CN116102412A - Method for preparing aldehyde by hydroformylation of Fischer-Tropsch mixed olefin - Google Patents
Method for preparing aldehyde by hydroformylation of Fischer-Tropsch mixed olefin Download PDFInfo
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- CN116102412A CN116102412A CN202310112705.1A CN202310112705A CN116102412A CN 116102412 A CN116102412 A CN 116102412A CN 202310112705 A CN202310112705 A CN 202310112705A CN 116102412 A CN116102412 A CN 116102412A
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- fischer
- tropsch
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- olefin
- rhodium
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- 150000001336 alkenes Chemical class 0.000 title claims abstract description 92
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 238000007037 hydroformylation reaction Methods 0.000 title claims abstract description 64
- 238000000034 method Methods 0.000 title claims abstract description 36
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 title claims abstract 5
- 239000003054 catalyst Substances 0.000 claims abstract description 50
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 42
- 239000010948 rhodium Substances 0.000 claims abstract description 42
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims abstract description 41
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 25
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 22
- 239000003446 ligand Substances 0.000 claims description 62
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 29
- 239000007789 gas Substances 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 19
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 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 14
- CXNIUSPIQKWYAI-UHFFFAOYSA-N xantphos Chemical compound C=12OC3=C(P(C=4C=CC=CC=4)C=4C=CC=CC=4)C=CC=C3C(C)(C)C2=CC=CC=1P(C=1C=CC=CC=1)C1=CC=CC=C1 CXNIUSPIQKWYAI-UHFFFAOYSA-N 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 13
- -1 phenyl tris (2, 4-di-tert-butylphenyl) phosphite Chemical compound 0.000 claims description 12
- 239000002243 precursor Substances 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 11
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- GGRQQHADVSXBQN-FGSKAQBVSA-N carbon monoxide;(z)-4-hydroxypent-3-en-2-one;rhodium Chemical group [Rh].[O+]#[C-].[O+]#[C-].C\C(O)=C\C(C)=O GGRQQHADVSXBQN-FGSKAQBVSA-N 0.000 claims description 9
- 239000004711 α-olefin Substances 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 claims description 8
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 7
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 7
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 claims description 6
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 claims description 6
- DCTOHCCUXLBQMS-UHFFFAOYSA-N 1-undecene Chemical compound CCCCCCCCCC=C DCTOHCCUXLBQMS-UHFFFAOYSA-N 0.000 claims description 6
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 claims description 6
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 6
- DIOQZVSQGTUSAI-UHFFFAOYSA-N n-butylhexane Natural products CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 claims description 6
- ZWRUINPWMLAQRD-UHFFFAOYSA-N nonan-1-ol Chemical compound CCCCCCCCCO ZWRUINPWMLAQRD-UHFFFAOYSA-N 0.000 claims description 6
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 claims description 6
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 5
- ILPBINAXDRFYPL-UHFFFAOYSA-N 2-octene Chemical compound CCCCCC=CC ILPBINAXDRFYPL-UHFFFAOYSA-N 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- VURFVHCLMJOLKN-UHFFFAOYSA-N diphosphane Chemical compound PP VURFVHCLMJOLKN-UHFFFAOYSA-N 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- ADOQBZAVKYCFOI-HWKANZROSA-N (E)-2-dodecene Chemical compound CCCCCCCCC\C=C\C ADOQBZAVKYCFOI-HWKANZROSA-N 0.000 claims description 3
- IICQZTQZQSBHBY-HWKANZROSA-N (e)-non-2-ene Chemical compound CCCCCC\C=C\C IICQZTQZQSBHBY-HWKANZROSA-N 0.000 claims description 3
- JOHIXGUTSXXADV-HWKANZROSA-N (e)-undec-2-ene Chemical compound CCCCCCCC\C=C\C JOHIXGUTSXXADV-HWKANZROSA-N 0.000 claims description 3
- 239000005968 1-Decanol Substances 0.000 claims description 3
- IICQZTQZQSBHBY-UHFFFAOYSA-N 2t-nonene Natural products CCCCCCC=CC IICQZTQZQSBHBY-UHFFFAOYSA-N 0.000 claims description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- UXRZLDREKITWRO-UHFFFAOYSA-N P(c1ccccc1)c1ccccc1.CC1(C)c2ccccc2Oc2ccccc12 Chemical compound P(c1ccccc1)c1ccccc1.CC1(C)c2ccccc2Oc2ccccc12 UXRZLDREKITWRO-UHFFFAOYSA-N 0.000 claims description 3
- 239000012670 alkaline solution Substances 0.000 claims description 3
- YKNMBTZOEVIJCM-UHFFFAOYSA-N dec-2-ene Chemical compound CCCCCCCC=CC YKNMBTZOEVIJCM-UHFFFAOYSA-N 0.000 claims description 3
- 229940069096 dodecene Drugs 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- DIOQZVSQGTUSAI-NJFSPNSNSA-N decane Chemical compound CCCCCCCCC[14CH3] DIOQZVSQGTUSAI-NJFSPNSNSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 75
- 150000001299 aldehydes Chemical class 0.000 description 46
- 239000000047 product Substances 0.000 description 20
- 238000004458 analytical method Methods 0.000 description 13
- 239000002994 raw material Substances 0.000 description 11
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 10
- 238000004817 gas chromatography Methods 0.000 description 8
- 239000003245 coal Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 238000005070 sampling Methods 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 7
- GGQQNYXPYWCUHG-RMTFUQJTSA-N (3e,6e)-deca-3,6-diene Chemical compound CCC\C=C\C\C=C\CC GGQQNYXPYWCUHG-RMTFUQJTSA-N 0.000 description 6
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- 230000002349 favourable effect Effects 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 150000001868 cobalt Chemical class 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000006317 isomerization reaction Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 230000003335 steric effect Effects 0.000 description 2
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- YPPQDPIIWDQYRY-UHFFFAOYSA-N [Ru].[Rh] Chemical compound [Ru].[Rh] YPPQDPIIWDQYRY-UHFFFAOYSA-N 0.000 description 1
- LOFWCYKHINEUQF-UHFFFAOYSA-N [hydroxy(phosphonooxy)phosphoryl] diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)(OP(O)(=O)OP(O)(=O)O)OC1=CC=CC=C1 LOFWCYKHINEUQF-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003283 rhodium Chemical class 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1845—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
- B01J31/185—Phosphites ((RO)3P), their isomeric phosphonates (R(RO)2P=O) and RO-substitution derivatives thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/32—Addition reactions to C=C or C-C triple bonds
- B01J2231/321—Hydroformylation, metalformylation, carbonylation or hydroaminomethylation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/822—Rhodium
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention provides a method for preparing aldehyde by hydroformylation of Fischer-Tropsch mixed olefin. The method comprises the following steps: carrying out hydroformylation reaction on Fischer-Tropsch mixed olefin and synthesis gas in the presence of a rhodium-containing catalyst to obtain aldehyde; wherein the Fischer-Tropsch mixed olefin contains mixed olefins of C8-C12; the synthesis gas is H 2 And CO. The hydroformylation reaction has mild condition and can reach higher conversion rate and selectivity.
Description
Technical Field
The invention relates to the technical field of chemistry and chemical engineering, in particular to a method for preparing aldehyde by hydroformylation of Fischer-Tropsch mixed olefin.
Background
The hydroformylation reaction is also called OXO reaction, and refers to a reaction in which carbon monoxide and hydrogen can be added to an olefin in one step by a transition metal complex catalyst, and an aldehyde having one more carbon atom than the original olefin can be produced with an atom utilization efficiency of 100%. Generally, linear aldehydes and branched aldehydes produced by hydroformylation can be further hydrogenated, oxidized and aminated to convert them into alcohols, carboxylic acids and amines, etc., which are used in bulk chemicals, plasticizers, paints and other optical materials, etc.
The industry has catalyzed olefin hydroformylation using cobalt-based catalysts, with BASF corporation employing unmodified cobalt carbonyl HCo (CO) 4 As a catalyst, in the actual industrial application process, the unmodified cobalt catalyst usually needs higher reaction temperature (140-180 ℃) and reaction pressure (20-35 MPa) during the catalytic hydroformylation reaction, the reaction conditions are harsh, and the selectivity of aldehyde in the reaction product is lower (Heck R F, breslow D.S. the reaction of cobalt hydrotetracarbonyl with olefins [ J)]Journal of the American Chemical Society,1961,83 (19): 4023 to 4027. Further, shell modified cobalt catalysts with trialkyl phosphines, such as tri-n-butyl-phosphorus, to form HCo (CO) 3 (PR 3 ) A catalyst of the type which requires a reduced pressure (5-10 MPa) compared to BASF processes for the hydroformylation of olefins, but still requires a higher temperature (170-210 ℃) and the selectivity of the aldehydes in the product is still not satisfactory (US 3239569; US 3448157). Compared with the harsh reaction conditions of cobalt catalysts, rhodium catalysts have been attracting attention because of the mildness of the reaction conditions and good selectivity of the reaction products, DAVY company, UCC company, BASF company all use triphenylphosphine as phosphine ligand to modify rhodium catalysts to expect formation of HRh (CO) during the reaction x (PPh 3 ) 4-x The catalyst has a catalytic active center, and the reaction pressure is smaller (usually 1-15 MPa) and the reaction temperature is lower (100-130 ℃) when the catalyst is practically applied in industry (Rhodiumcatalyzed hydroformylation [ M)].Springer Science&Business Media,2002.)。
Because the internal olefin is easier to generate side products such as branched aldehyde, branched alkane and the like than the terminal olefin, the hydroformylation effect is more complex, and the normal and iso ratio of aldehyde products is lower. The coal-based Fei Tuogao carbon olefin raw material contains 34-39% of linear alpha-olefin and 14-20% of beta-olefin, and in the existing coal-based Fischer-Tropsch olefin hydroformylation technology, the Fischer-Tropsch olefin carbon chain length for coal-based Fischer-Tropsch olefin hydroformylation is still short, the conversion rate of internal olefin is low, the selectivity of linear aldehyde is not high, and the normal-to-abnormal ratio of product aldehyde is still low, so that the problems need to be solved.
Patent CN111646885A provides a method for preparing aldehyde based on Fischer-Tropsch low-carbon olefin hydroformylation, which adopts C in Fischer-Tropsch synthesis product 2 ～C 5 The components mainly comprise propylene and butene which are used as raw materials, triphenylphosphine is used as phosphine ligand to form a catalyst with rhodium complex, and the catalyst catalyzes the hydroformylation of the propylene and the butene to prepare butyraldehyde and valeraldehyde under the condition that the rhodium concentration reaches 200ppm and the reaction temperature of 97 ℃ and the synthesis gas pressure of 2.2 MPa. After the reaction is finished, separating aldehyde from unreacted alkane in the reaction product, wherein the conversion rate of alkene can reach 97%, and the purity of product aldehyde can reach 99wt%.
Patent CN106622376B provides a method and a catalyst for isomerization and hydroformylation of internal olefins, which adopt a catalytic system of rhodium-ruthenium bimetallic complex and diphenyl triphosphate ligand, in the hydroformylation of 2-octene (cis-trans mixture), the conversion rate of olefins reaches 81.3%, the selectivity of linear aldehyde reaches 97.9%, and the isomerization is 1.0%.
However, the above patent has limitations, so it is necessary to provide a method suitable for C 8 ～C 12 A method for hydroformylation of coal-based Fischer-Tropsch mixed olefins containing internal olefins.
Disclosure of Invention
The invention aims to provide a method for preparing aldehyde by hydroformylation of Fischer-Tropsch mixed olefin, which aims to solve the problem of C in the prior art 8 ～C 12 The coal-based Fischer-Tropsch mixed olefin hydroformylation process has the problem that high conversion rate and selectivity are difficult to realize.
In order to achieve the above object, according to one aspect of the present invention, there is provided a feeA process for the hydroformylation of a trop mixed olefin to produce an aldehyde, the process comprising: carrying out hydroformylation reaction on Fischer-Tropsch mixed olefin and synthesis gas in the presence of a rhodium-containing catalyst to obtain aldehyde; wherein the Fischer-Tropsch mixed olefin contains C 8 ～C 12 Is a mixed olefin of (a) and (b); the synthesis gas is H 2 And CO.
Further, the rhodium-containing catalyst is a complex formed by a rhodium precursor and a ligand; preferably, the weight ratio of rhodium precursor to ligand is 1 (9-40), more preferably 1 (10-19).
Further, the rhodium precursor is Rh (acac) (CO) 2 And/or HRh (CO) 4 。
Further, the ligand is a monophosphine ligand or a biphosphine ligand; preferably, the ligand is one or more of triphenylphosphine, triphenyl phosphite, phenyl tris (2, 4-di-tert-butylphenyl) phosphite, 4, 5-bis-diphenylphosphine-9, 9-dimethylxanthene and 6- (2 '- (4, 8-di-tert-butyl-3, 9-dimethoxydibenzo [ d, f ] [1,3,2] dioxol-6-yl) oxy) -3,3',5 '-tetramethyl- [1,1' -biphenyl ] -2-yl) oxy) -2,3,8,10-tetramethyldibenzo [ d, f ] [1,3,2] dioxaphosph-ne; more preferably, the ligand is 4, 5-bis (diphenylphosphine) -9, 9-dimethylxanthene and/or 6- (2 '- (4, 8-di-tert-butyl-3, 9-dimethoxydibenzo [ d, f ] [1,3,2] dioxaphosphorin-6-yl) oxy) -3,3',5 '-tetramethyl- [1,1' -biphenyl ] -2-yl) oxy) -2,3,8,10-tetramethyldibenzo [ d, f ] [1,3,2] dioxaphosph-ropene.
Further, the rhodium-containing catalyst is HRh (CO) 2 (PPh 3 ) 2 、HRh(CO)(PPh 3 ) 3 、HRh(CO) 2 (TTP) 2 、HRh(CO) 2 (TDP) 2 、HRh(CO) 2 (XantPhos) and HRh (CO) 2 (bisphosphites) one or more of the following.
Further, the weight ratio of the rhodium-containing catalyst to the Fischer-Tropsch mixed olefin is 1 (40-80); preferably, a solvent is also present in the hydroformylation reaction, more preferably a rhodium-containing catalyst, the solvent and the Fischer-Tropsch mixed olefin in a weight ratio of 1: (8-20): (40-80); most preferably the solvent is one or more of toluene, xylene and benzene.
Further, C 8 ～C 12 The weight percentage of the mixed olefins in the Fischer-Tropsch mixed olefins is 48-60%.
Further, C 8 ～C 12 Comprises one or more of 1-octene, 2-octene, 1-nonene, 2-nonene, 1-decene, 2-decene, 1-undecene, 2-undecene, 1-dodecene, 2-dodecene.
Further, the Fischer-Tropsch mixed olefin comprises 34 to 39 percent of linear alpha-olefin, 14 to 20 percent of beta-olefin and 34 to 38 percent of alkane in percentage by weight, and the balance of oxygen-containing compound; preferably, the alkane is one or more of octane, nonane, decane, undecane and dodecane; the oxygen-containing compound comprises one or more of 1-nonanol and 1-decanol.
Further, H in the synthesis gas 2 And the molar ratio of CO is (1-2): 1.
Further, the temperature of the hydroformylation reaction is 80-120 ℃, the time is 1-10 h, and the pressure is 1-5 MPa; preferably, the hydroformylation reaction is carried out with stirring, more preferably at a stirring rate of 400 to 800r/min.
Further, before the hydroformylation reaction, the method further comprises the step of deacidifying the Fischer-Tropsch mixed olefin to obtain deacidified Fischer-Tropsch mixed olefin; preferably, the acid value of the Fischer-Tropsch mixed olefin is 0.79-2.85 mgKOH/g, and the acid value of the Fischer-Tropsch mixed olefin after deacidification is less than or equal to 0.05mgKOH/g; more preferably, the deacidification treatment is carried out at a temperature of 20-40 ℃, a pressure of 0.01-0.1 MPa and a time of 100-200 min; more preferably, the deacidification treatment is performed under stirring, and the stirring rate is preferably 400 to 800r/min.
Further, deacidifying is carried out by using alkali liquor, preferably the weight ratio of Fischer-Tropsch mixed olefin to alkali liquor is 1 (1-2); preferably, the lye is present in a weight concentration of 0.5 to 5wt%.
By applying the technical scheme of the invention, the method for preparing aldehyde by hydroformylation of Fischer-Tropsch mixed olefin is provided. The rhodium-containing catalyst is selected to catalyze the hydroformylation reaction, and the catalyst can be suitable for complex composition components of coal-based Fei Tuogao carbon olefin raw materials, so that the Fischer-Tropsch mixed olefin achieves higher conversion rate, and the aldehyde in the product has good selectivity. The rhodium-containing catalyst has the advantage of mild reaction conditions in industrial application, has low reaction temperature and pressure and high selectivity of product aldehyde when being applied to the hydroformylation of Fischer-Tropsch mixed olefin, and can effectively utilize raw materials.
Detailed Description
It should be noted that, in the case of no conflict, the embodiments and features in the embodiments may be combined with each other. The present invention will be described in detail with reference to examples.
In order to solve the above-mentioned problems of the prior art, according to an aspect of the present invention, there is provided a method for preparing aldehydes by hydroformylation of Fischer-Tropsch mixed olefins, the method comprising: carrying out hydroformylation reaction on Fischer-Tropsch mixed olefin and synthesis gas in the presence of a rhodium-containing catalyst and a solvent to obtain aldehyde; wherein the Fischer-Tropsch mixed olefin contains C 8 ～C 12 Is a mixed olefin of (a) and (b); the synthesis gas is H 2 And CO.
The rhodium-containing catalyst is selected to catalyze the hydroformylation reaction, and the catalyst can be suitable for complex composition components of coal-based Fei Tuogao carbon olefin raw materials, so that the Fischer-Tropsch mixed olefin achieves higher conversion rate, and the aldehyde in the product has good selectivity. The rhodium-containing catalyst has the advantage of mild reaction conditions in industrial application, has low reaction temperature and pressure and high selectivity of product aldehyde when being applied to the hydroformylation of Fischer-Tropsch mixed olefin, and can effectively utilize raw materials.
Internal olefins may or may not be included in the Fischer-Tropsch mixed olefins, to which the invention is applicable. The internal olefin is easier to generate branched aldehydes, branched paraffins and other byproducts than the terminal olefin, and the method provided by the invention can effectively overcome the technical problem. Those skilled in the art will appreciate that the rhodium-containing catalysts provided by the present invention are equally applicable to Fischer-Tropsch mixed olefins which do not contain internal olefins.
In a preferred embodiment, to further increase the selectivity of the product aldehyde, the rhodium-containing catalyst is a complex of a rhodium precursor and a ligand; preferably, the weight ratio of rhodium precursor to ligand is 1 (9-40), more preferably 1 (10-19). Preferably, the ligand modified rhodium-containing catalyst is more beneficial to improving the conversion rate of internal olefin and the selectivity of product aldehyde in the hydroformylation reaction. Through a great deal of research and experiments, the inventor finds that the weight ratio of rhodium precursor to ligand is preferable, the selectivity of product aldehyde is more favorable to be improved, and the positive-to-negative ratio of the product aldehyde can be more than 40 by configuring the catalyst within the preferable range of the invention.
In practice, the rhodium precursor, ligand and Fischer-Tropsch mixed olefin are preferably mixed together to effect the hydroformylation reaction.
In a preferred embodiment, the rhodium precursor is Rh (acac) (CO) 2 And/or HRh (CO) 4 . Preferably, the rhodium carbonyl precursor is more efficiently complexed with the ligand without the need for an activation reaction.
In a preferred embodiment, the ligand is a monophosphine ligand or a biphosphine ligand; preferably, the ligand is triphenylphosphine (PPh 3 ) Triphenyl phosphite (TPP), phenyl tris (2, 4-di-t-butylphenyl) phosphite (TDP), 4, 5-bis-diphenylphosphine-9, 9-dimethylxanthene (XantPhos) and 6- (2' - (4, 8-di-t-butyl-3, 9-dimethoxy dibenzo [ d, f)][1,3,2]Dioxyphosphol-6-yl) oxy) -3,3', 5' -tetramethyl- [1,1' -biphenyl]-2-yl) oxy) -2,3,8,10-tetramethyldibenzo [ d, f][1,3,2]One or more of the two oxo-phospho-phenylpropanes (abbreviated as bisphosphite ligands). The structural formula of the ligand is as follows:
more preferably, the ligand is 4, 5-bis (diphenylphosphine) -9, 9-dimethylxanthene and/or 6- (2 '- (4, 8-di-tert-butyl-3, 9-dimethoxydibenzo [ d, f ] [1,3,2] dioxaphosphorin-6-yl) oxy) -3,3',5 '-tetramethyl- [1,1' -biphenyl ] -2-yl) oxy) -2,3,8,10-tetramethyldibenzo [ d, f ] [1,3,2] dioxaphosph-ropene.
In the preferred organophosphorus ligand-modified catalysts described above, the electronic as well as steric effects of the phosphine ligand provide beneficial effects on the degree of hydrogenation. Both electron and space effects of the ligand determine the reactivity of the modified catalyst in the homogeneous hydroformylation reaction.
Phosphites are less susceptible to oxidation and loss of complexation than typical phosphine ligands, and are easier to synthesize. At the same time the substances are weak sigma - Electron donor, strong pi - The electron acceptor has larger steric hindrance, and can obtain better catalytic activity in the hydroformylation reaction by taking the electron acceptor as a ligand.
The internal olefin conversion rate can be achieved when triphenyl phosphite (TPP), tri (2, 4-di-tert-butylphenyl) phenyl phosphite (TDP) and bisphosphite ligand are used for the hydroformylation reaction>99, while triphenylphosphine (PPh) 3 ) The reason why the conversion of internal olefins is higher than that of 4, 5-bis-diphenylphosphine-9, 9-dimethylxanthene (XantPhos) in the hydroformylation reaction is related to the nature of the three groups bonded to the phosphine atom.
The rhodium catalyst modified by the double phosphite has higher reaction speed and better regioselectivity than a monodentate phosphine ligand in the hydroformylation reaction. Tolman et al propose the concept of "cone angle" and electrical constant (x) to measure the steric and electronic effects of a monodentate phosphine ligand, the larger the value of θ, the more pronounced the steric effect of the phosphine ligand. The skeleton of the bidentate phosphine ligand and the bond angle of the bidentate phosphine ligand and the metal chelate play a decisive role in the selectivity of the hydroformylation reaction, and the generation of linear hydroformylation products is facilitated when the actual bond angle between P-Rh-P of the bidentate phosphine ligand is close to 120 degrees. The selectivity of normal aldehyde is thus higher when the biphosphine ligand is used for hydroformylation catalysis than when the monophosphine ligand is used for hydroformylation.
In a preferred embodiment, the rhodium-containing catalyst is HRh (CO) 2 (PPh 3 ) 2 、HRh(CO)(PPh 3 ) 3 、HRh(CO) 2 (TTP) 2 、HRh(CO) 2 (TDP) 2 、HRh(CO) 2 (XantPhos) and HRh (CO) 2 (bisphosphites) one or more of the following. The rhodium-containing catalyst is preferable, and the conversion rate of the raw material and the selectivity of the product can be improved better.
In a preferred embodiment, the weight ratio of rhodium-containing catalyst to Fischer-Tropsch mixed olefin is 1 (40 to 80) for better reaction; preferably, a solvent is also present in the hydroformylation reaction, more preferably a rhodium-containing catalyst, the solvent and the Fischer-Tropsch mixed olefin in a weight ratio of 1: (8-20): (40-80); most preferably the solvent is one or more of toluene, xylene and benzene.
In a preferred embodiment, C 8 ～C 12 The weight percentage of the mixed olefins in the Fischer-Tropsch mixed olefins is 48-60%.
In a preferred embodiment, C 8 ～C 12 Comprises one or more of 1-octene, 2-octene, 1-nonene, 2-nonene, 1-decene, 2-decene, 1-undecene, 2-undecene, 1-dodecene, 2-dodecene.
In a preferred embodiment, the Fischer-Tropsch mixed olefins comprise 34 to 39% of linear alpha-olefins, 14 to 20% of beta-olefins and 34 to 38% of alkanes, the balance being oxygenates, by weight percent of the Fischer-Tropsch mixed olefins; preferably, the alkane is one or more of octane, nonane, decane, undecane and dodecane; the oxygenate comprises one or more of 1-nonanol, 1-decanol. The above-mentioned oxygen-containing compound has a certain toxicity to catalyst.
In a preferred embodiment, H in the synthesis gas 2 And the molar ratio of CO is (1-2): 1.
In a preferred embodiment, the hydroformylation reaction is carried out at a temperature of 80 to 120℃for a period of 1 to 10 hours and at a pressure of 1 to 5MPa; preferably, the hydroformylation reaction is carried out with stirring, more preferably at a stirring rate of 400 to 800r/min.
In actual operation, it is preferred to first charge the reaction vessel with synthesis gas to displace air and subsequently charge the synthesis gas to maintain the pressure. The above conditions are more advantageous in promoting the hydroformylation reaction.
In order to further improve the stability of the catalyst, in a preferred embodiment, before the hydroformylation reaction, the method further comprises deacidifying the Fischer-Tropsch mixed olefin to obtain deacidified Fischer-Tropsch mixed olefin; preferably, the acid value of the Fischer-Tropsch mixed olefin is 0.79-2.85 mgKOH/g, and the acid value of the Fischer-Tropsch mixed olefin after deacidification is less than or equal to 0.05mgKOH/g; more preferably, the deacidification treatment is carried out at a temperature of 20 to 40 ℃, a pressure of 0.01 to 0.1MPa, and a time of 100 to 200 minutes. The deacidification treatment is preferably carried out, so that the problem of acid poisoning of the oxo catalyst is further solved, the hydroformylation reaction is further promoted, and the raw material conversion rate is improved.
In actual operation, the deacidification treatment is preferably performed under stirring, preferably at a stirring rate of 400 to 800r/min.
In a preferred embodiment, the deacidification treatment is carried out by using alkali liquor, preferably the weight ratio of Fischer-Tropsch mixed olefin to alkali liquor is 1 (1-2); preferably, the lye is present in a weight concentration of 0.5 to 5wt%. The deacidification method is more favorable for reducing the emulsification phenomenon and improving the deacidification effect.
In actual practice, the alkaline substance in the alkaline solution is not particularly limited, and may be, for example, one or more selected from sodium hydroxide, potassium hydroxide, ammonia, dimethylamine, ethylamine and triethylamine.
The present application is described in further detail below in conjunction with specific embodiments, which should not be construed as limiting the scope of the claims.
In the following examples, the undeacidification Fischer-Tropsch mixed olefin composition is shown in Table 1, and the deacidified Fischer-Tropsch mixed olefin composition is shown in Table 2, and, unless otherwise specified, the various raw materials used were all commercially available.
TABLE 1 non-deacidified Fischer Tropsch C 8 -C 12 Fraction raw material composition
| Numbering device | Component (A) | Content/wt% |
| 1 | Alkanes | 36.78 |
| 2 | Alpha-olefins | 40.05 |
| 3 | Beta-olefins | 17.57 |
| 4 | Alcohol substance | 3.02 |
| 5 | Acid value | 2.63mgKOH/g |
TABLE 2 Fischer-Tropsch C after deacidification 8 -C 12 Fraction raw material composition
Wherein the alkane comprises: 1-octane, 1-nonane, 1-decane, 1-undecane, 1-dodecane.
Example 1
Will be 8.5 mg Rh (acac) (CO) 2 0.25 g of bisphosphite ligand and 41.6mL of a Fischer-Tropsch mixed olefin (as shown in Table 2) were charged to an autoclave equipped with a temperature controller and a magnetic stirrer, and P was introduced into the autoclave H2 ：P CO (molar ratio) =1: 1, replacing air for three times, then adding the synthesis gas into a kettle to enable the pressure of the system to be 1MPa, stopping the reaction after the reaction is carried out for 4 hours under the conditions that the temperature is 110 ℃ and the stirring speed is 500rpm, decompressing the reaction kettle after the temperature of the reaction kettle is reduced to room temperature, sampling and carrying out gas chromatography analysis, and the analysis results are shown in table 3.
Example 2
The difference from example 1 is that the reaction temperature is 95 ℃.
Example 3
The difference from example 1 is that the reaction temperature is 90 ℃.
Example 4
The difference from example 1 is that 0.866 g of toluene are added and the reaction temperature is 90 ℃.
Example 5
The difference from example 1 is that the reaction time is 8h.
Example 6
The difference from example 1 is that the reaction time is 10h.
Example 7
The difference from example 1 is that the reaction temperature is 85℃and the reaction time is 10h.
Example 8
The difference from example 1 is that the bisphosphite ligand is used in an amount of 0.13g.
Example 9
The difference from example 1 is that the bisphosphite ligand is used in an amount of 0.13g, and the reaction temperature is 90 ℃.
Example 10
The difference from example 1 is that the amount of bisphosphite ligand used is 0.13g, and the reaction temperature is 85 ℃.
Example 11
The difference from example 1 is that the amount of bisphosphite ligand used is 0.13g, the reaction temperature is 85℃and the reaction time is 10 hours.
Example 12
Will be 8.5 mg Rh (acac) (CO) 2 0.09 g PPh 3 And 41.6mL of a Fischer-Tropsch mixed olefin (as in Table 2) were charged to a high pressure reactor equipped with a temperature controller and a magnetic stirrer, and P was introduced into the reactor H2 ：P CO (molar ratio) =1: 1, replacing air for three times, then adding the synthesis gas into a kettle to enable the pressure of the system to be 1MPa, stopping the reaction after the reaction is carried out for 4 hours under the conditions that the temperature is 90 ℃ and the stirring speed is 500rpm, decompressing the reaction kettle after the temperature of the reaction kettle is reduced to room temperature, sampling and carrying out gas chromatography analysis, and the analysis results are shown in table 3.
Example 13
Will be 8.5 mg Rh (acac) (CO) 2 0.11 g TPP and 41.6mL Fischer-Tropsch mixed olefins (as in Table 2) were charged to an autoclave equipped with a temperature controller and a magnetic stirrer, and P was introduced into the autoclave H2 ：P CO (molar ratio) =1: 1, replacing air for three times, then adding the synthesis gas into a kettle to enable the pressure of the system to be 1MPa, stopping the reaction after the reaction is carried out for 10 hours under the conditions that the temperature is 90 ℃ and the stirring speed is 500rpm, decompressing the reaction kettle after the temperature of the reaction kettle is reduced to room temperature, sampling and carrying out gas chromatography analysis, and the analysis results are shown in table 3.
Example 14
Will be 8.5 mg Rh (acac) (CO) 2 0.21 g of TDP and 41.6mL of a Fischer-Tropsch mixed olefin (as in Table 2) were charged into an autoclave equipped with a temperature controller and a magnetic stirrer, and P was introduced into the autoclave H2 ：P CO (molar ratio) =1: 1, replacing air for three times, then adding the synthesis gas into a kettle to enable the pressure of the system to be 1MPa, stopping the reaction after the reaction is carried out for 4 hours under the conditions that the temperature is 85 ℃ and the stirring speed is 500rpm, decompressing the reaction kettle after the temperature of the reaction kettle is reduced to room temperature, sampling and carrying out gas chromatography analysis, and the analysis results are shown in table 3.
Example 15
Will be 8.5 mg Rh (acac) (CO) 2 0.19 g XantPhos and 41.6mL Fischer-Tropsch mixed olefins (as in Table 2) were charged to a high pressure reactor equipped with a temperature controller and a magnetic stirrer, and P was introduced into the reactor H2 ：P CO (molar ratio) =1: 1, replacing air for three times, then adding the synthesis gas into a kettle to enable the pressure of the system to be 1MPa, stopping the reaction after reacting for 5 hours at the temperature of 110 ℃ and the stirring speed of 500rpm, decompressing and opening the kettle after the temperature of the reaction kettle is reduced to room temperature, sampling and carrying out gas chromatographic analysis, wherein the analysis result is shown in table 3.
Example 16
Will be 8.5 mg Rh (acac) (CO) 2 0.13g of bisphosphite ligand and 41.6mL of a non-deacidified Fischer-Tropsch mixed olefin (as in Table 2) were charged to a high pressure reactor equipped with a temperature controller and a magnetic stirrer, and P was introduced into the reactor H2 ：P CO (molar ratio) =1: 1, replacing air for three times, then adding the synthesis gas into a kettle to enable the pressure of the system to be 1MPa, stopping the reaction after reacting for 10 hours under the conditions that the temperature is 85 ℃ and the stirring speed is 500rpm, decompressing and opening the kettle after the temperature of the reaction kettle is reduced to room temperature, sampling and carrying out gas chromatography analysis, and the analysis results are shown in table 3.
Comparative example 1
0.17 g of Co 2 (CO) 8 0.39 g of triphenylphosphine ligand, 10mL of sulfolane, 25mL of 2-ethylhexanol, 16mL of Fischer-Tropsch mixed olefin were charged into an autoclave equipped with a temperature controller and a magnetic stirrer, and P was introduced into the autoclave H2 ：P CO (molar ratio) =2: 1, replacing air for three times, then adding the synthesis gas into a kettle to enable the pressure of the system to be 6MPa, stopping the reaction after 7 hours of reaction under the conditions that the temperature is 160 ℃ and the stirring speed is 500rpm, decompressing and opening the kettle after the temperature of the reaction kettle is reduced to room temperature, sampling and carrying out gas chromatography analysis, and the analysis results are shown in table 3.
The testing method comprises the following steps:
the products of the examples and comparative examples were analyzed by gas chromatography, instrument model GC-2014. Gas chromatography detection conditions: sample injection amount 0.2 mu L, split ratio 100, sample inlet temperatureThe temperature of the detector is 25 ℃, the temperature of the detector is 250 ℃, the temperature of the chromatographic column is programmed to be 35 ℃ (15 min) -2 ℃/min-200 ℃ (0 min), and nitrogen (95 kPa) is carried out. Chromatographic column: HP-PONA (50 m.times.0.2 mm.times.0.5 μm). Wherein alpha-olefin means C 8 -C 12 The aldehydes in the selectivity of the product aldehydes include C 9 -C 13 Normal aldehyde and isomeric aldehyde of (2), the normal-to-iso ratio of product aldehyde refers to C in the product 9 -C 13 Normal aldehyde and C 9 -C 13 Is used as the catalyst.
The conversion rate and the like are calculated as follows:
TABLE 3 Table 3
From the above description, it can be seen that the above embodiments of the present invention achieve the following technical effects:
as can be seen from the results of Table 3, in examples 1 to 15, the conversion of the alpha-olefin was not less than 98, and the conversion of the beta-olefin was greatly different, indicating that the alpha-olefin was more reactive. From example 1, example 2The results of examples 3 and 8, 9 and 10 show that the hydroformylation reaction is carried out with bisphosphite ligands, the higher the temperature, the more advantageous the internal olefin reaction is, the ligand: the selectivity of aldehyde is slightly higher when the rhodium mass ratio is 15.3; as can be seen from the results of examples 1 and 8, the conversion of alpha-olefin and beta-olefin was not less than 93.5, but the positive-to-iso ratio of aldehyde was not more than 17.6, indicating that the reaction at 110℃was favorable for the reaction of internal olefin but unfavorable for the formation of normal aldehyde, and the color of the catalyst after the reaction was darker (severe oxidation) at this temperature, unfavorable for the recovery of the catalyst, so that the reaction temperature was not selected to be 110 ℃. As can be seen from the results of examples 3 and 4, the hydroformylation reaction was carried out with the bisphosphite ligand, and the conversion of beta-olefin was increased after the addition of toluene as a solvent, but the selectivity of aldehyde was not greatly changed from the normal-to-iso ratio. From the results of examples 3, 5 and 6, it can be seen that the hydroformylation reaction with bisphosphite ligand is carried out for a suitably prolonged period of time to facilitate the reaction of internal olefins. From the results of example 7 and example 11, it can be seen that the hydroformylation reaction was carried out with bisphosphite ligand, ligand: the conversion of beta-olefin is larger and the selectivity of aldehyde is slightly higher when the rhodium mass ratio is 15.3, and the above results indicate that the ligand: rhodium mass ratio of 15.3 is more favorable for aldehyde formation. From the results of examples 11 and 16, it can be seen that the deacidified Fischer-Tropsch olefins have higher feedstock conversion and higher product aldehyde selectivity than the non-deacidified Fischer-Tropsch olefins, indicating that the deacidified Fischer-Tropsch olefins provide better catalyst activity. As can be seen from the results of examples 12, 13 and 14, the monophosphine ligand PPh 3 The monophosphine ligand TTP and the monophosphine ligand TDP are subjected to hydroformylation reaction, so that the normal-iso ratio of the generated aldehyde is less than or equal to 1.5, which indicates that the monophosphine ligand is unfavorable for generating normal aldehyde. From the results of example 15, it can be seen that the beta-olefin does not participate in the hydroformylation reaction with the Xantphos ligand.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (13)
1. A process for the hydroformylation of a fischer-tropsch mixed olefin to produce an aldehyde, the process comprising:
carrying out hydroformylation reaction on Fischer-Tropsch mixed olefin and synthesis gas in the presence of a rhodium-containing catalyst to obtain aldehyde; wherein,,
the Fischer-Tropsch mixed olefin contains C 8 ～C 12 Is a mixed olefin of (a) and (b);
the synthesis gas is H 2 And CO.
2. The method of claim 1, wherein the rhodium-containing catalyst is a complex of a rhodium precursor and a ligand; preferably, the weight ratio of rhodium precursor to ligand is 1 (9-40), more preferably 1 (10-19).
3. The method of claim 2, wherein the rhodium precursor is Rh (acac) (CO) 2 And/or HRh (CO) 4 。
4. The method of claim 2, wherein the ligand is a monophosphine ligand or a biphosphine ligand; preferably, the ligand is one or more of triphenylphosphine, triphenyl phosphite, phenyl tris (2, 4-di-tert-butylphenyl) phosphite, 4, 5-bis-diphenylphosphine-9, 9-dimethylxanthene and 6- (2 '- (4, 8-di-tert-butyl-3, 9-dimethoxydibenzo [ d, f ] [1,3,2] dioxol-6-yl) oxy) -3,3',5 '-tetramethyl- [1,1' -biphenyl ] -2-yl) oxy) -2,3,8,10-tetramethyl dibenzo [ d, f ] [1,3,2] dioxaphospho-phenyl propane;
more preferably, the ligand is 4, 5-bis (diphenylphosphine) -9, 9-dimethylxanthene and/or 6- (2 '- (4, 8-di-tert-butyl-3, 9-dimethoxydibenzo [ d, f ] [1,3,2] dioxaphosphorin-6-yl) oxy) -3,3',5 '-tetramethyl- [1,1' -biphenyl ] -2-yl) oxy) -2,3,8,10-tetramethyldibenzo [ d, f ] [1,3,2] dioxaphosph-ropene.
5. The process of any one of claims 2 to 4, wherein the rhodium-containing catalyst is
HRh(CO) 2 (PPh 3 ) 2 、HRh(CO)(PPh 3 ) 3 、HRh(CO) 2 (TTP) 2 、HRh(CO) 2 (TDP) 2 、HRh(CO) 2 (XantPhos) and HRh (CO) 2 (bisphosphites) one or more of the following.
6. The process according to any one of claims 1 to 5, wherein the weight ratio of the rhodium-containing catalyst to the fischer-tropsch mixed olefin is 1 (40 to 80); preferably, a solvent is also present in the hydroformylation reaction, more preferably the weight ratio of the rhodium-containing catalyst, the solvent and the Fischer-Tropsch mixed olefin is 1: (8-20): (40-80); most preferably the solvent is one or more of toluene, xylene and benzene.
7. The method according to any one of claims 1 to 6, wherein C 8 ～C 12 The weight percentage of the mixed olefins in the Fischer-Tropsch mixed olefins is 48-60%.
8. The method of claim 7, wherein the C 8 ～C 12 Comprises one or more of 1-octene, 2-octene, 1-nonene, 2-nonene, 1-decene, 2-decene, 1-undecene, 2-undecene, 1-dodecene, 2-dodecene.
9. The process according to any one of claims 1 to 8, characterized in that the fischer-tropsch mixed olefins comprise, in weight percent of the fischer-tropsch mixed olefins, 34-39% of linear alpha-olefins, 14-20% of beta-olefins and 34-38% of alkanes, the balance being oxygenates; preferably, the alkane is one or more of octane, nonane, decane, undecane and dodecane; the oxygen-containing compound comprises one or more of 1-nonanol and 1-decanol.
10. The method according to any one of claims 1 to 9, wherein the H in the synthesis gas 2 And the molar ratio of the CO is (1-2): 1.
11. The process according to any one of claims 1 to 10, wherein the hydroformylation reaction is carried out at a temperature of 80 to 120 ℃ for a time of 1 to 10 hours and at a pressure of 1 to 5MPa;
preferably, the hydroformylation reaction is carried out under stirring, more preferably at a stirring rate of 400 to 800r/min.
12. The process according to any one of claims 1 to 11, further comprising, prior to the hydroformylation, deacidifying the fischer-tropsch mixed olefin to obtain a deacidified fischer-tropsch mixed olefin;
preferably, the acid value of the Fischer-Tropsch mixed olefin is 0.79-2.85 mgKOH/g, and the acid value of the deacidified Fischer-Tropsch mixed olefin is less than or equal to 0.05mgKOH/g;
more preferably, the deacidification treatment is carried out at a temperature of 20-40 ℃, a pressure of 0.01-0.1 MPa and a time of 100-200 min;
more preferably, the deacidification treatment is performed under stirring, and preferably the stirring rate is 400 to 800r/min.
13. The process according to claim 12, characterized in that the deacidification treatment is carried out with an alkaline solution, preferably the weight ratio of the fischer-tropsch mixed olefins to the alkaline solution is 1 (1-2); preferably, the alkali liquor is present in a weight concentration of 0.5 to 5wt%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN202310112705.1A CN116102412A (en) | 2023-02-14 | 2023-02-14 | Method for preparing aldehyde by hydroformylation of Fischer-Tropsch mixed olefin |
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