CN115010586A - Hydroformylation reaction method and system - Google Patents
Hydroformylation reaction method and system Download PDFInfo
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- 238000007037 hydroformylation reaction Methods 0.000 title claims abstract description 88
- 238000000034 method Methods 0.000 title claims abstract description 37
- 238000006243 chemical reaction Methods 0.000 claims abstract description 81
- 239000003054 catalyst Substances 0.000 claims abstract description 79
- 150000001336 alkenes Chemical class 0.000 claims abstract description 59
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 57
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 52
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 40
- 239000002904 solvent Substances 0.000 claims abstract description 28
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 25
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 23
- IUZCCOPYZPLYBX-UHFFFAOYSA-N cobalt;phosphane Chemical compound P.[Co] IUZCCOPYZPLYBX-UHFFFAOYSA-N 0.000 claims abstract description 22
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims abstract description 17
- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
- 239000000047 product Substances 0.000 claims description 9
- 230000001476 alcoholic effect Effects 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 150000002430 hydrocarbons Chemical class 0.000 claims description 4
- 238000005192 partition Methods 0.000 claims description 4
- 239000004215 Carbon black (E152) Substances 0.000 claims 2
- 229930195733 hydrocarbon Natural products 0.000 claims 2
- 239000002815 homogeneous catalyst Substances 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 239000003921 oil Substances 0.000 description 11
- 238000000926 separation method Methods 0.000 description 11
- 229910017052 cobalt Inorganic materials 0.000 description 10
- 239000010941 cobalt Substances 0.000 description 10
- 238000000605 extraction Methods 0.000 description 10
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 8
- PFNHSEQQEPMLNI-UHFFFAOYSA-N 2-methyl-1-pentanol Chemical compound CCCC(C)CO PFNHSEQQEPMLNI-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- FXNDIJDIPNCZQJ-UHFFFAOYSA-N 2,4,4-trimethylpent-1-ene Chemical compound CC(=C)CC(C)(C)C FXNDIJDIPNCZQJ-UHFFFAOYSA-N 0.000 description 5
- BODRLKRKPXBDBN-UHFFFAOYSA-N 3,5,5-Trimethyl-1-hexanol Chemical compound OCCC(C)CC(C)(C)C BODRLKRKPXBDBN-UHFFFAOYSA-N 0.000 description 5
- 239000003446 ligand Substances 0.000 description 5
- 239000007791 liquid phase Substances 0.000 description 5
- 229910052703 rhodium Inorganic materials 0.000 description 4
- 239000010948 rhodium Substances 0.000 description 4
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 4
- HLZKNKRTKFSKGZ-UHFFFAOYSA-N tetradecan-1-ol Chemical compound CCCCCCCCCCCCCCO HLZKNKRTKFSKGZ-UHFFFAOYSA-N 0.000 description 4
- 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 4
- VQOXUMQBYILCKR-UHFFFAOYSA-N 1-Tridecene Chemical compound CCCCCCCCCCCC=C VQOXUMQBYILCKR-UHFFFAOYSA-N 0.000 description 3
- MHNNAWXXUZQSNM-UHFFFAOYSA-N 2-methylbut-1-ene Chemical compound CCC(C)=C MHNNAWXXUZQSNM-UHFFFAOYSA-N 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- -1 alcohol hydrocarbon compounds Chemical class 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 239000007857 degradation product Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000013505 freshwater Substances 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- 238000009616 inductively coupled plasma Methods 0.000 description 2
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- 239000000376 reactant Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- QDTDKYHPHANITQ-UHFFFAOYSA-N 7-methyloctan-1-ol Chemical compound CC(C)CCCCCCO QDTDKYHPHANITQ-UHFFFAOYSA-N 0.000 description 1
- 239000004439 Isononyl alcohol Substances 0.000 description 1
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 238000004804 winding Methods 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
- C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
- C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions
- C07C45/505—Asymmetric hydroformylation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/36—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
- C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
-
- 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
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
- C07C45/81—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C45/82—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
-
- 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 hydroformylation reaction process and system, the hydroformylation reaction process comprising: (1) carrying out pre-reaction on a cobalt-phosphine complex catalyst, an alcohol-containing solvent and synthesis gas to obtain a pre-reaction product; (2) the pre-reaction product is mixed and contacted with olefin to carry out hydroformylation reaction to obtain alcohol or aldehyde. The hydroformylation reaction system comprises a pre-reactor and a main reactor which are connected in series. The method and the system provided by the invention firstly activate the homogeneous catalyst in the pre-reactor, and then carry out hydroformylation reaction on the olefin and the synthesis gas, so that the catalytic activity and the selectivity of the homogeneous cobalt-phosphine complex catalyst can be obviously improved, and the consumption of the catalyst is reduced.
Description
Technical Field
The invention relates to a hydroformylation reaction method and a hydroformylation reaction system.
Background
Hydroformylation, also known as oxo-synthesis, is the reaction of olefins with synthesis gas (CO and H) 2 ) The aldehyde and alcohol with one more carbon atom than the olefin are generated under the action of the catalyst.
The carbonyl complex of transition metal has catalytic action for hydroformylation, and the general industrial production adopts cobalt and rhodium. The cobalt-based catalyst has higher reaction temperature and reaction pressure, but lower cost; rhodium-based catalysts have lower reaction temperatures and pressures, but are more costly. The existing catalyst introduces more organic phosphine ligands, which can improve the selectivity and reduce the reaction temperature and pressure.
The technology of rhodium-based catalyst is adopted to carry out hydroformylation reaction, the catalyst is generally used on olefin with less than 6 carbon atoms, the selectivity of rhodium is higher, and the reaction of olefin saturation hydrogenation into alkane is less. The exotherm is therefore low and no pre-reaction is required.
The technology of the cobalt-based catalyst is adopted, when the catalyst does not contain a ligand, the reaction pressure reaches over 28MPa, the method of heat extraction in the reactor is not suitable, heat is extracted between the reactors, and a heat extractor is arranged to remove heat after each reaction section.
By adopting the cobalt-based catalyst + ligand technology, the reaction pressure can be reduced to be below 12MPa, and a mode of taking heat in a reactor can be adopted. Because the ligand exists, a pre-reactor is needed to be arranged, and the catalyst and the ligand are activated again.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a hydroformylation reaction method and a reaction system for realizing the method, wherein the method has high olefin conversion rate and high alcohol selectivity.
In a first aspect, the present invention provides a hydroformylation reaction process comprising:
(1) dissolving a cobalt-phosphine complex catalyst in an alcohol-containing solvent, and carrying out pre-reaction with synthesis gas to obtain a pre-reaction product;
(2) the pre-reaction product is mixed with olefin to contact, and then hydroformylation is carried out to obtain alcohol or aldehyde.
In a second aspect, the invention provides a hydroformylation reaction system, which comprises a pre-reactor and a main reactor, wherein the pre-reactor is provided with a raw material inlet and an intermediate reactant outlet, and a cobalt-phosphine complex catalyst dissolved in an alcohol-containing solvent and synthesis gas are pre-reacted in the pre-reactor; the main reactor is provided with an inlet and a product outlet, the inlet is communicated with the intermediate reactant outlet, and in the main reactor, the olefin and the pre-reaction product are subjected to hydroformylation reaction to obtain alcohol or aldehyde, and the alcohol or aldehyde is discharged through the product outlet.
Compared with the prior art, the hydroformylation reaction method and the hydroformylation reaction system have the beneficial effects that:
according to the hydroformylation reaction method and system, the synthesis gas and the homogeneous catalyst dissolved in the solvent are firstly subjected to pre-reaction, the homogeneous catalyst is activated, and then the olefin and the synthesis gas are subjected to hydroformylation reaction, so that the catalytic activity and selectivity of the homogeneous cobalt-phosphine complex catalyst can be remarkably improved, and the consumption of the catalyst is reduced.
Drawings
FIG. 1 is a schematic flow diagram of a hydroformylation reaction process and system provided by the present invention.
Wherein:
1-synthesis gas, 2-alcohol-containing solvent, 3-olefin, 4-pre-reaction product, 5-reaction product, 6, 7 and 8-pipelines, 9-pre-reactor, 10-main reactor and 11-intermediate tank.
Detailed Description
The following describes the embodiments of the present invention in detail.
In a first aspect, the present invention provides a hydroformylation reaction process comprising:
(1) dissolving a cobalt-phosphine complex catalyst in an alcohol-containing solvent, and carrying out pre-reaction with synthesis gas to obtain a pre-reaction product;
(2) the pre-reaction product is mixed with olefin to contact, and then hydroformylation is carried out to obtain alcohol or aldehyde.
In the hydroformylation reaction method provided by the invention, the step (1) and the step (2) both adopt continuous reaction, the pre-reaction temperature of the step (1) is 60-300 ℃, the pressure is 1-12 MPa, and the airspeed is 0.3h -1 -3h -1 (ii) a Preferably, the pre-reaction temperature is 75-270 ℃, the pressure is 3-11 MPa, and the space velocity is 0.5h -1 -2.5h -1 More preferably, the temperature is 120-240 ℃, the pressure is 5-9 MPa, and the space velocity is 1.2h -1 -1.8h -1 。
The hydroformylation reaction of the step (2) is carried out at the temperature of 60-300 ℃, the pressure of 1-12 MPa and the space velocity of 0.01h -1 -2h -1 (ii) a Preferably the temperature is 75-270 ℃, the pressure is 3-11 MPa, and the space velocity is 0.03h -1 -1h -1 (ii) a More preferably, the temperature is 120-250 ℃, the pressure is 5-9 MPa, and the space velocity is 0.2h -1 -0.35h -1 。
Preferably, the pre-reaction temperature in step (1) is 5-30 ℃ lower than that in the main reaction in step (2).
Optionally, a heat extraction structure is arranged in the step (2), and the reaction temperature is controlled by heat extraction.
In the hydroformylation reaction method provided by the invention, the olefin CO is H 2 The molar ratio of (1), (1-5), (1-10), preferably (1), (1-4), (1-8), more preferably (1), (1-3), (1-6); the mass ratio of olefin to solvent to catalyst is 1 (0.17-6): 0.001-0.2), preferably 1 (0.2-5): 0.003-0.1, more preferably 1 (0.25-4): 0.005-0.06.
In the hydroformylation reaction process provided by the present invention, the number of carbon atoms of the olefin is from 3 to 19, preferably from 4 to 17, and more preferably from 5 to 14.
In the hydroformylation reaction method provided by the invention, the alcohol-containing solvent contains alcohol and other non-alcohol hydrocarbon compounds, wherein the mass content of the non-alcohol hydrocarbon compounds is 0-50%, preferably 0-40%, and more preferably 0-25%; wherein the alcohol has from 4 to 20, preferably from 5 to 18, more preferably from 6 to 15 carbon atoms; the alcohol is preferably the alcohol obtained by the olefin hydroformylation reaction; the number of carbon atoms of the non-alcoholic hydrocarbon compound is 4 to 26, preferably 5 to 24, more preferably 6 to 21.
In a second aspect, a hydroformylation reaction system comprises a pre-reactor and a main reactor which are connected in series, wherein the pre-reactor is provided with a raw material inlet and a pre-reactor outlet, the main reactor is provided with an inlet and a product outlet, and the pre-reactor outlet is communicated with the main reactor inlet; in a pre-reactor, pre-reacting a cobalt-phosphine complex catalyst dissolved in an alcohol-containing solvent with synthesis gas; in the main reactor, the olefin and the pre-reaction product are subjected to hydroformylation reaction to obtain alcohol or aldehyde, and the alcohol or aldehyde is discharged through a product outlet.
Preferably, a heat extraction structure is arranged in the main reactor. The main reactor can adopt a tubular reactor, a winding tubular reactor or a plate reactor.
Preferably, a partition plate is arranged in the main reactor, wherein one side of the main reactor is a reaction zone, and the other side of the main reactor is a heat exchange zone. The hydroformylation reaction is carried out in a reaction zone, and heat is cyclically extracted in a heat exchange zone by a heat extraction medium.
In the hydroformylation reaction system provided by the invention, the heat taking medium is circulated to take heat in a thermosiphon or pumping mode, the heat taking medium is provided with the intermediate tank, and water and heat conducting oil are preferably selected as the heat taking medium. When the heat-taking medium adopts thermosiphon heat-taking, the installation height of the intermediate tank is higher than that of the main reactor.
The raw material inlet of the pre-reactor is communicated with an alcohol feeding pipeline and a synthesis gas feeding pipeline, and the synthesis gas pipeline can be connected into the alcohol feeding pipeline or directly connected onto the pre-reactor.
The main reactor inlet is communicated with an olefin pipeline and the pre-reactor outlet, and the olefin pipeline can be communicated with a pipeline of the pre-reactor outlet connected with the main reactor or directly connected to the main reactor inlet.
The main reaction of hydroformylation is the reaction of an olefin having N carbon atoms with H 2 CO reacts to generate alcohol and aldehyde containing N +1 carbon atoms. Side reactions being olefins containing N carbon atoms, with H 2 Reacting to generate saturated alkane with N carbon atoms. The alcohol is both the product of the hydroformylation and the solvent for the catalyst. The cobalt-phosphine complex catalyst is dissolved in isononyl alcohol to become a homogeneous catalyst, and is separated for recycling after reaction. There are also instances where the catalyst degrades during the recycle process. Therefore, a small portion of the catalyst needs to be thrown out and the fresh catalyst needs to be replenished.
The hydroformylation reaction is a strongly exothermic process, the heat of reaction is above 100kJ/mol, and the heat of reaction needs to be removed in time to prevent temperature runaway. The hydroformylation reaction has high requirement on temperature control, and the applicable temperature range of the catalyst is narrow, so the reaction temperature needs to be controlled in a small range, and the olefin conversion rate, the alcohol yield and the catalyst consumption are influenced by overhigh or overlow reaction temperature.
According to the hydroformylation reaction method and the hydroformylation reaction system, the heat extraction structure is arranged in the main reactor under the optimal condition, and heat is extracted in time in the olefin hydroformylation reaction, so that the temperature runaway condition can be avoided, the side reaction is reduced, the service life of the catalyst is prolonged, and the selectivity of the hydroformylation reaction is improved.
The following describes in detail embodiments of the present invention with reference to the drawings. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
FIG. 1 is a schematic flow diagram of a hydroformylation process provided by the present invention, as shown in FIG. 1, a synthesis gas 1 and an alcohol-containing solvent 2 are added into a pre-reactor 9, the alcohol-containing solvent 2 dissolves a homogeneous cobalt-phosphine complex catalyst, and part of the active components of the cobalt-phosphine complex catalyst may be temporarily deactivated, and the activity is recovered again under the action of CO in the synthesis gas. When the temperature of the pre-reactor is not matched with the temperature of the main reactor, a heat exchanger is added in the pre-reactor to raise or lower the temperature so as to match the reaction temperature.
The pre-reaction product 4 at the outlet of the pre-reactor and the olefin 3 are added into the main reactor 10 for reaction, and the reaction product is post-treated through a pipeline 5. The hydroformylation is a strong exothermic reaction, and if heat is not removed in time, the temperature of the reactor is higher and higher, and even a local hot spot and a temperature runaway condition are generated. Therefore, it is necessary to provide a heat extraction system, one side of which performs the hydroformylation reaction, and the other side of which removes heat through a heat extraction medium. The heat taking medium can be water or heat conducting oil. Generally, when the temperature is lower (for example, below 220 ℃), the mode of water vaporization and heat removal is preferably considered; when the temperature is higher (for example, more than 250 ℃), heat transfer oil is preferably taken into consideration; when the temperature is between 220 ℃ and 250 ℃, the appropriate heat extraction mode can be determined after comprehensive consideration.
When heat is extracted by means of water evaporation thermosiphon, fresh water is fed via line 6 into the intermediate tank 11, the intermediate tank 11 being installed at a higher level than the main reactor 10. The circulating hot water is vaporized in the main reactor 10 through the pipeline 8, the density of two phases is reduced to form thermosiphon, and then the hot water returns to the intermediate tank 11 for gas-liquid separation, and the generated steam is discharged out of the boundary area through the pipeline 7.
When water evaporation forced circulation is adopted, a circulating pump needs to be additionally arranged, fresh water is added into an intermediate tank 11 through a pipeline 6, circulating hot water is conveyed into a main reactor 10 through a pipeline 8 by the circulating pump to be evaporated and heated, then the hot water returns into the intermediate tank 11 to be subjected to gas-liquid separation, and generated steam is discharged out of a boundary area through a pipeline 7.
When heat is extracted by using heat conduction oil, a circulating pump needs to be additionally arranged, the circulating heat conduction oil is conveyed into the main reactor 10 by the circulating pump through the pipeline 8 to extract heat, and the heat conduction oil after heat extraction is cooled (such as steam generation) and then returns to the intermediate tank 11. The heat conducting oil is lost in the running process, part of the heat conducting oil is thrown outwards through a pipeline 7, and meanwhile, fresh heat conducting oil is replenished through a pipeline 6.
The invention will be further illustrated by the following examples, but is not to be construed as being limited thereto.
In the examples and comparative examples:
2,4, 4-trimethyl-1-pentene, 3,5, 5-trimethyl-1-hexanol, 2-methyl-1-butene, 2-methyl-1-pentanol, n-tridecene and n-tetradecanol are commercially available from Exxon Mobil. Cobalt carbonyl, triphenylphosphine, NaOH are commercially available from the company AlfaeSa.
The preparation method of the cobalt-phosphine complex catalyst comprises the following steps: cobalt carbonyl, triphenylphosphine and NaOH are mixed according to a molar ratio of 1: 1: 1 was mixed at 50 ℃ for 1 hour.
Example 1
(1) Dissolving a cobalt-phosphine complex catalyst in 3,5, 5-trimethyl-1-hexanol, and carrying out pre-reaction with synthesis gas to obtain a pre-reaction product;
(2) the pre-reaction product is mixed and contacted with 2,4, 4-trimethyl-1-pentene, hydroformylation reaction is carried out to obtain alcohol or aldehyde, and the reaction effluent is a hydroformylation reaction product. The reactor is internally provided with a heat taking device, and the heat taking medium is water.
(3) Separating the hydroformylation reaction product obtained in the step (2) by adopting a rectification method, which comprises the following steps: a. the hydroformylation reaction product is subjected to gas-liquid separation to obtain the product containing CO and H 2 The gas phase returns to the reaction system for recycling, and the obtained liquid phase enters a first rectifying tower; b. distilling CO and H from the top of the first rectifying tower 2 Discharging the liquid phase at the bottom of the tower to enter a second rectifying tower; c. unreacted olefin and alkane generated by side reaction are obtained at the top of the second rectifying tower, and liquid phase discharged from the bottom of the second rectifying tower enters a third rectifying tower; d. alcohol and aldehyde are obtained at the top of the third rectifying tower, one part of the liquid phase discharged from the bottom of the third rectifying tower is circulated into the reaction system, and the other part isFeeding the mixture into a fourth rectifying tower; e. the alcohol generated by the main hydroformylation reaction is obtained at the top of the fourth rectifying tower, and the liquid phase at the bottom of the tower is a catalyst degradation product and heavy oil; f. and (4) allowing the tower bottom material flow of the fourth rectifying tower to enter a fifth rectifying tower, obtaining heavy oil at the tower top of the fifth rectifying tower, and obtaining a catalyst degradation product at the tower bottom.
(4) And measuring the amount of the external throwing material, measuring the cobalt content in the external throwing material by adopting an inductively coupled plasma spectrometer (ICP), and calculating the amount of the external throwing catalyst.
The catalyst consumption is the amount of catalyst thrown out, which means the mass of catalyst per hour of alcohol product 100%, in kg catalyst per ton alcohol.
Wherein, the ratio of olefin: solvent: the mass ratio of the catalyst is 1: 2: 0.04, prereactor and main reactor reaction conditions are shown in Table 1. The catalyst consumption, olefin conversion and alcohol selectivity after separation are shown in Table 1.
Wherein the olefin conversion is the total conversion of olefins/total olefin amount × 100%.
The total conversion of olefins-olefin content after reaction-olefin content before reaction, which can be obtained by chromatographic analysis.
Alcohol selectivity is the olefin/total olefin converted to alcohol x 100%.
The content of the olefins converted into alcohols/molecular weight of the alcohols can be determined by chromatographic analysis.
Example 2
(1) Dissolving the cobalt-phosphine complex catalyst in 2-methyl-1-pentanol, and carrying out pre-reaction on the cobalt-phosphine complex catalyst and synthesis gas to obtain a pre-reaction product;
(2) the pre-reaction product and 2-methyl-1-butylene are mixed and contacted to carry out hydroformylation reaction to obtain C5 alcohol or aldehyde, and the reaction effluent is a hydroformylation reaction product. The reactor is internally provided with a heat taking device, and the heat taking medium is water.
(3) The hydroformylation reaction product obtained in the step (2) is separated by a rectification method, which is the same as that in the example 1.
(4) And (4) measuring the cobalt content in the material thrown outwards, and calculating the amount of the catalyst thrown outwards and the catalyst consumption.
Wherein, the ratio of olefin: solvent: the mass ratio of the catalyst is 1: 1.8: 0.04, prereactor and main reactor reaction conditions are shown in Table 1. The catalyst consumption, olefin conversion and alcohol selectivity after separation are shown in Table 1.
Example 3
(1) Dissolving a cobalt-phosphine complex catalyst in n-tetradecanol, and performing a pre-reaction with synthesis gas to obtain a pre-reaction product;
(2) the pre-reaction product is mixed and contacted with the n-tridecene, the hydroformylation reaction is carried out to obtain the C14 alcohol or aldehyde, and the reaction effluent is the hydroformylation reaction product. The reactor is internally provided with a heat taking device, and a heat taking medium is heat conducting oil.
(3) The hydroformylation reaction product obtained in the step (2) is separated by adopting a rectification method, which is the same as the embodiment 1.
(4) And (4) measuring the cobalt content in the material thrown outwards, and calculating the amount of the catalyst thrown outwards and the catalyst consumption.
Wherein, the ratio of olefin: solvent: the mass ratio of the catalyst is 1: 2.2: 0.04, prereactor and main reactor reaction conditions are shown in Table 2. The catalyst consumption, olefin conversion and alcohol selectivity after separation are shown in Table 2.
Example 4
(1) Dissolving a cobalt-phosphine complex catalyst in 3,5, 5-trimethyl-1-hexanol, and carrying out pre-reaction with synthesis gas to obtain a pre-reaction product;
(2) the pre-reaction product is mixed and contacted with 2,4, 4-trimethyl-1-pentene, hydroformylation reaction is carried out to obtain alcohol or aldehyde, and the reaction effluent is a hydroformylation reaction product. The reactor is not provided with a heat taking device and a heat taking medium.
(3) The hydroformylation reaction product obtained in the step (2) is separated by adopting a rectification method, which is the same as the embodiment 1.
(4) And (4) measuring the cobalt content in the external throwing material, and calculating the amount of the externally thrown catalyst and the catalyst consumption.
Wherein, the ratio of olefin: solvent: the mass ratio of the catalyst is 1: 2: 0.005, prereactor and main reactor reaction conditions are shown in Table 2. The catalyst consumption, olefin conversion and alcohol selectivity after separation are shown in Table 2.
Comparative example 1
(1) The cobalt-phosphine complex catalyst is dissolved in 3,5, 5-trimethyl-1-hexanol, and is introduced into a reactor together with 2,4, 4-trimethyl-1-pentene and synthesis gas to carry out hydroformylation reaction, and the reaction effluent is a hydroformylation reaction product. The reactor is internally provided with a heat taking device, and the heat taking medium is water.
(2) The hydroformylation reaction product was separated by distillation, as in example 1.
Wherein, the ratio of olefin: solvent: the mass ratio of the catalyst is 1: 2: 0.04 and the reaction conditions are shown in Table 1. The catalyst consumption, olefin conversion and alcohol selectivity after separation are shown in Table 1.
Comparative example 2
(1) The cobalt-phosphine complex catalyst is dissolved in 2-methyl-1-pentanol, and is introduced into a reactor together with 2-methyl-1-butene and synthesis gas for hydroformylation reaction, and the reaction effluent is a hydroformylation reaction product. The reactor is internally provided with a heat taking device, and the heat taking medium is water.
(2) The hydroformylation reaction product was separated by distillation, as in example 2.
Wherein, the ratio of olefin: solvent: the mass ratio of the catalyst is 1: 1.8: 0.04 and the reaction conditions are shown in Table 1. The catalyst consumption, olefin conversion and alcohol selectivity after separation are shown in Table 1.
Comparative example 3
(1) The cobalt-phosphine complex catalyst is dissolved in n-tetradecanol, and is introduced into a reactor together with n-tridecene and synthesis gas for hydroformylation reaction, and the reaction effluent is a hydroformylation reaction product. A heat taking device is arranged in the reactor, and a heat taking medium is heat conducting oil.
(2) The hydroformylation reaction product is separated by rectification, which is the same as in example 3.
Wherein, the ratio of olefin: solvent: the mass ratio of the catalyst is 1: 2.2: 0.04 and the reaction conditions are shown in Table 2. The catalyst consumption, olefin conversion and alcohol selectivity after separation are shown in Table 2.
Comparative example 4
(1) The cobalt-phosphine complex catalyst is dissolved in 3,5, 5-trimethyl-1-hexanol, and is introduced into a reactor together with 2,4, 4-trimethyl-1-pentene and synthesis gas to carry out hydroformylation reaction, and the reaction effluent is a hydroformylation reaction product. The reactor is not provided with a heat taking device and a heat taking medium.
(2) The hydroformylation reaction product is separated by rectification, which is the same as in example 4.
Wherein, the ratio of olefin: solvent: the mass ratio of the catalyst is 1: 2: 0.005 and the reaction conditions are shown in Table 2. The catalyst consumption, olefin conversion and alcohol selectivity after separation are shown in Table 2.
TABLE 1
TABLE 2
As can be seen from the reaction results of the comparative example and the example, the hydroformylation reaction method provided by the invention is provided with the pre-reactor, and adopts two-stage reaction, so that the olefin conversion rate and the alcohol selectivity are obviously improved, and the catalyst consumption is reduced. This is because in the pre-reactor, part of the active components of the catalyst are activated, so that the catalyst activity is increased.
Claims (10)
1. A hydroformylation reaction process, comprising:
(1) pre-reacting a cobalt-phosphine complex catalyst with an alcohol-containing solvent and synthesis gas to obtain a pre-reaction product;
(2) the pre-reaction product is mixed and contacted with olefin to carry out hydroformylation reaction to obtain alcohol or aldehyde.
2. The hydroformylation reaction process according to claim 1, wherein the pre-reaction in step (1) is carried out at a reaction temperature of 60 ℃ to 300 ℃, a pressure of 1MPa to 12MPa, and a space velocity of 0.3h -1 -3h -1 (ii) a The hydroformylation reaction in the step (2) is carried out at the temperature of 60-300 ℃, the reaction pressure of 1-12 MPa and the airspeed of 0.01h -1 -2h -1 。
3. The hydroformylation process as claimed in claim 2, wherein the preliminary reaction in step (1) is carried out at a temperature of 75 ℃ to 270 ℃, a pressure of 3MPa to 11MPa and a space velocity of 0.5h -1 -2.5h -1 (ii) a The reaction temperature of the hydroformylation reaction in the step (2) is 75-270 ℃, the pressure is 3-11 MPa, and the space velocity is 0.03h -1 -1h -1 。
4. The hydroformylation reaction process according to claim 3, wherein the pre-reaction temperature in the step (1) is 120 ℃ to 240 ℃, the reaction pressure is 5MPa to 9MPa, and the space velocity is 1.20h -1 -1.80h -1 (ii) a The hydroformylation reaction of the step (2) is carried out at the temperature of 120-250 ℃, the pressure of 5-9 MPa and the space velocity of 0.20h -1 -0.35h -1 。
5. A hydroformylation process according to claim 4, wherein the temperature in step (1) is 5 to 30 ℃ lower than that in step (2).
6. The hydroformylation process according to any one of claims 1 to 5, wherein the olefin CO is H 2 The molar ratio of the alkene to the alcohol-containing solvent to the catalyst is 1 (1-5) to (1-10), and the mass ratio of the alkene to the alcohol-containing solvent to the catalyst is 1 (0.17-6) to (0.001-0.2);
preferably, the olefin CO H 2 The molar ratio of the olefin to the alcohol-containing solvent to the catalyst is 1 (1-4) to (1-8), and the mass ratio of the olefin to the alcohol-containing solvent to the catalyst is 1 (0.2-5) to (0.003-0.1);
more preferably, the alkene is CO H 2 The molar ratio of (1), (1-3) to (1-6), and the mass ratio of the olefin, the alcohol-containing solvent and the catalyst is 1, (0.25-4) to (0.005-0.06).
7. A hydroformylation process according to claim 6, wherein the olefin has from 3 to 19, preferably from 4 to 17, more preferably from 5 to 14 carbon atoms.
8. A hydroformylation process according to any one of claims 1 to 4, wherein the alcoholic solvent contains an alcohol and the remainder is a non-alcoholic hydrocarbon, wherein the non-alcoholic hydrocarbon is present in an amount of from 0 to 50% by weight, preferably from 0 to 40% by weight, more preferably from 0 to 25% by weight;
the number of carbon atoms of the alcohol is from 4 to 20, preferably from 5 to 18, more preferably from 6 to 15;
the alcohol is preferably the alcohol obtained from the hydroformylation of the olefin;
the number of carbon atoms of the non-alcoholic hydrocarbon compound is 4 to 26, preferably 5 to 24, more preferably 6 to 21.
9. A hydroformylation reaction system is characterized by comprising a pre-reactor and a main reactor which are connected in series, wherein the pre-reactor is provided with a raw material inlet and a raw material outlet, the main reactor is provided with an inlet and a product outlet, the outlet of the pre-reactor is communicated with the main reaction inlet, and a cobalt-phosphine complex catalyst dissolved in an alcohol-containing solvent and synthesis gas are pre-reacted in the pre-reactor; in the main reactor, the olefin and the pre-reaction product are subjected to hydroformylation reaction to obtain alcohol or aldehyde, and the alcohol or aldehyde is discharged through a product outlet.
10. The hydroformylation reaction system according to claim 9, wherein the main reactor is provided with a heat-taking structure, and the pre-reactor is provided with a heat-exchanging structure.
Preferably, a partition board is arranged in the main reactor, one side of the partition board is a reaction zone, and the other side of the partition board is used for circularly taking heat from a heat taking medium.
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| CN116251542A (en) * | 2023-05-16 | 2023-06-13 | 北京弗莱明科技有限公司 | Winding pipe reactor for continuously producing 2-butenoic acid |
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