CN115850041B - Method for preparing aldehyde by olefin hydroformylation, application of phenolic antioxidant and method for improving stability of catalytic system - Google Patents
Method for preparing aldehyde by olefin hydroformylation, application of phenolic antioxidant and method for improving stability of catalytic system Download PDFInfo
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- CN115850041B CN115850041B CN202211528004.8A CN202211528004A CN115850041B CN 115850041 B CN115850041 B CN 115850041B CN 202211528004 A CN202211528004 A CN 202211528004A CN 115850041 B CN115850041 B CN 115850041B
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- rhodium
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- 238000007037 hydroformylation reaction Methods 0.000 title claims abstract description 61
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 57
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 40
- 239000002530 phenolic antioxidant Substances 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 31
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 title claims abstract 14
- 239000003446 ligand Substances 0.000 claims abstract description 88
- 239000003054 catalyst Substances 0.000 claims abstract description 59
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 53
- 239000010948 rhodium Substances 0.000 claims abstract description 53
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims abstract description 53
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims abstract description 50
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 23
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 23
- 238000004519 manufacturing process Methods 0.000 claims abstract description 4
- 238000002360 preparation method Methods 0.000 claims abstract 5
- 239000007789 gas Substances 0.000 claims description 25
- GGRQQHADVSXBQN-FGSKAQBVSA-N carbon monoxide;(z)-4-hydroxypent-3-en-2-one;rhodium Chemical compound [Rh].[O+]#[C-].[O+]#[C-].C\C(O)=C\C(C)=O GGRQQHADVSXBQN-FGSKAQBVSA-N 0.000 claims description 19
- -1 rhodium tris (triphenylphosphine) carbonyl chloride Chemical compound 0.000 claims description 18
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims description 16
- 150000008301 phosphite esters Chemical class 0.000 claims description 15
- 235000010354 butylated hydroxytoluene Nutrition 0.000 claims description 14
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 claims description 12
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 claims description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 12
- 125000003545 alkoxy group Chemical group 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 12
- BGNXCDMCOKJUMV-UHFFFAOYSA-N Tert-Butylhydroquinone Chemical compound CC(C)(C)C1=CC(O)=CC=C1O BGNXCDMCOKJUMV-UHFFFAOYSA-N 0.000 claims description 10
- 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 10
- JZODKRWQWUWGCD-UHFFFAOYSA-N 2,5-di-tert-butylbenzene-1,4-diol Chemical compound CC(C)(C)C1=CC(O)=C(C(C)(C)C)C=C1O JZODKRWQWUWGCD-UHFFFAOYSA-N 0.000 claims description 9
- IMOYOUMVYICGCA-UHFFFAOYSA-N 2-tert-butyl-4-hydroxyanisole Chemical compound COC1=CC=C(O)C=C1C(C)(C)C IMOYOUMVYICGCA-UHFFFAOYSA-N 0.000 claims description 8
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000004250 tert-Butylhydroquinone Substances 0.000 claims description 7
- 235000019281 tert-butylhydroquinone Nutrition 0.000 claims description 7
- IKEHOXWJQXIQAG-UHFFFAOYSA-N 2-tert-butyl-4-methylphenol Chemical compound CC1=CC=C(O)C(C(C)(C)C)=C1 IKEHOXWJQXIQAG-UHFFFAOYSA-N 0.000 claims description 6
- QENZQARJPIQZGX-UHFFFAOYSA-K Cl[Rh](Cl)Cl.C=1C=CC=CC=1P(C=1C=CC=CC=1)(C=1C=CC=CC=1)C(=O)P(C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 Chemical compound Cl[Rh](Cl)Cl.C=1C=CC=CC=1P(C=1C=CC=CC=1)(C=1C=CC=CC=1)C(=O)P(C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 QENZQARJPIQZGX-UHFFFAOYSA-K 0.000 claims description 6
- 229910021604 Rhodium(III) chloride Inorganic materials 0.000 claims description 6
- 125000000732 arylene group Chemical group 0.000 claims description 6
- FERQZYSWBVOPNX-UHFFFAOYSA-N carbonyl dichloride;rhodium;triphenylphosphane Chemical compound [Rh].ClC(Cl)=O.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 FERQZYSWBVOPNX-UHFFFAOYSA-N 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- HOXDXGRSZJEEKN-UHFFFAOYSA-N cycloocta-1,5-diene;rhodium Chemical compound [Rh].C1CC=CCCC=C1 HOXDXGRSZJEEKN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- 150000002367 halogens Chemical class 0.000 claims description 6
- 125000005515 organic divalent group Chemical group 0.000 claims description 6
- 150000003284 rhodium compounds Chemical class 0.000 claims description 6
- SVOOVMQUISJERI-UHFFFAOYSA-K rhodium(3+);triacetate Chemical compound [Rh+3].CC([O-])=O.CC([O-])=O.CC([O-])=O SVOOVMQUISJERI-UHFFFAOYSA-K 0.000 claims description 6
- FCQRKDSALKMOGU-UHFFFAOYSA-K rhodium(3+);triphenylphosphane;trichloride Chemical compound Cl[Rh](Cl)Cl.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 FCQRKDSALKMOGU-UHFFFAOYSA-K 0.000 claims description 6
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 claims description 6
- RMLOZYVMENRVSS-UHFFFAOYSA-N formaldehyde;rhodium Chemical compound [Rh].O=C RMLOZYVMENRVSS-UHFFFAOYSA-N 0.000 claims description 5
- 238000001704 evaporation Methods 0.000 claims description 4
- 230000008020 evaporation Effects 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 230000001502 supplementing effect Effects 0.000 abstract 2
- 238000006243 chemical reaction Methods 0.000 description 63
- 238000000354 decomposition reaction Methods 0.000 description 19
- 239000000243 solution Substances 0.000 description 18
- FXNDIJDIPNCZQJ-UHFFFAOYSA-N 2,4,4-trimethylpent-1-ene Chemical group CC(=C)CC(C)(C)C FXNDIJDIPNCZQJ-UHFFFAOYSA-N 0.000 description 15
- 238000004128 high performance liquid chromatography Methods 0.000 description 12
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 10
- 150000001299 aldehydes Chemical class 0.000 description 10
- JRPPVSMCCSLJPL-UHFFFAOYSA-N 7-methyloctanal Chemical compound CC(C)CCCCCC=O JRPPVSMCCSLJPL-UHFFFAOYSA-N 0.000 description 9
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 8
- 238000001514 detection method Methods 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 8
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 7
- 239000003963 antioxidant agent Substances 0.000 description 7
- 235000006708 antioxidants Nutrition 0.000 description 7
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N pentanal Chemical compound CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 7
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- WTPYRCJDOZVZON-UHFFFAOYSA-N 3,5,5-Trimethylhexanal Chemical compound O=CCC(C)CC(C)(C)C WTPYRCJDOZVZON-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 238000004587 chromatography analysis Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 4
- GYHFUZHODSMOHU-UHFFFAOYSA-N nonanal Chemical compound CCCCCCCCC=O GYHFUZHODSMOHU-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 3
- NCCTVAJNFXYWTM-UHFFFAOYSA-N 2-tert-butylcyclohexa-2,5-diene-1,4-dione Chemical compound CC(C)(C)C1=CC(=O)C=CC1=O NCCTVAJNFXYWTM-UHFFFAOYSA-N 0.000 description 3
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical group OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 3
- 235000010323 ascorbic acid Nutrition 0.000 description 3
- 229960005070 ascorbic acid Drugs 0.000 description 3
- 239000011668 ascorbic acid Substances 0.000 description 3
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 150000003254 radicals Chemical group 0.000 description 3
- GHKOFFNLGXMVNJ-UHFFFAOYSA-N Didodecyl thiobispropanoate Chemical group CCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCC GHKOFFNLGXMVNJ-UHFFFAOYSA-N 0.000 description 2
- 239000003508 Dilauryl thiodipropionate Substances 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 239000007853 buffer solution Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 235000019304 dilauryl thiodipropionate Nutrition 0.000 description 2
- 150000002118 epoxides Chemical class 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- 239000012062 aqueous buffer Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 150000001556 benzimidazoles Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- BDDWSAASCFBVBK-UHFFFAOYSA-N rhodium;triphenylphosphane Chemical compound [Rh].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 BDDWSAASCFBVBK-UHFFFAOYSA-N 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
Abstract
The invention provides a method for preparing aldehyde by olefin hydroformylation, application of phenolic antioxidants and a method for improving stability of a catalytic system. A process for preparing aldehydes by hydroformylation of olefins: the olefin and the synthesis gas are subjected to hydroformylation under the action of a rhodium catalyst, phosphite ligands and phenolic antioxidants. Phenolic antioxidants are used to improve the stability of catalytic systems comprising rhodium catalysts and phosphite ligands in the hydroformylation of olefins to produce aldehydes. A method for improving stability of a catalytic system in preparing aldehyde by olefin hydroformylation reaction is characterized in that a phenolic antioxidant is added into the catalytic system, and the catalytic system comprises a rhodium catalyst and a phosphite ligand. The invention prolongs the cycle service life of the catalyst ligand, reduces the supplementing amount and the supplementing frequency of the catalyst ligand, and improves the stability of the catalytic system in the preparation of aldehyde by the hydroformylation reaction of olefin.
Description
Technical Field
The invention relates to the technical field of petrochemical industry, in particular to a method for preparing aldehyde by olefin hydroformylation, application of a phenolic antioxidant and a method for improving stability of a catalytic system.
Background
Hydroformylation is an important reaction for the synthesis of aldehydes, and has been rapidly developed since 1938 by professor Otto Roelen (Chem Abstr,1994, 38-550) as the most industrially accepted homogeneous catalytic reaction. The catalyst for the hydroformylation reaction is mainly a carbonyl complex of a group VIII metal. The rhodium catalyst has the best catalytic performance, and the catalytic performance of cobalt is only one thousandth of rhodium, but has high temperature resistance and better poison resistance. Rhodium/phosphite ligand catalytic systems show excellent catalytic activity and selectivity in olefin hydroformylation reactions, but researches show that trace oxygen, water and other substances existing in the reaction system tend to cause oxidation or hydrolysis deactivation of phosphite ligands, so that the catalytic activity and stability of rhodium catalysts are reduced, and therefore, the stability of the catalysts and the ligands is still one of important problems of great concern in the field.
To improve the stability of rhodium/phosphite catalytic systems, patent US4567306 discloses the neutralization of acidic compounds by adding organic amine compounds such as benzimidazoles, which prevent further promotion of phosphite hydrolysis, but the addition of organic amines promotes condensation of aldehydes, and does not describe how the added organic amine compounds are removed from the reaction system, if not removed, which would accumulate until a precipitate is formed. Patent US8110709 also uses amines to neutralize acidic impurities, followed by removal of the amine salts using ion exchange columns, resulting in increased costs and added complexity to the overall process. Both patents US5364950 and US6693219 increase the stability of rhodium/phosphite catalytic systems by reducing the acid concentration in the reaction mixture by adding an appropriate amount of epoxide.
The use of weakly basic ion exchange resins in patents US4599206 and US4712775 removes the phosphoric acid byproduct from ligand hydrolysis from the reaction system, thereby preventing phosphoric acid from again promoting ligand hydrolysis. The method increases investment costs to some extent and catalyst adsorption is liable to occur to cause catalyst loss.
Patent US5471944 discloses a method of removing acidic impurities in a reaction system by extraction using a buffer solution, and US9328047B2 first adds epoxide to the reaction system and then extracts acidic compounds in the reactants using a buffer solution. CN107469862a discloses a two-step countercurrent extraction method for removing acidic substances generated by the decomposition of catalyst ligands. All the methods adopt aqueous buffer solution, so that water is easily introduced into a reaction system, and the hydrolysis reaction is easily promoted.
Disclosure of Invention
In view of the above-mentioned drawbacks of the prior art, an object of the present invention is to provide a method for preparing aldehydes by hydroformylation of olefins, use of phenolic antioxidants and a method for improving stability of a catalytic system, which prolong the cycle life of a catalyst ligand, reduce the addition amount and the addition frequency of the catalyst ligand, and improve the stability of the catalytic system in preparing aldehydes by hydroformylation of olefins.
To achieve the above and other related objects, a first aspect of the present invention provides a process for preparing aldehydes by hydroformylation of olefins, which hydroformylation of olefins and synthesis gas takes place under the influence of a rhodium catalyst, phosphite ligands and phenolic antioxidants.
Preferably, the method further comprises: and (3) removing evaporation components from a reaction product obtained by the hydroformylation reaction through evaporation separation, and circularly carrying out the hydroformylation reaction on the residual materials.
Preferably, the method further comprises at least one of the following technical features:
a1 The rhodium catalyst is a metal rhodium compound;
a2 The phosphite ligands are mono-phosphite ligands and/or bisphosphite ligands;
a3 The phenolic antioxidant is a hindered phenolic antioxidant capable of terminating free radical chain growth during oxidation;
a4 A molar ratio of the rhodium catalyst to the phosphite ligand of 1: (10-100), such as 1: (10-50) or 1: (50-100);
a5 A molar ratio of the phenolic antioxidant to the phosphite ligand of 1: (0.5-20), such as 1: (0.5-1), 1: (1-2) or 1: (2-20);
a6 Rhodium is present in a concentration of 50 to 500ppm, such as 50 to 100ppm or 100 to 500ppm;
a7 The olefin is a single olefin or a mixed olefin of C2-C12; and/or the molar ratio of olefin to rhodium is 5000:1 to 15000:1, such as 5000:1 to 10000:1 or 10000:1 to 15000:1, a step of;
a8 CO) in the synthesis gas: h 2 The molar ratio is 1: (1-3);
a9 The hydroformylation reaction temperature is 70-120 ℃, such as 70-80 ℃, 80-110 ℃ or 110-120 ℃;
a10 The pressure of the hydroformylation reaction is 1.0 to 6.0MPa, such as 1.0 to 2.0MPa or 2.0 to 6.0MPa.
More preferably, at least one of the following technical features is further included:
a11 In feature a 1), the rhodium catalyst is selected from at least one of rhodium trichloride, rhodium acetate, carbonylbis (triphenylphosphine) rhodium chloride, rhodium dicarbonyl acetylacetonate, rhodium 1, 5-cyclooctadiene (acetylacetonate), rhodium (acetylacetonate) carbonyl (triphenylphosphine), rhodium carbonyl hydride, rhodium tris (triphenylphosphine) carbonyl chloride, rhodium bis (triphenylphosphine) carbonyl chloride, rhodium tris (triphenylphosphine) chloride, and rhodium tetrakis (triphenylphosphine) hydride;
a21 In the feature a 2), the phosphite ligand is selected from at least one of the following compounds represented by the general structural formula I or the general formula II:
wherein Y is a C6-C28 substituted or unsubstituted organic divalent bridging arylene group; r is R 1 ～R 8 Is hydrogen or independently substituted or unsubstituted C1-C8 alkyl or alkoxy; r is R 9 ～R 23 Is hydrogen or independently substituted or unsubstituted C1-C8 alkyl, C1-C8 alkoxy or halogen;
a31 In the step a 3), the phenolic antioxidant is at least one selected from the group consisting of 2, 6-di-tert-butyl-4-methylphenol, 2' -methylenebis (4-methyl-6-tert-butylphenol), tert-butylhydroquinone, 2, 5-di-tert-butylhydroquinone and tert-butyl-4-hydroxyanisole.
In a second aspect, the invention provides the use of a phenolic antioxidant to improve the stability of a catalytic system comprising a rhodium catalyst and a phosphite ligand in the hydroformylation of olefins to produce aldehydes. The phenolic antioxidant can inhibit the oxidation of phosphite ligands and inhibit the generation of acid, can effectively inhibit the acid-catalyzed hydrolysis of phosphite ligands, fundamentally solve the decomposition problem of phosphite ligands, prolong the cycle service life of catalyst ligands, and reduce the addition amount and the addition frequency of the ligands.
Preferably, the method further comprises at least one of the following technical characteristics:
b1 The rhodium catalyst is a metal rhodium compound;
b2 The phosphite ligands are mono-phosphite ligands and/or bisphosphite ligands;
b3 The phenolic antioxidant is a hindered phenolic antioxidant capable of terminating free radical chain growth during oxidation;
b4 A molar ratio of the rhodium catalyst to the phosphite ligand of 1: (10-100), such as 1: (10-50) or 1: (50-100);
b5 A molar ratio of the phenolic antioxidant to the phosphite ligand of 1: (0.5-20), such as 1: (0.5-1), 1: (1-2) or 1: (2-20);
b6 Rhodium is present in a concentration of 50 to 500ppm, such as 50 to 100ppm or 100 to 500ppm;
b7 The olefin is a single olefin or a mixed olefin of C2-C12; and/or the molar ratio of olefin to rhodium is 5000:1 to 15000:1, such as 5000:1 to 10000:1 or 10000:1 to 15000:1, a step of;
b8 Olefin hydroformylation of olefins with synthesis gas in which CO: h 2 The molar ratio is 1: (1-3);
b9 The hydroformylation reaction temperature is 70-120 ℃, such as 70-80 ℃, 80-110 ℃ or 110-120 ℃;
b10 The pressure of the hydroformylation reaction is 1.0 to 6.0MPa, such as 1.0 to 2.0MPa or 2.0 to 6.0MPa.
More preferably, at least one of the following technical features is further included:
b11 In feature b 1), the rhodium catalyst is selected from at least one of rhodium trichloride, rhodium acetate, carbonylbis (triphenylphosphine) rhodium chloride, rhodium dicarbonyl acetylacetonate, rhodium 1, 5-cyclooctadiene (acetylacetonate), rhodium (acetylacetonate) carbonyl (triphenylphosphine), rhodium carbonyl hydride, rhodium tris (triphenylphosphine) carbonyl chloride, rhodium bis (triphenylphosphine) carbonyl chloride, rhodium tris (triphenylphosphine) chloride, and rhodium tetrakis (triphenylphosphine) hydride;
b21 In the feature b 2), the phosphite ligand is selected from at least one of the following compounds represented by the general structural formula I or the general formula II:
wherein Y is a C6-C28 substituted or unsubstituted organic divalent bridging arylene group; r is R 1 ～R 8 Is hydrogen or independently substituted or unsubstituted C1-C8 alkyl or alkoxy; r is R 9 ～R 23 Is hydrogen or independently substituted or unsubstituted C1-C8 alkyl, C1-C8 alkoxy or halogen;
b31 In the step b 3), the phenolic antioxidant is at least one selected from the group consisting of 2, 6-di-tert-butyl-4-methylphenol, 2' -methylenebis (4-methyl-6-tert-butylphenol), tert-butylhydroquinone, 2, 5-di-tert-butylhydroquinone and tert-butyl-4-hydroxyanisole.
In a third aspect, the invention provides a method for improving stability of a catalytic system in preparing aldehyde by hydroformylation of olefin, wherein a phenolic antioxidant is added into the catalytic system, and the catalytic system comprises a rhodium catalyst and a phosphite ligand.
Preferably, the method further comprises at least one of the following technical characteristics:
c1 The rhodium catalyst is a metal rhodium compound;
c2 The phosphite ligands are mono-phosphite ligands and/or bisphosphite ligands;
c3 The phenolic antioxidant is a hindered phenolic antioxidant capable of terminating free radical chain growth during oxidation;
c4 A molar ratio of the rhodium catalyst to the phosphite ligand of 1: (10-100), such as 1: (10-50) or 1: (50-100);
c5 A molar ratio of the phenolic antioxidant to the phosphite ligand of 1: (0.5-20), such as 1: (0.5-1), 1: (1-2) or 1: (2-20);
c6 Rhodium is present in a concentration of 50 to 500ppm, such as 50 to 100ppm or 100 to 500ppm;
c7 The olefin is a single olefin or a mixed olefin of C2-C12; and/or the molar ratio of olefin to rhodium is 5000:1 to 15000:1, such as 5000:1 to 10000:1 or 10000:1 to 15000:1, a step of;
c8 Olefin hydroformylation of olefins with synthesis gas in which CO: h 2 The molar ratio is 1: (1-3);
c9 The hydroformylation reaction temperature is 70-120 ℃, such as 70-80 ℃, 80-110 ℃ or 110-120 ℃;
c10 The pressure of the hydroformylation reaction is 1.0 to 6.0MPa, such as 1.0 to 2.0MPa or 2.0 to 6.0MPa.
More preferably, at least one of the following technical features is further included:
c11 In feature c 1), the rhodium catalyst includes, but is not limited to, at least one selected from rhodium trichloride, rhodium acetate, rhodium carbonyl bis (triphenylphosphine) chloride, rhodium dicarbonyl acetylacetonate, rhodium 1, 5-cyclooctadiene (acetylacetonate), rhodium (acetylacetonate) carbonyl, (triphenylphosphine) rhodium, tris (triphenylphosphine) rhodium hydride carbonyl, rhodium bis (triphenylphosphine) carbonyl chloride, rhodium tris (triphenylphosphine) chloride, and rhodium tetrakis (triphenylphosphine) hydride;
c21 In feature c 2), the phosphite ligands include, but are not limited to, at least one selected from the group consisting of compounds represented by the following structural formula I or formula II:
wherein Y is a C6-C28 substituted or unsubstituted organic divalent bridging arylene group; r is R 1 ～R 8 Is hydrogen or independently substituted or unsubstituted C1-C8 alkyl or alkoxy; r is R 9 ～R 23 Is hydrogen or independently substituted or unsubstituted C1-C8 alkyl, C1-C8 alkoxy or halogen;
c31 In feature c 3), the phenolic antioxidants include, but are not limited to, at least one selected from the group consisting of 2, 6-di-tert-butyl-4-methylphenol (antioxidant 264), 2' -methylenebis (4-methyl-6-tert-butylphenol) (antioxidant 2246), tert-butylhydroquinone, 2, 5-di-tert-butylhydroquinone, and tert-butyl-4-hydroxyanisole, more preferably at least one selected from the group consisting of 2, 6-di-tert-butyl-4-methylphenol (antioxidant 264), tert-butylhydroquinone, and 2, 5-di-tert-butylhydroquinone.
As described above, the present invention has at least one of the following advantageous effects:
1) The phenolic antioxidant is added as the stabilizer to fundamentally inhibit the oxidation of the ligand and aldehyde and reduce the generation of acidic byproducts, so that the acid-catalyzed ligand decomposition reaction in the catalyst circulation process is effectively reduced, and the stability of the catalyst is improved;
2) Compared with other methods for improving the stability of the catalyst, the method is simple and effective, has small addition amount of the antioxidant and is not easy to cause side reaction;
3) Compared with other antioxidants, the phenolic antioxidants do not influence the normal operation of the hydroformylation reaction, the whole process condition does not need to be changed, other antioxidants such as sulfur-containing antioxidants and metal ion chelating agents can deactivate the catalyst, water-soluble antioxidants such as ascorbic acid and the like are not compatible with a homogeneous hydroformylation reaction system, and enzyme antioxidants can influence the smooth operation of the reaction;
4) The method of the invention does not need to additionally add purification devices such as an extraction tower, reduces equipment investment and improves economic benefit.
Detailed Description
The invention is further illustrated below with reference to examples. It is to be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention. The experimental methods and reagents not specifying the formulation in the following examples were carried out or configured under conventional conditions or conditions suggested by the manufacturer.
Example 1
Rhodium dicarbonyl acetylacetonate, phosphite ester ligand (formula 1) and toluene are prepared into raw material liquid, and the raw material liquid is added into a hydroformylation reaction kettle, wherein the concentration of the rhodium dicarbonyl acetylacetonate in the solution is 100ppm, and the molar ratio of the rhodium dicarbonyl acetylacetonate to the phosphite ester ligand (formula 1) is 1:10; t-butylbenzoquinone was added in a molar ratio of t-butylhydroquinone to phosphite ligand of 1:1, propylene is introduced, the mol ratio of the propylene to rhodium is controlled to be 10000:1, and then synthesis gas (CO: H in the synthesis gas) is introduced 2 The molar ratio is 1: 1) To 2.0MPa, and the reaction is carried out for 2 hours at the reaction temperature of 80 ℃. Cooling and decompressing after the reaction is finished, adding an internal standard substance into the obtained liquid phase product, and carrying out gas chromatographic analysis, wherein the result is as follows: propylene conversion was 98% and n-butyraldehyde selectivity was 96%.
The reaction solution is distilled and concentrated to obtain concentrated catalyst solution, the concentrated catalyst solution is added into a hydroformylation reaction kettle, propylene and synthesis gas are introduced to carry out hydroformylation reaction again, the operation is repeated for 10 times, the propylene conversion rate is 98%, the n-butyraldehyde selectivity is 95%, the catalytic effect is kept stable, and the ligand decomposition condition is detected by using HPLC analysis during the period, so that the ligand decomposition amount is 0.2% after 10 times of circulation.
Comparative example 1
Example 1 was repeated except that no phenolic antioxidant was added, the primary reaction effect was the same, the catalytic effect was reduced after 4 times of catalyst recycle reaction, the propylene conversion was reduced to 88%, the n-butyraldehyde selectivity was 70%, and the HPLC analysis and detection showed that the phosphite ligand decomposition amount was 30%.
Example 2
Rhodium dicarbonyl acetylacetonate, phosphite ester ligand (formula 2) and toluene are prepared into raw material liquid, and the raw material liquid is added into a hydroformylation reaction kettle, wherein the concentration of the rhodium dicarbonyl acetylacetonate in the solution is 100ppm, and the molar ratio of the rhodium dicarbonyl acetylacetonate to the phosphite ester ligand (formula 2) is 1:10; t-butylbenzoquinone was added in a molar ratio of t-butylhydroquinone to phosphite ligand of 1:1, introducing n-butene, controlling the molar ratio of the n-butene to rhodium to be 10000:1, and then introducing synthesis gas (CO: H in the synthesis gas) 2 The molar ratio is 1: 3) To 2.0MPa, and the reaction is carried out for 2 hours at the reaction temperature of 80 ℃. Cooling and decompressing after the reaction is finished, adding an internal standard substance into the obtained liquid phase product, and carrying out gas chromatographic analysis, wherein the result is as follows: the conversion rate of the n-butene is 98%, and the selectivity of the n-valeraldehyde is 96%.
The reaction solution is distilled and concentrated to obtain concentrated catalyst solution, the concentrated catalyst solution is added into a hydroformylation reaction kettle, normal butene and synthesis gas are introduced to carry out hydroformylation reaction again, the operation is repeated for 10 times, the conversion rate of the normal butene is 98%, the selectivity of the normal valeraldehyde is 96%, the catalytic effect is kept stable, and the ligand decomposition condition is detected by using HPLC analysis during the period, so that the result shows that the ligand decomposition amount is 0.5% after 10 times of circulation.
Comparative example 2
Example 2 was repeated except that no phenolic antioxidant was added, the primary reaction effect was the same, the catalytic effect was reduced after 6 times of catalyst recycle reaction, the n-butene conversion was reduced to 70%, the n-valeraldehyde selectivity was 66%, and the decomposition amount of phosphite ligand was 45% as shown by HPLC analysis and detection.
Example 3
Preparing raw material liquid of rhodium dicarbonyl acetylacetonate, phosphite ester ligand (formula 3) and diisobutylene, and adding the raw material liquid into a hydroformylation reaction kettle, wherein the concentration of rhodium dicarbonyl acetylacetonate in the solution is 100ppm, and the molar ratio of rhodium dicarbonyl acetylacetonate to the phosphite ester ligand (formula 3) is 1:50; adding2, 6-di-tert-butyl-4-methylphenol was added in a molar ratio of 2, 6-di-tert-butyl-4-methylphenol to phosphite ligand of 1:1, followed by the introduction of synthesis gas (CO: H in the synthesis gas) 2 The molar ratio is 1: 1) To 2.0MPa, the reaction was carried out at a reaction temperature of 110℃for 4h. Cooling and decompressing after the reaction is finished, adding an internal standard substance into the obtained liquid phase product, and carrying out gas chromatographic analysis, wherein the result is as follows: diisobutylene conversion rate is 90%, isononyl aldehyde selectivity is 99%.
The reaction solution is distilled and concentrated to obtain concentrated catalyst solution, the concentrated catalyst solution is added into a hydroformylation reaction kettle, normal butene and synthesis gas are introduced to carry out hydroformylation reaction again, the operation is repeated for 10 times, the diisobutylene conversion rate is 90%, the isononanal selectivity is 99%, the catalytic effect is kept stable, and the ligand decomposition condition is detected by using HPLC analysis during the period, so that the result shows that the ligand decomposition amount is 1% after 10 times of circulation.
Comparative example 3
Example 3 was repeated except that no phenolic antioxidant was added, the primary reaction effect was the same, the catalytic effect was reduced to 60% after 4 times of catalyst recycle reaction, the diisobutylene conversion was reduced to 98% n-valeraldehyde selectivity, and the decomposition amount of phosphite ligand was 33% as shown by HPLC analysis and detection.
Example 4
Example 3 was repeated, except that 2, 6-di-tert-butyl-4-methylphenol was replaced with antioxidant 2246, the molar ratio of antioxidant 2246 to phosphite ligand being 1:0.5, after the primary reaction, the diisobutylene conversion rate is 91%, and the isononanal selectivity is 99%. The catalyst is recycled for 10 times, the diisobutylene conversion rate is 90%, the isononyl aldehyde selectivity is 98%, the catalytic effect is stable, and the HPLC analysis and detection show that the decomposition amount of phosphite ester ligand is 0.5%.
Example 5
Example 3 was repeated, except that 2, 6-di-tert-butyl-4-methylphenol was replaced by 2, 5-di-tert-butylhydroquinone, the molar ratio of 2, 5-di-tert-butylhydroquinone to phosphite ligand being 0.5:1, after the primary reaction, the diisobutylene conversion rate is 88%, and the isononanal selectivity is 99%. The catalyst is recycled for 20 times, the diisobutylene conversion rate is 88%, the isononaldehyde selectivity is 98%, the catalytic effect is stable, and the HPLC analysis and detection show that the decomposition amount of phosphite ester ligand is 0.6%.
Example 6
Example 3 was repeated, except that 2, 6-di-tert-butyl-4-methylphenol was replaced by tert-butyl-4-hydroxyanisole, the molar ratio of tert-butyl-4-hydroxyanisole to phosphite ligand being 1:1, after the primary reaction, the diisobutylene conversion rate is 92%, and the isononanal selectivity is 98%. The catalyst is recycled for 20 times, the diisobutylene conversion rate is 90%, the isononyl aldehyde selectivity is 98%, the catalytic effect is stable, and the HPLC analysis and detection show that the decomposition amount of phosphite ester ligand is 0.6%.
Example 7
Example 1 was repeated, except that the reaction temperature was changed to 70℃and the propylene conversion after the initial reaction was 90% and the n-butyraldehyde selectivity was 96%. The catalyst is recycled for 20 times, the propylene conversion rate is 90%, and the selectivity of the n-butyraldehyde is 96%. The catalytic effect is kept stable, and HPLC analysis and detection show that the decomposition amount of phosphite ligand is 0.1%.
Example 8
Preparing raw material liquid of rhodium dicarbonyl acetylacetonate, phosphite ester ligand (formula 1) and 1-octene, and adding the raw material liquid into a hydroformylation reaction kettle, wherein the concentration of rhodium dicarbonyl acetylacetonate in the solution is 500ppm, and the molar ratio of rhodium dicarbonyl acetylacetonate to phosphite ester ligand (formula 1) is 1:100; t-butylbenzoquinone was added in a molar ratio of t-butylhydroquinone to phosphite ligand of 1:20, followed by the introduction of synthesis gas (CO: H in the synthesis gas) 2 The molar ratio is 1: 1) To 6.0MPa, and the reaction is carried out for 2 hours at the reaction temperature of 120 ℃. Cooling and decompressing after the reaction is finished, adding an internal standard substance into the obtained liquid phase product, and carrying out gas chromatographic analysis, wherein the result is as follows: the conversion rate of 1-octene is 99%, and the selectivity of n-nonanal is 95%.
The reaction solution is distilled and concentrated to obtain concentrated catalyst solution, the concentrated catalyst solution is added into a hydroformylation reaction kettle, 1-octene and synthesis gas are introduced to carry out hydroformylation reaction again, the operation is repeated for 10 times, the 1-octene conversion rate is 99%, the n-nonanal selectivity is 94%, the catalytic effect is kept stable, and the ligand decomposition condition is detected by using HPLC analysis during the period, so that the ligand decomposition amount is 0.3% after 10 times of circulation.
Example 9
Example 3 was repeated, except that rhodium dicarbonyl acetylacetonate was replaced with tris (triphenylphosphine) rhodium hydride, the concentration of the tris (triphenylphosphine) rhodium hydride in the solution was 50ppm, and the molar ratio of the tris (triphenylphosphine) rhodium hydride to the phosphite ligand (formula 3) was 1:100; the pressure of the synthesis gas is 1.0MPa, the conversion rate of diisobutylene is 96% and the selectivity of isononyl aldehyde is 99% after the primary reaction. The catalyst is recycled for 10 times, the diisobutylene conversion rate is 95%, the isononaldehyde selectivity is 99%, the catalytic effect is stable, and the HPLC analysis and detection show that the decomposition amount of phosphite ester ligand is 0.3%.
Comparative example 4
Example 3 was repeated, except that 2, 6-di-tert-butyl-4-methylphenol was replaced with dilauryl thiodipropionate, a sulfur-containing antioxidant, in a molar ratio of dilauryl thiodipropionate to phosphite ligand of 1:1, after the primary reaction, the diisobutylene conversion rate is 20 percent and the isononanal selectivity is 51 percent.
Comparative example 5
Example 3 was repeated, except that 2, 6-di-tert-butyl-4-methylphenol was replaced by ascorbic acid, the molar ratio of ascorbic acid to phosphite ligand being 1:1, after the primary reaction, the diisobutylene conversion rate is 60%, and the isononanal selectivity is 85%.
Comparative example 6
Example 3 was repeated, except that 2, 6-di-tert-butyl-4-methylphenol was replaced with ethylenediamine tetraacetic acid (EDTA), the molar ratio of EDTA to phosphite ligand being 1:1, after the primary reaction, the diisobutylene conversion rate is 32%, and the isononanal selectivity is 15%.
The above examples are provided to illustrate the disclosed embodiments of the invention and are not to be construed as limiting the invention. In addition, many modifications and variations of the methods and compositions of the invention set forth herein will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the invention. While the invention has been specifically described in connection with various specific preferred embodiments thereof, it should be understood that the invention should not be unduly limited to such specific embodiments. Indeed, various modifications of the described modes for carrying out the invention which are obvious to those skilled in the art are intended to be within the scope of the present invention.
Claims (10)
1. A method for preparing aldehyde by hydroformylation of olefin is characterized in that the hydroformylation of olefin and synthesis gas takes place under the action of rhodium catalyst, phosphite ligand and phenolic antioxidant; the phosphite ester ligand is selected from at least one of the following compounds represented by the general structural formula I or the general formula II:
；
；
y is a C6-C28 substituted or unsubstituted organic divalent bridging arylene group; R1-R8 are hydrogen or each independently substituted or unsubstituted C1-C8 alkyl or alkoxy; R9-R23 are hydrogen or each independently substituted or unsubstituted C1-C8 alkyl, C1-C8 alkoxy or halogen;
the phenolic antioxidant is at least one selected from 2, 6-di-tert-butyl-4-methylphenol, 2' -methylenebis (4-methyl-6-tert-butylphenol), tert-butylhydroquinone, 2, 5-di-tert-butylhydroquinone and tert-butyl-4-hydroxyanisole.
2. The process for the preparation of aldehydes by hydroformylation of olefins according to claim 1, further comprising: and (3) removing evaporation components from a reaction product obtained by the hydroformylation reaction through evaporation separation, and circularly carrying out the hydroformylation reaction on the residual materials.
3. The process for preparing aldehydes by hydroformylation of olefins according to claim 1, further comprising at least one of the following technical features:
a1 The rhodium catalyst is a metal rhodium compound;
a2 A molar ratio of the rhodium catalyst to the phosphite ligand of 1: (10-100);
a3 A molar ratio of the phenolic antioxidant to the phosphite ligand of 1: (0.5-20);
a4 Rhodium concentration of 50-500 ppm;
a5 The olefin is a single olefin or a mixed olefin of C2-C12; and/or the molar ratio of olefin to rhodium is 5000: 1-15000: 1, a step of;
a6 CO) in the synthesis gas: h 2 The molar ratio is 1: (1-3);
a7 The temperature of the hydroformylation reaction is 70-120 ℃;
a8 The pressure of the hydroformylation reaction is 1.0-6.0 Mpa.
4. The process for preparing aldehydes by hydroformylation of olefins according to claim 3, further comprising the technical features of:
a11 In feature a 1), the rhodium catalyst is selected from at least one of rhodium trichloride, rhodium acetate, carbonylbis (triphenylphosphine) rhodium chloride, rhodium dicarbonyl acetylacetonate, rhodium 1, 5-cyclooctadiene (acetylacetonate), rhodium (acetylacetonate) carbonyl (triphenylphosphine), rhodium carbonyl hydride, rhodium tris (triphenylphosphine) carbonyl chloride, rhodium bis (triphenylphosphine) carbonyl chloride, rhodium tris (triphenylphosphine) chloride, and rhodium tetrakis (triphenylphosphine) hydride.
5. Use of a phenolic antioxidant for improving the stability of a catalytic system comprising a rhodium catalyst and a phosphite ligand in the preparation of an aldehyde by hydroformylation of an olefin; the phosphite ester ligand is selected from at least one of the following compounds represented by the general structural formula I or the general formula II:
；
；
y is a C6-C28 substituted or unsubstituted organic divalent bridging arylene group; R1-R8 are hydrogen or each independently substituted or unsubstituted C1-C8 alkyl or alkoxy; R9-R23 are hydrogen or each independently substituted or unsubstituted C1-C8 alkyl, C1-C8 alkoxy or halogen;
the phenolic antioxidant is at least one selected from 2, 6-di-tert-butyl-4-methylphenol, 2' -methylenebis (4-methyl-6-tert-butylphenol), tert-butylhydroquinone, 2, 5-di-tert-butylhydroquinone and tert-butyl-4-hydroxyanisole.
6. The use of a phenolic antioxidant according to claim 5, further comprising at least one of the following technical features:
b1 The rhodium catalyst is a metal rhodium compound;
b2 A molar ratio of the rhodium catalyst to the phosphite ligand of 1: (10-100);
b3 A molar ratio of the phenolic antioxidant to the phosphite ligand of 1: (0.5-20);
b4 Rhodium concentration of 50-500 ppm;
b5 The olefin is a single olefin or a mixed olefin of C2-C12; and/or the molar ratio of olefin to rhodium is 5000: 1-15000: 1, a step of;
b6 Olefin hydroformylation of olefins with synthesis gas in which CO: h 2 The molar ratio is 1: (1-3);
b7 The temperature of the hydroformylation reaction is 70-120 ℃;
b8 The pressure of the hydroformylation reaction is 1.0-6.0 Mpa.
7. The use of a phenolic antioxidant according to claim 6, further comprising the technical features of:
b11 In feature b 1), the rhodium catalyst is selected from at least one of rhodium trichloride, rhodium acetate, carbonylbis (triphenylphosphine) rhodium chloride, rhodium dicarbonyl acetylacetonate, rhodium 1, 5-cyclooctadiene (acetylacetonate), rhodium (acetylacetonate) carbonyl (triphenylphosphine), rhodium carbonyl hydride, rhodium tris (triphenylphosphine) carbonyl chloride, rhodium bis (triphenylphosphine) carbonyl chloride, rhodium tris (triphenylphosphine) chloride, and rhodium tetrakis (triphenylphosphine) hydride.
8. A method for improving stability of a catalytic system in preparing aldehyde by olefin hydroformylation reaction is characterized in that a phenolic antioxidant is added into the catalytic system, and the catalytic system comprises a rhodium catalyst and a phosphite ligand; the phosphite ester ligand is selected from at least one of the following compounds represented by the general structural formula I or the general formula II:
；
；
y is a C6-C28 substituted or unsubstituted organic divalent bridging arylene group; R1-R8 are hydrogen or each independently substituted or unsubstituted C1-C8 alkyl or alkoxy; R9-R23 are hydrogen or each independently substituted or unsubstituted C1-C8 alkyl, C1-C8 alkoxy or halogen;
the phenolic antioxidant is at least one selected from 2, 6-di-tert-butyl-4-methylphenol, 2' -methylenebis (4-methyl-6-tert-butylphenol), tert-butylhydroquinone, 2, 5-di-tert-butylhydroquinone and tert-butyl-4-hydroxyanisole.
9. The method for improving the stability of a catalytic system in the preparation of aldehydes by hydroformylation of olefins according to claim 8, further comprising at least one of the following technical features:
c1 The rhodium catalyst is a metal rhodium compound;
c2 A molar ratio of the rhodium catalyst to the phosphite ligand of 1: (10-100);
c3 A molar ratio of the phenolic antioxidant to the phosphite ligand of 1: (0.5-20);
c4 Rhodium concentration of 50-500 ppm;
c5 The olefin is a single olefin or a mixed olefin of C2-C12; and/or the molar ratio of olefin to rhodium is 5000: 1-15000: 1, a step of;
c6 Olefin hydroformylation of olefins with synthesis gas in which CO: h 2 The molar ratio is 1: (1-3);
c7 The temperature of the hydroformylation reaction is 70-120 ℃;
c8 The pressure of the hydroformylation reaction is 1.0-6.0 Mpa.
10. The method for improving the stability of a catalytic system in the preparation of aldehydes by hydroformylation of olefins according to claim 9, further comprising the technical features of:
c11 In feature c 1), the rhodium catalyst is selected from at least one of rhodium trichloride, rhodium acetate, carbonylbis (triphenylphosphine) rhodium chloride, rhodium dicarbonyl acetylacetonate, rhodium 1, 5-cyclooctadiene (acetylacetonate), rhodium (acetylacetonate) carbonyl (triphenylphosphine), rhodium carbonyl hydride, rhodium tris (triphenylphosphine) carbonyl chloride, rhodium bis (triphenylphosphine) carbonyl chloride, rhodium tris (triphenylphosphine) chloride, and rhodium tetrakis (triphenylphosphine) hydride.
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