CN116143600A - Method for preparing aldehyde compound by liquid-liquid continuous flow micro-channel - Google Patents
Method for preparing aldehyde compound by liquid-liquid continuous flow micro-channel Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 24
- 239000007788 liquid Substances 0.000 title claims abstract description 23
- -1 aldehyde compound Chemical class 0.000 title claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 44
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000012074 organic phase Substances 0.000 claims abstract description 36
- 239000000243 solution Substances 0.000 claims abstract description 36
- 239000008346 aqueous phase Substances 0.000 claims abstract description 28
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 17
- 150000001336 alkenes Chemical class 0.000 claims abstract description 13
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000003446 ligand Substances 0.000 claims abstract description 11
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 10
- 239000010948 rhodium Substances 0.000 claims abstract description 10
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims abstract description 9
- 239000008098 formaldehyde solution Substances 0.000 claims abstract description 8
- 239000007864 aqueous solution Substances 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 77
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 claims description 28
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 16
- XSRWPJFTHDOKTA-UHFFFAOYSA-M [Rh]Cl.C1CC=CCCC=C1 Chemical group [Rh]Cl.C1CC=CCCC=C1 XSRWPJFTHDOKTA-UHFFFAOYSA-M 0.000 claims description 14
- 239000011261 inert gas Substances 0.000 claims description 8
- CEUWWRFKARIADH-UHFFFAOYSA-N 1,1'-biphenyl;diphenylphosphane Chemical group C1=CC=CC=C1C1=CC=CC=C1.C=1C=CC=CC=1PC1=CC=CC=C1 CEUWWRFKARIADH-UHFFFAOYSA-N 0.000 claims description 4
- LVEYOSJUKRVCCF-UHFFFAOYSA-N 1,3-bis(diphenylphosphino)propane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CCCP(C=1C=CC=CC=1)C1=CC=CC=C1 LVEYOSJUKRVCCF-UHFFFAOYSA-N 0.000 claims description 4
- 238000007037 hydroformylation reaction Methods 0.000 abstract description 9
- 230000015572 biosynthetic process Effects 0.000 abstract description 7
- 238000003786 synthesis reaction Methods 0.000 abstract description 7
- 239000012071 phase Substances 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 abstract description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 abstract 3
- 150000001299 aldehydes Chemical class 0.000 description 19
- CXNIUSPIQKWYAI-UHFFFAOYSA-N xantphos Chemical compound C=12OC3=C(P(C=4C=CC=CC=4)C=4C=CC=CC=4)C=CC=C3C(C)(C)C2=CC=CC=1P(C=1C=CC=CC=1)C1=CC=CC=C1 CXNIUSPIQKWYAI-UHFFFAOYSA-N 0.000 description 18
- 239000007789 gas Substances 0.000 description 16
- 239000000047 product Substances 0.000 description 14
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 8
- 229910002091 carbon monoxide Inorganic materials 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 6
- 238000004587 chromatography analysis Methods 0.000 description 6
- 238000010790 dilution Methods 0.000 description 6
- 239000012895 dilution Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 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 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- YGCZTXZTJXYWCO-UHFFFAOYSA-N 3-phenylpropanal Chemical compound O=CCCC1=CC=CC=C1 YGCZTXZTJXYWCO-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 238000007210 heterogeneous catalysis Methods 0.000 description 2
- 238000007172 homogeneous catalysis Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- KRIOVPPHQSLHCZ-UHFFFAOYSA-N phenyl propionaldehyde Natural products CCC(=O)C1=CC=CC=C1 KRIOVPPHQSLHCZ-UHFFFAOYSA-N 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- PKIIQFSCPSSBFW-UHFFFAOYSA-N benzene;propanal Chemical compound CCC=O.C1=CC=CC=C1 PKIIQFSCPSSBFW-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- VURFVHCLMJOLKN-UHFFFAOYSA-N diphosphane Chemical compound PP VURFVHCLMJOLKN-UHFFFAOYSA-N 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- MYAJTCUQMQREFZ-UHFFFAOYSA-K tppts Chemical compound [Na+].[Na+].[Na+].[O-]S(=O)(=O)C1=CC=CC(P(C=2C=C(C=CC=2)S([O-])(=O)=O)C=2C=C(C=CC=2)S([O-])(=O)=O)=C1 MYAJTCUQMQREFZ-UHFFFAOYSA-K 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- BGEHHAVMRVXCGR-UHFFFAOYSA-N tridecanal Chemical compound CCCCCCCCCCCCC=O BGEHHAVMRVXCGR-UHFFFAOYSA-N 0.000 description 1
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- 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
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
- C07C45/69—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by addition to carbon-to-carbon double or triple bonds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0093—Microreactors, e.g. miniaturised or microfabricated reactors
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for preparing an aldehyde compound by a liquid-liquid continuous flow micro-channel, and belongs to the technical field of aldehyde synthesis. Dissolving rhodium catalyst, an organic phosphine ligand and olefin in a solvent to prepare an organic phase solution; dissolving formaldehyde in water to prepare aqueous solution; respectively injecting the organic phase solution and the aqueous phase solution into a T-shaped micro mixer through an injector to mix to form a liquid-liquid intermittent flow, and then allowing the liquid-liquid intermittent flow to enter a micro channel to react; after the reaction is finished, outputting the product through a pipeline to obtain a target product. The invention takes formaldehyde as a C1 source, and makes the olefin react with the formaldehyde to generate the aldehyde mixture which takes the straight-chain aldehyde as the main component through a liquid-liquid two-phase continuous flow micro-reaction technology, compared with the traditional hydroformylation reaction which uses CO as the C1 source, the formaldehyde solution is safer, and the formaldehyde solution is easy to transport, process, store and use, and has a certain industrial application prospect.
Description
Technical Field
The invention relates to the technical field of aldehyde synthesis, in particular to a method for preparing an aldehyde compound by a liquid-liquid continuous flow micro-channel.
Background
Hydroformylation is a process for the industrial production of aldehydes by the reaction of olefins with hydrogen and carbon monoxide (synthesis gas) under high pressure heating and transition metal catalysis. The method is firstly discovered by Otto Roelen, is one of the most widely used homogeneous catalytic reactions in industry at present, and the product aldehyde is an important fine chemical product and can be used as a synthetic raw material of a plurality of products. The hydroformylation has two production processes of homogeneous catalysis and heterogeneous catalysis, the homogeneous catalysis condition is mild, the chemical selectivity and the regioselectivity are good, but the problems of too high byproducts, catalyst deactivation and the like caused by too high distillation temperature due to the need of using a distillation process in the subsequent separation are solved, so that the catalyst is only suitable for olefins with lower boiling points of C6 and below. Although heterogeneous catalysis can reduce separation requirements, a kettle-type or tower-type reactor influences mass transfer effect of a heterogeneous system, and the required reaction conditions are harsh, so that the chemical selectivity and the regional selectivity are low, and the energy consumption is high. At present, research by researchers in this field focuses more on the development of novel catalysts, ligands and reaction media, trying to reduce reaction conditions and improve reaction efficiency and selectivity of product aldehydes, there are few improvements to hydroformylation by changing mass transfer modes. In addition, carbon monoxide (CO) is used as a traditional hydroformylation C1 source, and has the safety problems of high toxicity, inflammability, storage and transportation with special equipment and the like, so that the method has important significance in further optimizing the existing hydroformylation process and searching for a CO substitute with low price and convenient storage and transportation.
In recent years, microchannel reaction is getting more attention as an emerging technical means, compared with the traditional batch reactor, because the diameter of the microchannel and the characteristic dimension are very small, reactants can be instantaneously mixed, and the microchannel reaction has the advantages of high mass and heat transfer efficiency, good control of reaction temperature and residence time and good intrinsic safety performance, so that the microchannel reaction can be applied to the hydroformylation reaction, and mass transfer and safety problems can be effectively solved.
Disclosure of Invention
Aiming at the defects existing in the prior art, the technical problem to be solved by the invention is to provide a method for preparing aldehyde compounds by using a liquid-liquid continuous flow micro-channel, so as to solve the safety problem of CO as a C1 source, the safety problem of a traditional batch reactor, and the like, and the method has the advantages of safety, controllability and the like.
In order to solve the technical problems, the invention adopts the following technical scheme:
a method for preparing aldehyde compounds by liquid-liquid continuous flow micro-channel: dissolving rhodium catalyst, organic phosphine ligand and olefin in solvent to prepare organic phase solution; dissolving formaldehyde in water to prepare aqueous solution; respectively injecting the organic phase solution and the aqueous phase solution into a T-shaped micro mixer through an injector to mix to form a liquid-liquid intermittent flow, and then allowing the liquid-liquid intermittent flow to enter a micro channel to react; after the reaction is finished, outputting the product through a pipeline to obtain a target product.
The rhodium catalyst is (1, 5-cyclooctadiene) chlororhodium dimer, and the organic phosphine ligand is 4, 5-bis-diphenylphosphine-9, 9-dimethyl xanthene and 2,2 '-bis (diphenylphosphine) biphenyl, or 4, 6-bis (diphenylphosphine) phenazine and 2,2' -bis (diphenylphosphine) biphenyl, or 1, 3-bis (diphenylphosphine) propane. The olefin concentration is 0.67mol/L, and the molar ratio of the olefin, the rhodium catalyst and the organic phosphine ligand is 1:0.01:0.02.
The olefin is 1-decene and styrene, and the solvent is toluene.
The solvent needs to be deaerated, and the organic phase solution needs to be placed in inert gas for configuration.
The formaldehyde aqueous solution is 37wt% formaldehyde aqueous solution.
The pipeline size of the microchannel reactor is 1/16 inch; the mixer material and the interface material are 316L stainless steel material and Peek material; the pipeline is made of 316L stainless steel and PTFE.
The reaction temperature was 100deg.C, pressure was 40psi, and reaction residence time was 40 minutes.
The flow ratio of the water phase to the organic phase is 1:4.
The beneficial effects are that: compared with the prior art, the invention has the following advantages:
1) The invention provides a method for preparing an aldehyde compound by olefin two-phase hydroformylation, which uses rhodium and a biphosphine ligand to form a catalytic system, uses formaldehyde aqueous solution to replace CO as a C1 source, and has the advantages of only 40psi pressure, production cost and energy consumption saving and safer.
2) The invention uses the microchannel liquid-liquid two-phase reaction to replace the traditional batch reaction device, the volume of the production device is more than one tenth of that of the kettle type reaction, the cost is lower, the operation is convenient, the safety performance is better, and the invention is suitable for continuous production.
Drawings
FIG. 1 is a schematic diagram of a process apparatus for preparing aldehydes by liquid-liquid continuous flow micro-channels according to the present application.
Detailed Description
The invention will be further illustrated with reference to specific examples.
The liquid-liquid continuous flow micro-channel reaction apparatus used in the following examples is shown in fig. 1, and includes an organic phase pressure-resistant injector, an aqueous phase pressure-resistant injector, a T-type micro-mixer, a micro-channel reactor, a back pressure valve, and a product tank; the organic phase pressure-resistant injector and the aqueous phase pressure-resistant injector are respectively communicated with a T-shaped micro-mixer, the T-shaped micro-mixer is communicated with a micro-channel reactor, and the micro-channel reactor is communicated with a product tank through a back pressure valve. Wherein the microchannel reactor employs 1/16 inch microchannels. The mixer is made of 316L stainless steel, and the interface is made of Peek; the pipeline is made of 316L stainless steel and PTFE.
Example 1
1-decene, (1, 5-cyclooctadiene) chlororhodium dimer, xantphos, biphep and toluene were prepared as an organic phase solution in an inert gas atmosphere, added to an organic phase pressure-resistant syringe, and placed on a pressure-resistant feed pump, wherein the concentration of 1-decene in toluene was 0.66mol/L, and the molar ratio of 1-decene, (1, 5-cyclooctadiene) chlororhodium dimer, xantphos, biphep was 1:0.01:0.02:0.02. 37wt% aqueous formaldehyde solution was added as aqueous phase to an aqueous phase pressure-resistant syringe and placed on another pressure-resistant feed pump. The organic phase solution and the aqueous phase solution are simultaneously injected into a T-shaped micro mixer and are fed into a 1/16 inch micro channel, the flow rate of the organic phase is controlled to be 20 mu L/min, the flow rate of the aqueous phase is controlled to be 6 mu L/min, the intermittent flow ratio is controlled to be 1:4, the reaction temperature is controlled to be 100 ℃, the pressure of the micro channel reactor is controlled by a back pressure valve at the downstream of the system, the set pressure is 40psi, and the reaction residence time is 40 minutes. Adding acetone into the obtained pipeline outflow mixed liquid for dilution, and carrying out gas chromatographic analysis, wherein the result is as follows: the selectivity to undecalaldehyde was 36%, the selectivity to linear aldehyde was 94% and the selectivity to branched aldehyde was 6%.
Example 2
1-decene, (1, 5-cyclooctadiene) chlororhodium dimer, nixantphos, biphep and toluene were prepared as an organic phase solution in an inert gas atmosphere, added to an organic phase pressure-resistant syringe, and placed on a pressure-resistant feed pump, wherein the concentration of 1-decene in toluene was 0.66mol/L, and the molar ratio of 1-decene, (1, 5-cyclooctadiene) chlororhodium dimer, xantphos, biphep was 1:0.01:0.02:0.02. A37 wt% aqueous formaldehyde solution was added as an aqueous phase to the aqueous phase pressure-resistant syringe and placed on another pressure-resistant feed pump. The organic phase solution and the aqueous phase solution are simultaneously injected into a T-shaped micro mixer and are fed into a 1/16 inch micro channel, the flow rate of the organic phase is controlled to be 20 mu L/min, the flow rate of the aqueous phase is controlled to be 6 mu L/min, the intermittent flow ratio is controlled to be 1:4, the reaction temperature is controlled to be 100 ℃, the pressure of the micro channel reactor is controlled by a back pressure valve at the downstream of the system, the set pressure is 40psi, and the reaction residence time is 40 minutes. Adding acetone into the obtained pipeline outflow mixed liquid for dilution, and carrying out gas chromatographic analysis, wherein the result is as follows: the selectivity to undecalaldehyde was 18%, the selectivity to linear aldehyde was 80%, and the selectivity to branched aldehyde was 20%.
Example 3
Styrene, (1, 5-cyclooctadiene) chlororhodium dimer, xantphos, biphep and toluene are prepared into an organic phase solution in an inert gas atmosphere, the organic phase solution is added into an organic phase pressure-resistant injector, and the pressure-resistant injector is placed on a pressure-resistant feeding pump, wherein the concentration of the styrene in the toluene is 0.66mol/L, and the molar ratio of the (1, 5-cyclooctadiene) chlororhodium dimer to Xantphos, biphep is 1:0.01:0.02:0.02. Adding 37wt% formaldehyde aqueous solution as aqueous phase into an aqueous phase pressure-resistant injector, placing the aqueous phase pressure-resistant injector on another pressure-resistant conveying pump, simultaneously injecting the organic phase solution and the aqueous phase solution into a T-shaped micro-mixer, feeding the T-shaped micro-mixer into a 1/16 inch micro-channel, controlling the flow rate of the organic phase to be 20 mu L/min, the flow rate of the aqueous phase to be 6 mu L/min, controlling the intermittent flow ratio to be 1:4, controlling the reaction temperature to be 100 ℃, controlling the pressure of the micro-channel reactor by a back pressure valve at the downstream of the system, setting the pressure to be 40psi, and controlling the reaction residence time to be 40 minutes. Adding acetone into the obtained pipeline outflow mixed liquid for dilution, and carrying out gas chromatographic analysis, wherein the result is as follows: the benzene propionaldehyde selectivity was 22%, the linear aldehyde selectivity was 68%, and the branched aldehyde selectivity was 32%.
Example 4
Styrene, (1, 5-cyclooctadiene) chlororhodium dimer, xantphos, biphep and toluene are prepared into an organic phase solution in an inert gas atmosphere, the organic phase solution is added into an organic phase pressure-resistant injector, and the pressure-resistant injector is placed on a pressure-resistant feeding pump, wherein the concentration of the styrene in the toluene is 0.66mol/L, and the molar ratio of the (1, 5-cyclooctadiene) chlororhodium dimer to Xantphos, biphep is 1:0.01:0.02:0.02. A37 wt% aqueous formaldehyde solution was added as an aqueous phase to the aqueous phase pressure-resistant syringe and placed on another pressure-resistant feed pump. The organic phase solution and the aqueous phase solution are simultaneously injected into a T-shaped micro mixer and are fed into a 1/16 inch micro channel, the flow rate of the organic phase is controlled to be 20 mu L/min, the flow rate of the aqueous phase is controlled to be 6 mu L/min, the intermittent flow ratio is controlled to be 1:4, the reaction temperature is controlled to be 100 ℃, the pressure of the micro channel reactor is controlled by a back pressure valve at the downstream of the system, the set pressure is 20psi, and the reaction residence time is 40 minutes. Adding acetone into the obtained pipeline outflow mixed liquid for dilution, and carrying out gas chromatographic analysis, wherein the result is as follows: the selectivity to phenylpropionaldehyde was 7%, the selectivity to linear aldehyde was 70%, and the selectivity to branched aldehyde was 30%.
Example 5
Styrene, (1, 5-cyclooctadiene) chlororhodium dimer, 1, 3-bis (diphenylphosphine) propane and toluene are prepared into organic phase solution in inert gas atmosphere, the organic phase solution is added into an organic phase pressure-resistant injector and placed on a pressure-resistant conveying pump, wherein the concentration of the styrene in the toluene is 0.66mol/L, the molar ratio of the 1-decene, (1, 5-cyclooctadiene) chlororhodium dimer and the 1, 3-bis (diphenylphosphine) propane is 1:0.01:0.04. A37 wt% aqueous formaldehyde solution was added as an aqueous phase to the aqueous phase pressure-resistant syringe and placed on another pressure-resistant feed pump. The organic phase solution and the aqueous phase solution are simultaneously injected into a T-shaped micro mixer and are fed into a 1/16 inch micro channel, the flow rate of the organic phase is controlled to be 20 mu L/min, the flow rate of the aqueous phase is controlled to be 6 mu L/min, the intermittent flow ratio is controlled to be 1:4, the reaction temperature is controlled to be 100 ℃, the pressure of the micro channel reactor is controlled by a back pressure valve at the downstream of the system, the set pressure is 40psi, and the reaction residence time is 40 minutes. Adding acetone into the obtained pipeline outflow mixed liquid for dilution, and carrying out gas chromatographic analysis, wherein the result is as follows: the selectivity to phenylpropionaldehyde was 3%, the selectivity to linear aldehyde was 61%, and the selectivity to branched aldehyde was 39%.
Comparative example 1
The hydroformylation reaction was carried out using a kettle reactor, and 1-decene, (1, 5-cyclooctadiene) chlororhodium dimer, xantphos, biphep, toluene, 37wt% aqueous formaldehyde solution was prepared in an inert gas atmosphere and added to a test tube, wherein the concentration of 1-decene in toluene was 0.66mol/L, the molar ratio of 1-decene, (1, 5-cyclooctadiene) chlororhodium dimer, xantphos, biphep, and formaldehyde was 1:0.01:0.02:0.02:5. The reaction was carried out at a reaction temperature of 100℃for 20 hours. Adding acetone into the obtained mixed solution for dilution, and performing gas chromatographic analysis to obtain a result; the selectivity to undecalaldehyde was 5%, the selectivity to linear aldehyde was 84%, and the selectivity to branched aldehyde was 16%.
Comparative example 2
0.115 g of rhodium catalyst HRh (CO) (TPPTS) 3 2.8 g TPPDS,10 g diethylene glycol and 80 g methanol, 30 g 1-decene were added with stirrer and stirrer, respectivelyIn an autoclave with a temperature controller, introducing synthetic gas with the molar ratio of hydrogen to carbon monoxide of 1.0:1.0 into the autoclave to replace air in the autoclave for 3-5 times, then continuously introducing the synthetic gas into the autoclave until the total pressure in the autoclave reaches 3.0MPa, keeping the pressure constant, reacting for 1.5 hours at the temperature of 75 ℃ and the stirring speed of 1200rpm, cooling to room temperature, releasing the rest gas, and analyzing the reaction solution by gas chromatography to obtain the 1-decene with the conversion rate of 99.5 percent and the undecal selectivity of 95.7 percent, wherein the selectivity of the linear aldehyde is 73.3 percent.
See CN111606792a, example 13, paragraphs [0069] - [0070 ].
Comparative example 3
Rhodium dicarbonyl acetylacetonate, a water-soluble phosphine ligand L1 and deionized water are prepared into a catalyst solution, wherein the concentration of rhodium dicarbonyl acetylacetonate in water is 100ppm, the molar ratio of rhodium dicarbonyl acetylacetonate to the water-soluble phosphine ligand L1 is 1:100, the catalyst solution, synthesis gas and n-dodecene are simultaneously introduced into a micro-channel mixer 4, the molar ratio of n-dodecene to rhodium in the catalyst solution is controlled to be 5000:1 through a catalyst solution feeding pump 1 and a high-carbon olefin feeding pump 2, the molar ratio of synthesis gas to n-dodecene is controlled to be 2:1 through a gas flowmeter 3 and the high-carbon olefin feeding pump 2, and after mixing, the gas-liquid mixture is fed into a micro-channel reactor 5 for reaction at the reaction temperature of 100 ℃ and the reaction pressure of 1MPa, and the residence time is 60s. The obtained product is cooled by a cooler 6 and enters a three-phase separation tank 7, the separated recycle gas is mixed with fresh synthesis gas and then is introduced into a reaction system again for reaction, the water phase is recycled into the catalyst solution by a catalyst solution discharge pump 10, and the oil phase product enters a product collection tank 8.
The internal standard was added to the obtained product, and gas chromatography was performed, resulting in: the yield of the n-tridecyl aldehyde is 90 percent and the n-iso ratio is 21.
See CN113372206a, example 1, paragraphs [0027] to [0029 ].
Specific effects are shown in table 1 for comparison of the present examples and comparative examples.
Table 1 comparison of the present application with the prior art
| Reaction pressure | Reaction time | Product selectivity | Raw material (carbon source) | Reaction device | |
| Example 1 | 40psi | 40min | 36％(94：6) | Toluene (toluene) | Microchannel |
| Example 2 | 40psi | 40min | 18％(80：20) | Toluene (toluene) | Microchannel |
| Example 3 | 40psi | 40min | 22％(68：32) | Toluene (toluene) | Microchannel |
| Example 4 | 20psi | 40min | 70％(70：30) | Toluene (toluene) | Microchannel |
| Example 5 | 40psi | 40min | 3％(61：39) | Toluene (toluene) | Microchannel |
| Comparative example 1 | Atmospheric pressure | 20h | 5％(84：16) | Toluene (toluene) | Kettle type |
| Comparative example 2 | 3.0MPa | 1.5h | Unknown (73.3:26.6) | H 2 +CO | Kettle type |
| Comparative example 3 | 1.0MPa | 60s | Unknown (21:1) | Synthesis gas | Microchannel |
As can be seen from table 1, in the microchannel reactor of the present application, the organic phase and the aqueous phase can be fully mixed, so that the reaction efficiency is greatly improved, the reaction pressure is reduced, the reaction time is effectively shortened, the selectivity of the product aldehyde is improved, and the practicality and the safety are good.
Claims (10)
1. A method for preparing aldehyde compounds by liquid-liquid continuous flow micro-channel is characterized in that: dissolving rhodium catalyst, organic phosphine ligand and olefin in solvent to prepare organic phase solution; dissolving formaldehyde in water to prepare aqueous solution; respectively injecting the organic phase solution and the aqueous phase solution into a T-shaped micro mixer through an injector to mix to form a liquid-liquid intermittent flow, and then allowing the liquid-liquid intermittent flow to enter a micro channel to react; after the reaction is finished, outputting the product through a pipeline to obtain a target product.
2. The method for preparing aldehyde compound according to claim 1, wherein the rhodium catalyst is (1, 5-cyclooctadiene) chlororhodium dimer.
3. The method for preparing aldehyde compound according to claim 1, wherein the concentration of olefin is 0.66mol/L.
4. The method for preparing aldehyde compound according to claim 1, wherein the olefin is selected from 1-decene, styrene, and toluene.
5. The method for preparing aldehyde compound according to claim 1, wherein the solvent is degassed, and the organic phase solution is placed in inert gas.
6. The method for preparing aldehyde compounds according to claim 1, wherein the concentration of the aqueous formaldehyde solution is 37wt%.
7. The method for preparing aldehyde compounds according to claim 1, wherein the organic phosphine ligand is 4, 5-bis-diphenylphosphine-9, 9-dimethyl xanthene and 2,2 '-bis (diphenylphosphine) biphenyl, or 4, 6-bis (diphenylphosphine) phenazine and 2,2' -bis (diphenylphosphine) biphenyl, or 1, 3-bis (diphenylphosphine) propane.
8. The method for preparing aldehyde compounds according to claim 1, wherein the reaction temperature is 100 ℃, the pressure is 40psi, or the reaction residence time is 20psi, and the reaction residence time is 40 minutes.
9. The method for preparing aldehyde compounds according to claim 1, wherein the ratio of flow rates of the aqueous phase to the organic phase is 1:4.
10. The method for preparing aldehyde compounds according to claim 1, wherein the molar ratio of olefin, rhodium catalyst and organic phosphine ligand is 1:0.01:0.02.
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