CN110862307A - Method for preparing aldehyde by mixed carbon-four hydroformylation reaction - Google Patents
Method for preparing aldehyde by mixed carbon-four hydroformylation reaction Download PDFInfo
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- CN110862307A CN110862307A CN201810981610.2A CN201810981610A CN110862307A CN 110862307 A CN110862307 A CN 110862307A CN 201810981610 A CN201810981610 A CN 201810981610A CN 110862307 A CN110862307 A CN 110862307A
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- 238000007037 hydroformylation reaction Methods 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims abstract description 22
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 title 1
- 238000006243 chemical reaction Methods 0.000 claims abstract description 92
- 239000003054 catalyst Substances 0.000 claims abstract description 87
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims abstract description 85
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims abstract description 74
- BYGQBDHUGHBGMD-UHFFFAOYSA-N 2-methylbutanal Chemical compound CCC(C)C=O BYGQBDHUGHBGMD-UHFFFAOYSA-N 0.000 claims abstract description 68
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N pentanal Chemical compound CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 claims abstract description 51
- YGHRJJRRZDOVPD-UHFFFAOYSA-N 3-methylbutanal Chemical compound CC(C)CC=O YGHRJJRRZDOVPD-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000001893 (2R)-2-methylbutanal Substances 0.000 claims abstract description 34
- 150000001299 aldehydes Chemical class 0.000 claims abstract description 23
- IAQRGUVFOMOMEM-UHFFFAOYSA-N but-2-ene Chemical compound CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 17
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 16
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 13
- XNMQEEKYCVKGBD-UHFFFAOYSA-N dimethylacetylene Natural products CC#CC XNMQEEKYCVKGBD-UHFFFAOYSA-N 0.000 claims abstract description 11
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 239000003446 ligand Substances 0.000 claims description 32
- 150000003284 rhodium compounds Chemical class 0.000 claims description 29
- WJIBZZVTNMAURL-UHFFFAOYSA-N phosphane;rhodium Chemical group P.[Rh] WJIBZZVTNMAURL-UHFFFAOYSA-N 0.000 claims description 21
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 13
- -1 hydrocarbyl phosphine Chemical compound 0.000 claims description 13
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 7
- 229910019142 PO4 Inorganic materials 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 5
- 239000010452 phosphate Substances 0.000 claims description 5
- UOEHQMCXBPRFEY-UHFFFAOYSA-N O=[Rh](=O)=O Chemical compound O=[Rh](=O)=O UOEHQMCXBPRFEY-UHFFFAOYSA-N 0.000 claims description 2
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- ZJIPHXXDPROMEF-UHFFFAOYSA-N dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O ZJIPHXXDPROMEF-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- VXNYVYJABGOSBX-UHFFFAOYSA-N rhodium(3+);trinitrate Chemical compound [Rh+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VXNYVYJABGOSBX-UHFFFAOYSA-N 0.000 claims description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims description 2
- 239000000047 product Substances 0.000 abstract description 32
- 238000000926 separation method Methods 0.000 abstract description 28
- 239000007789 gas Substances 0.000 description 32
- 229910052799 carbon Inorganic materials 0.000 description 26
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 25
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 18
- 239000001273 butane Substances 0.000 description 16
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 16
- 239000007791 liquid phase Substances 0.000 description 12
- 239000010409 thin film Substances 0.000 description 12
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 12
- 238000009835 boiling Methods 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 238000001704 evaporation Methods 0.000 description 7
- 230000008020 evaporation Effects 0.000 description 7
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical group CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 6
- 150000001336 alkenes Chemical class 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- 229910052703 rhodium Inorganic materials 0.000 description 6
- 239000010948 rhodium Substances 0.000 description 6
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 4
- 239000012847 fine chemical Substances 0.000 description 4
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000011065 in-situ storage Methods 0.000 description 3
- XRBCRPZXSCBRTK-UHFFFAOYSA-N phosphonous acid Chemical compound OPO XRBCRPZXSCBRTK-UHFFFAOYSA-N 0.000 description 3
- IAQRGUVFOMOMEM-ONEGZZNKSA-N trans-but-2-ene Chemical compound C\C=C\C IAQRGUVFOMOMEM-ONEGZZNKSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 2
- 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 description 2
- IAQRGUVFOMOMEM-ARJAWSKDSA-N cis-but-2-ene Chemical compound C\C=C/C IAQRGUVFOMOMEM-ARJAWSKDSA-N 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 239000001282 iso-butane Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- 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 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000012808 vapor phase Substances 0.000 description 2
- LABRPRANVKSMGP-UHFFFAOYSA-N 1,3,2-dioxaphosphinane Chemical compound C1COPOC1 LABRPRANVKSMGP-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- NHOINWXDKMSOOA-UHFFFAOYSA-N [Rh+3].[Rh+3].[O-]P[O-].[O-]P[O-].[O-]P[O-] Chemical group [Rh+3].[Rh+3].[O-]P[O-].[O-]P[O-].[O-]P[O-] NHOINWXDKMSOOA-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- CPRFTFJQMGHRRM-UHFFFAOYSA-N carbon monoxide;pentane-2,4-dione;rhodium Chemical compound [Rh].[O+]#[C-].[O+]#[C-].CC(=O)CC(C)=O CPRFTFJQMGHRRM-UHFFFAOYSA-N 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000007792 gaseous phase Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 150000008301 phosphite esters Chemical class 0.000 description 1
- 239000008029 phthalate plasticizer Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
Images
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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
A method of preparing an aldehyde by a mixed carbo-tetrahydroformylation reaction, comprising: step S1, enabling the mixed C4 and the synthesis gas to contact in a first reaction area in the presence of a first catalyst to carry out hydroformylation reaction to obtain a first reaction product containing n-valeraldehyde and 2-methylbutyraldehyde; step S2, separating the first reaction product to obtain a mixture of n-valeraldehyde and 2-methylbutyraldehyde, unreacted raw materials and a material flow containing a first catalyst; step S3, in the presence of a second catalyst, enabling the unreacted raw materials and the synthesis gas to contact in a second reaction zone for hydroformylation reaction to obtain a second reaction product containing 3-methylbutyraldehyde, and optionally, purifying the second reaction product; the mixed C4 is a mixture containing 1-butene and isobutene obtained by removing 2-butene and 1, 3-butadiene. According to the invention, 1-butene and isobutene are respectively subjected to hydroformylation reaction in a sectional reaction mode to obtain different products, so that the advanced separation of 1-butene and isobutene is avoided.
Description
Technical Field
The invention relates to a method for preparing aldehyde by mixed carbon four hydroformylation.
Background
The hydroformylation of olefins with synthesis gas over a catalyst to produce aldehydes having one more carbon atom than the olefin is a well known process.
The hydroformylation reaction of olefins without isomers, such as ethylene and propylene, is relatively simple, and for olefins with more than four carbon atoms, because different isomers exist, the hydroformylation reaction conditions of various isomers are different, the structures of aldehyde products are also different, and the separation of the hydroformylation product aldehyde of some isomers is difficult, so that for olefins with more than four carbon atoms, the mixed olefins with more than four carbon atoms are not suitable for being simultaneously reacted in the same reaction zone, and need to be separated before the reaction.
Taking mixed C.sub.four as an example, possible compositions are 1-butene, trans-2-butene, cis-2-butene, isobutene, 1, 3-butadiene and butane. At present, the industrial separation of 1, 3-butadiene from four carbon components is well established, and for isobutene, a method for converting isobutene into methyl tert-butyl ether is adopted to realize the separation of isobutene from mixed four carbon components. The product of the mixed C.sub.D with isobutylene removed is generally referred to as C.sub.D.sub.etherate. However, in recent years, due to the safety problem of methyl t-butyl ether, some developed countries have legislation that prohibits the addition of methyl t-butyl ether to gasoline, rendering isobutylene a less important use, and the manner in which isobutylene is converted to methyl t-butyl ether has been limited. In this context, the composition of mixed C.sub.four would be 1-butene, trans-2-butene, cis-2-butene, isobutene and butane.
The boiling points of the components in the mixed carbon four can be seen in the following table:
as can be seen from the boiling points of the components in the mixed C4, the 2-butene has large difference with other components, and the 2-butene can be separated from the mixed C4 by the conventional rectification method, however, the boiling points of the isobutene and the 1-butene are very close, and the isobutene and the 1-butene are difficult to separate by the conventional method. Therefore, how to realize the effective utilization of the C4 resource and obtain the C4 reaction product with high purity is a technical problem to be solved by those skilled in the art.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a method for preparing aldehyde by mixed carbon four hydroformylation, which realizes the generation of different high-purity aldehyde products in two reaction zones by using a mode of carrying out reaction on raw materials in a subarea manner.
The invention is realized by the following technical scheme: a method of preparing an aldehyde by a mixed carbo-tetrahydroformylation reaction, comprising:
step S1, enabling the mixed C4 and the synthesis gas to contact in a first reaction area in the presence of a first catalyst to carry out hydroformylation reaction to obtain a first reaction product containing n-valeraldehyde and 2-methylbutyraldehyde;
step S2, separating the first reaction product to obtain a mixture of n-valeraldehyde and 2-methylbutyraldehyde, unreacted raw materials and a material flow containing a first catalyst;
step S3, in the presence of a second catalyst, enabling the unreacted raw materials and the synthesis gas to contact in a second reaction zone for hydroformylation reaction to obtain a second reaction product containing 3-methylbutyraldehyde, and optionally, purifying the second reaction product;
the mixed C4 is a mixture containing 1-butene and isobutene obtained by removing 2-butene and 1, 3-butadiene.
The synthesis gas is a mixed gas of hydrogen and carbon monoxide, preferably, the molar ratio of hydrogen to carbon monoxide is 1: 10-10: 1, preferably 1: 2-10: 1.
According to a preferred embodiment of the present invention, the first catalyst is a rhodium-phosphine complex catalyst generated from a rhodium compound and a hydrocarbyl phosphine-based ligand; the second catalyst is one or more selected from the group consisting of a rhodium-phosphine complex catalyst formed from a rhodium compound and a hydrocarbyl phosphine ligand, a rhodium-phosphine complex catalyst formed from a rhodium compound and a phosphite ligand, and a rhodium-phosphine complex catalyst formed from a rhodium compound and a phosphate ligand.
According to a preferred embodiment of the present invention, the first catalyst and/or the second catalyst are present in the form of a solution, and the solvent for dissolving the first catalyst and the second catalyst may be selected from one or more of alkanes having 1 to 30 carbon atoms, aromatic hydrocarbons, alcohols, ketones, ethers, esters, sulfoxides, and phenols.
According to a preferred embodiment of the present invention, the first catalyst is a rhodium-phosphine complex catalyst formed from a rhodium compound and a hydrocarbyl phosphine-based ligand, and the second catalyst is a rhodium-phosphine complex catalyst formed from a rhodium compound and a hydrocarbyl phosphine-based ligand; the conditions of the first reaction zone include: at a temperature of 60-120 ℃, preferably 88-100 ℃, and/or at a pressure of 0.5-2MPa, preferably 0.8-2.0 MPa; the conditions of the second reaction zone include: the temperature is 60-120 deg.C, preferably 90-110 deg.C, and/or the pressure is 0.5-4MPa, preferably 2.0-4.0 MPa.
According to a preferred embodiment of the present invention, the first catalyst is a rhodium-phosphine complex catalyst generated from a rhodium compound and a hydrocarbyl phosphine-based ligand; the second catalyst is selected from a rhodium-phosphine complex catalyst generated by a rhodium compound and a phosphite ligand, and/or a rhodium-phosphine complex catalyst generated by a rhodium compound and a phosphate ligand; the conditions of the first reaction zone include: at a temperature of 60-120 ℃, preferably 88-100 ℃, and/or at a pressure of 0.5-2MPa, preferably 0.8-2.0 MPa; the conditions of the second reaction zone include: at a temperature of 60-120 ℃, preferably 70-100 ℃, and/or at a pressure of 0.5-4Mpa, preferably 0.8-2.0 Mpa.
According to a preferred embodiment of the invention, the rhodium compound is selected from one or more of rhodium acetylacetonate dicarbonyl, rhodium trioxide, dodecacarbonyltetrarhodium, hexadecahonylhexarhodium, rhodium nitrate and rhodium acetate.
According to the bookIn a preferred embodiment of the present invention, the hydrocarbyl phosphine ligand has the structure
Wherein R is1、R2And R3Each independently selected from the group consisting of H, alkyl, aryl, aralkyl, and alkaryl.
According to a preferred embodiment of the invention, the phosphite ligand is selected from one or more of the group consisting of monophosphites, diphosphites and triphosphites.
According to a preferred embodiment of the invention, the 2-butene content of the mixed C4 is below 1 wt%, preferably below 0.1 wt%.
According to a preferred embodiment of the present invention, the content of isobutylene in the mixed C4 is 10 wt% or more.
According to a preferred embodiment of the invention, the unreacted starting material is essentially isobutene, which also contains small amounts of unreacted 1-butene, and the inert component butane. The unreacted feed has a 1-butene content of less than 1.5 wt%, preferably less than 1.0 wt%, and a 2-methylbutanal content of less than 500ppm, preferably less than 200 ppm.
According to a preferred embodiment of the invention, said stream comprising the first catalyst is recycled to the first reaction zone. The first catalyst-containing stream includes a first catalyst and a solvent that dissolves the first catalyst.
According to a preferred embodiment of the present invention, the second reaction product is separated to obtain unreacted carbon four (inert components methane and a small amount of isobutylene), a stream containing the second catalyst, and 3-methylbutyraldehyde, the stream containing the second catalyst is recycled to the second reaction zone, and 3-methylbutyraldehyde is withdrawn as a product of the second reaction zone. The second catalyst containing stream includes the second catalyst and a solvent that dissolves the first catalyst.
The inventors have found that, when a rhodium-phosphine complex catalyst is used which is formed from a rhodium compound and a hydrocarbyl phosphine ligand, under the same conditions, the reaction rate of 1-butene is high, and the hydroformylation reaction can be carried out under a low partial pressure of carbon monoxide and hydrogen, but the reaction is hardly carried out under the conditions for 2-butene and isobutene. The rhodium-phosphine complex catalyst generated by the rhodium compound and the phosphite ligand and/or the rhodium-phosphine complex catalyst generated by the rhodium compound and the phosphate ligand, whether 1-butene, 2-butene or isobutene, can obtain higher hydroformylation reaction speed under lower partial pressure of carbon monoxide and hydrogen. The hydroformylation products of 1-butene and 2-butene are n-valeraldehyde and 2-methylbutyraldehyde, and the specific structure of isobutylene is such that the hydroformylation product is almost 100% of 3-methylbutyraldehyde. However, the inventors have found that both 2-methylbutyraldehyde and the hydroformylation product of isobutylene, 3-methylbutyraldehyde, are close in boiling point and are difficult to separate by conventional rectification means. Further, since the reaction rates of 2-butene and isobutylene are relatively close to each other under the same conditions, in order to maintain the purity of 3-methylbutyraldehyde which is an isobutylene product at a high level, in the present invention, 2-butene is separated from mixed C.sub.C.sub.C.sub.C.to obtain mixed C.sub.C.sub.C.sub.C.sub.C.sub.C.sub.C.sub.C.sub.C.sub.C.sub.C.sub.C.sub.C.sub.C.sub.C.sub.C.sub.C.sub.C.. In the invention, 1-butene and isobutene react in different reaction zones by reacting in two stages under different reaction conditions and/or different catalysts, so that high-purity products are respectively obtained. Since the reaction speed of 1-butene is relatively fast, 1-butene can also react at a relatively fast speed to generate a small amount of 2-methylbutyraldehyde under the reaction conditions of isobutene, so in order to avoid the influence of 2-methylbutyraldehyde on isobutene products, in the invention, the reaction conditions are controlled to achieve a relatively high conversion rate of 1-butene in the first reaction zone, preferably the conversion rate of 1-butene in the first reaction zone is more than 97%, preferably more than 98.3%. And, the first reaction product is separated, i.e., unreacted starting material is separated from the product aldehyde, prior to hydroformylation of the isobutylene in the second reaction zone. Thereby controlling the higher purity of the 3-methyl butyraldehyde.
According to a preferred embodiment of the present invention, the separation of the first reaction product and the second reaction product can be carried out in a separation manner customary to the person skilled in the art, for example in a flash and/or rectification manner.
According to a preferred embodiment of the present invention, the reaction apparatus of the first reaction zone and the reaction apparatus of the second reaction zone are each independently a single reactor or a plurality of reactors connected in series, wherein the plurality of reactors connected in series are the same or different, and the reactors are tank reactors or tower reactors.
The method for producing different aldehyde products by two reaction zones is realized by utilizing different hydroformylation reaction characteristics of 1-butene and isobutene and adopting a mode of reacting the 1-butene and the isobutene in a partition manner; by means of an intermediate separation between the two reaction zones, a process is achieved for producing different aldehydes of high purity from the two reaction zones.
According to the invention, 1-butene and isobutene are respectively subjected to hydroformylation reaction in a sectional reaction mode to obtain different products, so that the advanced separation of 1-butene and isobutene is avoided.
Drawings
FIG. 1 is a schematic flow diagram of the present invention.
FIG. 2 is a schematic flow diagram of a first reaction zone in example 1 of the present invention.
FIG. 3 is a schematic flow diagram of a second reaction zone of example 1 of the present invention.
Detailed Description
The present invention will be described in detail with reference to examples, but the present invention is not limited to the examples.
The work flow diagram of the plant for the preparation of aldehydes by mixed C-C hydroformylation according to the invention is shown in block diagram form in FIG. 1, in which, for the sake of clarity, FIG. 1 omits the conventional elements required in the industrial plant, such as valves, pumps, heat exchangers, etc., and these conventional elements can be implemented in accordance with the prior art.
As shown in fig. 1: the mixed C-four stream 1, the synthesis gas 2 and the first catalyst solution stream 5 from the intermediate separation zone 102 enter a first reaction zone 101, and 1-butene in the first reaction zone 101 is subjected to hydroformylation reaction under the action of a first catalyst to generate n-valeraldehyde and 2-methylbutyraldehyde. The gas phase stream 4 produced from the first reaction zone 101 is removed from the first reaction zone 101 as off-gas or passed to other units for further processing. The liquid phase product 3 of the first reaction zone enters an intermediate separation zone 102, unreacted raw materials (including isobutene and butane) and product valeraldehyde (n-valeraldehyde and 2-methylbutyraldehyde) are separated from the first catalyst solution 5 in the intermediate separation zone 102, the unreacted raw materials (isobutene and butane) and the product valeraldehyde (n-valeraldehyde and 2-methylbutyraldehyde) are sent to a separation section 103 of the intermediate separation zone, and the first catalyst solution 5 returns to the first reaction zone. In the separation section 103 of the intermediate separation zone, the four carbon streams 8 (isobutylene and butane) are separated from the valeraldehyde 7 (n-valeraldehyde and 2-methylbutyraldehyde), and the four carbon streams 8 (isobutylene and butane) enter the second reaction zone 201 to react with the synthesis gas 9 and the catalyst solution 12 from the post-separation zone 202 in the second reaction zone 201. The gas phase stream 11 obtained from the second reaction zone 201 is discharged as off-gas or sent to other units for further processing. The liquid phase material flow 10 obtained from the second reaction area 201 enters the post-separation area 202, a small amount of unreacted isobutene, butane and product valeraldehyde are separated from the second catalyst solution 12 in the post-separation area 202, a small amount of unreacted isobutene, butane and product valeraldehyde are sent to the separation section 203 of the post-separation area, the second catalyst solution 12 returns to the second reaction area 201, in the separation section 203 of the post-separation area, the carbon four material flow 14 (a small amount of isobutene and butane) is separated from the 3-methyl butyraldehyde 15, the carbon four material flow 14 (a small amount of isobutene and butane) is taken as a byproduct, and the 3-methyl butyraldehyde 15 can be further refined to obtain the high-purity 3-methyl butyraldehyde if necessary.
The 1-butene content and the 2-methylbutanal content of the carbon four stream 8 (isobutylene and butane) entering the second reaction zone 201 are controlled. As noted above, due to the difficulty in separating the 2-methylbutyraldehyde from the 3-methylbutyraldehyde, the 1-butene content of the carbon four stream 8 entering the second reaction zone should be controlled to be less than 1.5 wt%, preferably less than 1.0 wt%, and the 2-methylbutyraldehyde content should be controlled to be less than 500ppm, preferably less than 200 ppm.
The first reaction zone 101 and the second reaction zone 201 may be a single tank reactor or a tower reactor, or may be a combination of a plurality of different or identical reactors connected together.
Example 1
The reaction of example 1 was carried out in an apparatus as shown in FIGS. 2 and 3:
the first reaction zone consists of two serially connected stirred tanks, and the intermediate separating zone consists of one film evaporator and one packed tower. The first catalyst used in the first reaction zone is a rhodium-triphenylphosphine complex catalyst generated in situ by a rhodium compound and triphenylphosphine, the rhodium compound is rhodium dicarbonyl acetylacetonate, and a solvent for dissolving the first catalyst is butyraldehyde.
Mixed butenes (having a composition of 36.2 wt% 1-butene, 0.1 wt% trans-2-butene, 55.2 wt% isobutene, 8.0 wt% isobutane and 0.5 wt% n-butane) from a storage tank (not shown in FIG. 2) are fed into the line 302 through the line 301 by means of the pump 503 at a flow rate of 200g/hr, mixed with the bottom discharge 323 from the thin film evaporator 507 and fed into the bottom of the reactor 501 through the bottom-inserted tube via the line 303, and simultaneously, synthesis gas (hydrogen: CO molar ratio of 1.05:1, flow rate of 47.4 normal liters/hr) is fed into the liquid phase of the reactor 501 through the gas distributor at the bottom of the reactor 501 via the line 304. Both the reactor 501 and the reactor 502 were 2L pressure-resistant stainless steel stirred tanks. The gas phase outlet of the reactor 501 was equipped with a back pressure valve (not shown in FIG. 2) to control the pressure inside the reactor to 1.5MPa, and the temperature of the reactor 501 was controlled to 90 ℃ by means of an oil bath (not shown in FIG. 2). The concentration of the first catalyst in the first catalyst solution in reactor 501 is about 200ppm, calculated as rhodium metal, and the solution also contains 12% by mass of triphenylphosphine ligand. The synthesis gas reacts with 1-butene in the presence of a first catalyst in reactor 501, the gaseous phase output from reactor 501 is fed via line 306 into the liquid phase of reactor 502 along with synthesis gas from 312 (hydrogen: CO molar ratio 1.05:1, flow 9.3 normal liters/hr) via the bottom gas distributor of reactor 502; the liquid phase output from reactor 501 is fed via pump 504 via line 307 to reactor 502.
The temperature of the reactor 502 was controlled at 95 ℃ by means of an oil bath (not shown in FIG. 2), and a back pressure valve (not shown in FIG. 2) was provided at the gas phase outlet of the reactor 502 to control the pressure inside the reactor at 1.4 MPa. The catalyst in reactor 502 is the same as in reactor 501, the concentration of the first catalyst in the first catalyst solution in reactor 502 is about 200ppm as metallic rhodium, and the solution also contains about 12% by mass of triphenylphosphine ligand.
The gaseous output from reactor 502 is passed through condenser 505 wherein a small amount of aldehyde is condensed and the remaining gas is discharged as tail gas via line 308. The liquid phase output from the reactor 502 is depressurized by a line 309 via a pressure-reducing valve 506 and fed via a line 310 into a thin-film evaporator 507 where a preliminary separation takes place, the carbon four components (isobutene, butane and small amounts of 1-butene) and the product aldehydes (n-valeraldehyde, 2-methylbutyraldehyde) are fed in gaseous form from the top of the thin-film evaporator 507 via a line 313 into a condenser 509 for condensation, and the first catalyst solution is returned from the bottom of the thin-film evaporator 507 via a pump 508 via a line 323 into the reactor 501. The pressure of the thin film evaporator 507 is normal pressure, the evaporation temperature is controlled by an oil bath, the general temperature range is 105-115 ℃, the evaporation temperature is lower than 105 ℃ due to the lower content of high boiling substances in the solution in the initial reaction period, and the evaporation temperature range is generally 110-115 ℃ when the content of the high boiling substances is stable after the operation for a period of time.
After the carbon four components (isobutene, butane and a small amount of 1-butene) and the product aldehydes (n-valeraldehyde, 2-methylbutyraldehyde) are condensed in the condenser 509, a small amount of non-condensable gas is discharged as tail gas from the pipeline 314, the carbon four components and valeraldehyde are fed into the rectifying tower 511 from the pipeline 315 by the pump 510 in liquid phase, and the feeding position is about the fifth theoretical plate in the middle of the rectifying tower 511. The rectifying tower 511 is a packed tower with 8-10 theoretical plates, the pressure at the top of the tower is 0.3MPa, and the temperature at the bottom of the tower is about 150 ℃. After separation in the rectifying tower 511, the product aldehydes (n-valeraldehyde, 2-methylbutyraldehyde) are extracted from the bottom of the rectifying tower 511 by a pump 512 through a pipeline 319 and sent into a storage tank 513. The ratio of n-valeraldehyde to 2-methylbutyraldehyde in the product aldehyde is about 10:1, the mixed aldehyde can be further separated to obtain highly purified n-valeraldehyde and 2-methylbutyraldehyde, and the highly purified n-valeraldehyde and 2-methylbutyraldehyde can be sold as fine chemicals and can also be used for preparing C10 alcohol, and the alcohol can be used for preparing a phthalate plasticizer. Carbon four is directly fed into the second reaction zone from the top of the rectification column through a pipeline 322 by a pump 515 through a pipeline 324 to continue the reaction, or the carbon four can be fed into a storage tank firstly and protected by nitrogen and then fed into the second reaction zone to carry out the reaction. The content of 1-butene in the carbon four composition entering the second reaction zone is 0.9wt percent, and the content of 2-methyl butyraldehyde is less than 200 ppm.
The second reaction zone consists of two serially connected stirred tanks, and the post-separating zone consists of one film evaporator and one packed tower. The second catalyst used in the second reaction zone is a rhodium-triphenylphosphine catalyst generated by a rhodium compound and triphenylphosphine in situ, the rhodium compound is acetylacetonatodicarbonylrhodium, and a solvent used for dissolving the second catalyst is butyraldehyde.
The carbon four components (composition: 1-butene 0.9 wt%, isobutene 85.4 wt%, isobutane 12.5 wt%, n-butane 1.2 wt%) from line 324 were mixed via line 401 at a flow rate of 130g/hr with the bottom discharge 404 from the thin film evaporator 606 and fed together via line 402 via a dip tube to the bottom of the reactor 601, while the synthesis gas (hydrogen to CO molar ratio 1.05:1, flow rate 56.5 normal liter/hr) was fed from line 403 via a gas distributor at the bottom of the reactor 601 into the liquid phase of the reactor 601. Both the reactor 601 and the reactor 602 were 2L pressure-resistant stainless steel stirred tanks, and a back pressure valve (not shown in FIG. 3) was installed at the gas phase outlet of the reactor 601 to control the pressure inside the reactor 601 to 3.3MPa, and the temperature of the reactor 601 was controlled to 100 ℃ by an oil bath (not shown in FIG. 3). The concentration of the second catalyst in the second catalyst solution in reactor 601 is about 400ppm as metallic rhodium, and the solution also contains about 5% by mass of triphenylphosphine ligand. The synthesis gas reacts with isobutene in the presence of a second catalyst in reactor 601, the gaseous output from reactor 601 being fed via line 406 together with the synthesis gas from 412 (hydrogen: CO molar ratio 1.05:1, flow 17.4 normal liters/hr) via the bottom gas distributor of the second reactor 602 into the liquid phase of the reactor 602; the liquid phase output from reactor 601 is fed via pump 604 via line 607 to second reactor 602.
The temperature of the reactor 602 was controlled at 105 ℃ by means of an oil bath (not shown in FIG. 3), and a back pressure valve (not shown in FIG. 3) was provided at the gas phase outlet of the reactor 602 to control the pressure inside the reactor at 3.2 MPa. The concentration of the second catalyst in the second catalyst solution in reactor 602 is about 400ppm as rhodium metal and the solution also contains about 5% by mass of triphenylphosphine ligand.
The gaseous output from the reactor 602 is passed through a condenser 603 in which a small amount of aldehyde is condensed and the remaining gas is discharged as off-gas via line 408. The liquid phase output from reactor 602 is reduced in pressure by line 409 via pressure reducing valve 605 and fed via line 410 to thin film evaporator 606 where it is initially separated, the carbon four components (butane and minor amounts of unreacted isobutylene) and the product aldehyde (3-methylbutyraldehyde) are fed in vapor phase from the top of thin film evaporator 606 via line 413 to condenser 608 where they are condensed and the second catalyst solution is returned from the bottom of thin film evaporator 606 via pump 607 to reactor 601 via line 404. The pressure of the thin film evaporator 606 is normal pressure, the evaporation temperature is controlled by oil bath, the general temperature range is 105-115 ℃, the evaporation temperature is lower than 105 ℃ in the initial reaction stage due to the lower content of high boiling substances in the solution, and the evaporation temperature range is generally 110-115 ℃ when the content of high boiling substances is stable after the operation for a period of time.
The carbon four components (butane and a small amount of unreacted isobutylene) and 3-methylbutyraldehyde are condensed in the condenser 608, a small amount of non-condensable gas is discharged as a tail gas through the line 414, and the carbon four components and 3-methylbutyraldehyde are fed as a liquid phase into the rectifying column 610 through the line 415 by the pump 609, at a feed position at about the fifth theoretical plate in the middle of the rectifying column 610. The rectifying tower 610 is a packed tower with 8-10 theoretical plates, the pressure at the top of the tower is 0.5MPa, and the temperature at the bottom of the tower is about 155 ℃. After separation in the rectifying tower 610, the carbon four is sent from the top of the rectifying tower through a pipeline 422 and a pump 614 to a storage tank through a pipeline 424, protected by nitrogen and stored as a byproduct. 3-methylbutyraldehyde is withdrawn from the bottom of the rectifying column via a line 419 by a pump 611 and fed into a storage tank 612. Since the feed contains about 0.9 wt% of 1-butene, the reaction produces a small amount of n-valeraldehyde (about 1 wt%) and a trace amount of 2-methylbutyraldehyde (about 0.2 wt%), and the 3-methylbutyraldehyde can be further distilled intermittently or continuously to obtain a product with a purity of more than 99.5 wt%, which can meet the requirements of fine chemicals. In the example, the total utilization rate of 1-butene is more than 98.4%, and the total utilization rate of isobutene is more than 77.2%.
Example 2
Example 2 the same process as in example 1 was used, the conditions of the first reaction zone and the intermediate separation zone were the same as in example 1, and the difference between example 2 and example 1 was that:
the second catalyst adopted in the second reaction zone is rhodium-phosphonite catalyst generated in situ by rhodium compound and phosphite ester, the rhodium compound is acetylacetone dicarbonyl rhodium, phosphonite ligand is 6,6 ' - [ (3,3 ', 5,5 ' -tetra-tert-butyl-1-1 ' -biphenyl) 2,2 ' -dioxy ] -bis-benzo [ d, f ] [1,3,2] dioxaphosphorinane, and solvent used for dissolving the second catalyst is butyraldehyde. Rhodium concentration 200pm and phosphonite ligand concentration 0.6 wt% in reactor 601; in reactor 602, the rhodium concentration was 200ppm and the phosphonite ligand concentration was 0.6 wt%. The total pressure of the reactor 601 is 1.3MPa, the temperature is 80 ℃, the total pressure of the reactor 602 is 1.2MPa, and the temperature is 85 ℃. The pressure at the top of the rectifying tower 610 is 0.5MPa, and the temperature at the bottom of the rectifying tower is about 158 ℃. The flow of syngas into reactor 601 was 65.9 standard liters/hr and the flow of syngas into reactor 602 was 19.5 standard liters/hr.
The purity of the 3-methylbutyraldehyde finally obtained in the example is 99.6%, the total utilization rate of 1-butene is more than 98.8%, and the total utilization rate of isobutene is more than 88.5%.
Comparative example 1
Comparative example 1 the composition of mixed carbon four in the first reaction zone was the same as that of example 1, the reaction conditions in the first reactor 501 and the second reactor 502 were the same as those of example 1, and the evaporation conditions in the thin film evaporator were the same, and comparative example 1 differs from example 1 in that the condensate in the vapor phase evaporated in the condenser 509, which was fed directly to the second reaction zone via the line 315 via the pump 510 without separation in the rectifying column 511, contained more than 4% by weight of 2-methylbutyraldehyde.
The reaction conditions of the second reaction zone, the conditions of the thin film evaporator 606 and the rectifying tower 610 are the same as those of the example 1, the mixed aldehyde (n-valeraldehyde, 2-methylbutyraldehyde, 3-methylbutyraldehyde) product finally extracted from the pipeline 419 is rectified, the content of the 2-methylbutyraldehyde in the 3-methylbutyraldehyde product obtained from the tower top exceeds 5 wt%, and the purity of the final product is less than 95 wt% because the material entering the second reactor contains a certain amount of 2-methylbutyraldehyde and the subsequent separation unit and the 3-methylbutyraldehyde are difficult to separate, so that the requirement of fine chemical products cannot be met.
Comparative example 2
Comparative example 2 differs from example 1 only in that the first reaction zone reduced the temperature of reactor 501 to 85 c and reactor 502 to 87 c, resulting in a 6.8 wt% 1-butene content in the four carbon composition withdrawn via line 324. Because the material entering the second reaction zone contains a certain amount of 1-butene, the hydroformylation reaction is carried out in the second reaction zone to produce a certain amount of n-valeraldehyde and 2-methylbutyraldehyde, the n-valeraldehyde and the 2-methylbutyraldehyde are difficult to separate from the main product 3-methylbutyraldehyde in the second reaction zone, and finally, the content of the 2-methylbutyraldehyde in the 3-methylbutyraldehyde product exceeds 1 wt%, so that the purity of the 3-methylbutyraldehyde is reduced, and the requirement of fine chemical products cannot be met.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (10)
1. A method of preparing an aldehyde by a mixed carbo-tetrahydroformylation reaction, comprising:
step S1, enabling the mixed C4 and the synthesis gas to contact in a first reaction area in the presence of a first catalyst to carry out hydroformylation reaction to obtain a first reaction product containing n-valeraldehyde and 2-methylbutyraldehyde;
step S2, separating the first reaction product to obtain a mixture of n-valeraldehyde and 2-methylbutyraldehyde, unreacted raw materials and a material flow containing a first catalyst;
step S3, in the presence of a second catalyst, enabling the unreacted raw materials and the synthesis gas to contact in a second reaction zone for hydroformylation reaction to obtain a second reaction product containing 3-methylbutyraldehyde, and optionally, purifying the second reaction product;
the mixed C4 is a mixture containing 1-butylene and isobutylene obtained by removing 2-butylene and 1, 3-butadiene from the C four component.
2. The process according to claim 1, wherein the first catalyst is a rhodium-phosphine complex catalyst formed from a rhodium compound and a hydrocarbyl phosphine-based ligand; the second catalyst is one or more selected from the group consisting of a rhodium-phosphine complex catalyst formed from a rhodium compound and a hydrocarbyl phosphine ligand, a rhodium-phosphine complex catalyst formed from a rhodium compound and a phosphite ligand, and a rhodium-phosphine complex catalyst formed from a rhodium compound and a phosphate ligand.
3. The process according to claim 1 or 2, wherein the first catalyst is a rhodium-phosphine complex catalyst formed from a rhodium compound and a hydrocarbyl phosphine-based ligand, and the second catalyst is a rhodium-phosphine complex catalyst formed from a rhodium compound and a hydrocarbyl phosphine-based ligand; the conditions of the first reaction zone include: at a temperature of 60-120 ℃, preferably 88-100 ℃, and/or at a pressure of 0.5-2.0MPa, preferably 0.8-2.0 MPa; the conditions of the second reaction zone include: the temperature is 60-120 deg.C, preferably 90-110 deg.C, and/or the pressure is 0.5-4MPa, preferably 2.0-4.0 MPa.
4. The process according to claim 1 or 2, wherein the first catalyst is a rhodium-phosphine complex catalyst formed from a rhodium compound and a hydrocarbyl phosphine-based ligand; the second catalyst is selected from a rhodium-phosphine complex catalyst generated by a rhodium compound and a phosphite ligand, and/or a rhodium-phosphine complex catalyst generated by a rhodium compound and a phosphate ligand; the conditions of the first reaction zone include: at a temperature of 60-120 ℃, preferably 88-100 ℃, and/or at a pressure of 0.5-2MPa, preferably 0.8-2.0 MPa; the conditions of the second reaction zone include: the temperature is 60-120 deg.C, preferably 70-100 deg.C, and the reaction pressure is 0.5-4MPa, preferably 0.8-2.0 MPa.
5. The method according to any one of claims 2 to 4, characterized in thatCharacterized in that the rhodium compound is selected from one or more of rhodium acetylacetonate dicarbonyl, rhodium trioxide, dodecacarbonyltetrarhodium, hexadecahonylhexarhodium, rhodium nitrate and rhodium acetate; and/or, the hydrocarbyl phosphine ligand has the structure
Wherein R is1、R2And R3Each independently selected from the group consisting of H, alkyl, aryl, aralkyl, and alkaryl; and/or the phosphite ligand is selected from one or more of monophosphite, diphosphite and triphosphite.
6. The method according to any one of claims 1-5, wherein: the content of 2-butene in the mixed C4 is less than 1 wt%, preferably less than 0.1 wt%.
7. The method of any one of claims 1-6, wherein the isobutylene content of the mixed C4 is greater than 10 wt%.
8. The process according to any one of claims 1 to 7, characterized in that the content of 1-butene in the unreacted feedstock is less than 1.5 wt%, preferably less than 1.0 wt%, and the content of 2-methylbutanal is less than 500ppm, preferably less than 200 ppm.
9. A process according to any one of claims 1 to 8, characterised in that the stream comprising the first catalyst is recycled to the first reaction zone.
10. The process of any one of claims 1 to 9, wherein the reaction apparatus of the first reaction zone and the reaction apparatus of the second reaction zone are each independently a single reactor or a plurality of reactors in series, wherein the plurality of reactors in series are the same or different, and wherein the reactors are tank reactors or column reactors.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114621067A (en) * | 2020-12-14 | 2022-06-14 | 中国科学院大连化学物理研究所 | High-value utilization method of carbon-tetracarbon |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1856460A (en) * | 2003-09-23 | 2006-11-01 | 埃克森美孚化学专利公司 | Hydroformylation of butenes comprising isobutylene |
| CN101054342A (en) * | 2006-04-11 | 2007-10-17 | 中国科学院兰州化学物理研究所 | Process of continuously preparing n-pentanal |
| CN101293818A (en) * | 2007-04-28 | 2008-10-29 | 中国石油化工股份有限公司 | Two-stage reaction method for mixed butylene hydroformylation |
| CN102826973A (en) * | 2011-06-17 | 2012-12-19 | 中国石油化工股份有限公司 | Method for preparing aldehydes through hydroformylation of low carbon olefins |
| CN104370718A (en) * | 2014-11-07 | 2015-02-25 | 中国海洋石油总公司 | Method for preparing valeraldehyde by etherified C4 hydroformylation |
| CN104854118A (en) * | 2012-10-12 | 2015-08-19 | 赢创德固赛有限公司 | Mixture of different asymmetrical bisophosphites and use thereof as a catalyst mixture for hydroformylation |
| CN106008184A (en) * | 2016-05-30 | 2016-10-12 | 大庆高新利华环保科技有限公司 | Method for preparing 3-methyl butyraldehyde from isobutylene |
| CN106622376A (en) * | 2016-12-08 | 2017-05-10 | 武汉凯特立斯科技有限公司 | Internal olefin isomerization and hydroformylation reaction method, and catalyst |
-
2018
- 2018-08-27 CN CN201810981610.2A patent/CN110862307A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1856460A (en) * | 2003-09-23 | 2006-11-01 | 埃克森美孚化学专利公司 | Hydroformylation of butenes comprising isobutylene |
| CN101054342A (en) * | 2006-04-11 | 2007-10-17 | 中国科学院兰州化学物理研究所 | Process of continuously preparing n-pentanal |
| CN101293818A (en) * | 2007-04-28 | 2008-10-29 | 中国石油化工股份有限公司 | Two-stage reaction method for mixed butylene hydroformylation |
| CN102826973A (en) * | 2011-06-17 | 2012-12-19 | 中国石油化工股份有限公司 | Method for preparing aldehydes through hydroformylation of low carbon olefins |
| CN104854118A (en) * | 2012-10-12 | 2015-08-19 | 赢创德固赛有限公司 | Mixture of different asymmetrical bisophosphites and use thereof as a catalyst mixture for hydroformylation |
| CN104370718A (en) * | 2014-11-07 | 2015-02-25 | 中国海洋石油总公司 | Method for preparing valeraldehyde by etherified C4 hydroformylation |
| CN106008184A (en) * | 2016-05-30 | 2016-10-12 | 大庆高新利华环保科技有限公司 | Method for preparing 3-methyl butyraldehyde from isobutylene |
| CN106622376A (en) * | 2016-12-08 | 2017-05-10 | 武汉凯特立斯科技有限公司 | Internal olefin isomerization and hydroformylation reaction method, and catalyst |
Non-Patent Citations (2)
| Title |
|---|
| 于超英等: "铑配合物催化丁烯氢甲酰化性能的研究", 《分子催化》 * |
| 张之翔等: "异丁烯氢甲酰化合成异戊醛的研究", 《应用化工》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114621067A (en) * | 2020-12-14 | 2022-06-14 | 中国科学院大连化学物理研究所 | High-value utilization method of carbon-tetracarbon |
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