * | 2010-06-10 | 2014-11-03 | 주식회사 엘지화학 | 올레핀의 하이드로포밀화 반응촉매의 분리 장치와 이를 이용한 분리 방법 |
US10351503B2 (en) * | 2015-11-10 | 2019-07-16 | Dow Technology Investments Llc | Process for producing aldehydes |
KR102192718B1 (ko) | 2019-04-10 | 2020-12-17 | 최상식 | 건강관리를 고려한 메뉴 기반 식재료 주문 시스템 및 방법 |
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CN102143933A (zh) * | 2008-07-03 | 2011-08-03 | 陶氏技术投资有限公司 | 控制再循环催化剂料流中重物质的方法 |
KR20100058712A (ko) * | 2008-11-25 | 2010-06-04 | 주식회사 엘지화학 | 고효율 기화기 및 이를 이용한 알데히드 및 촉매의 분리방법 |
CN104001548A (zh) * | 2014-03-28 | 2014-08-27 | 山东华鲁恒升化工股份有限公司 | 羰基合成丁醛的均相催化体系及其制备和应用 |
CN106278844A (zh) * | 2016-09-13 | 2017-01-04 | 天津渤化永利化工股份有限公司 | 一种降低丙烯羰基化过程中原料消耗的装置及方法 |
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EP4008711A4 (en) | 2022-12-07 |
KR20220037341A (ko) | 2022-03-24 |
CN114521194A (zh) | 2022-05-20 |
US20220402846A1 (en) | 2022-12-22 |
EP4008711A1 (en) | 2022-06-08 |
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