CN114478214B - Hydroformylation method and separation method of hydroformylation product - Google Patents
Hydroformylation method and separation method of hydroformylation product Download PDFInfo
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- 238000007037 hydroformylation reaction Methods 0.000 title claims abstract description 90
- 238000000034 method Methods 0.000 title claims abstract description 63
- 238000000926 separation method Methods 0.000 title abstract description 20
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 31
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 31
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 31
- 150000001336 alkenes Chemical class 0.000 claims abstract description 27
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 20
- 150000002736 metal compounds Chemical class 0.000 claims abstract description 20
- 239000003446 ligand Substances 0.000 claims abstract description 19
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 16
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 13
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims abstract description 13
- 239000001257 hydrogen Substances 0.000 claims abstract description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000011541 reaction mixture Substances 0.000 claims abstract description 7
- 150000001869 cobalt compounds Chemical class 0.000 claims abstract description 5
- 150000003284 rhodium compounds Chemical class 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 76
- 229910052703 rhodium Inorganic materials 0.000 claims description 13
- 239000010948 rhodium Substances 0.000 claims description 13
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 13
- 229920002401 polyacrylamide Polymers 0.000 claims description 11
- 239000002202 Polyethylene glycol Substances 0.000 claims description 9
- 239000012071 phase Substances 0.000 claims description 9
- 229920001223 polyethylene glycol Polymers 0.000 claims description 9
- 239000012295 chemical reaction liquid Substances 0.000 claims description 8
- 239000007795 chemical reaction product Substances 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 229910017052 cobalt Inorganic materials 0.000 claims description 7
- 239000010941 cobalt Substances 0.000 claims description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 abstract description 23
- 238000004821 distillation Methods 0.000 abstract description 8
- 239000007791 liquid phase Substances 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 25
- 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 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 14
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 11
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- MBVAQOHBPXKYMF-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;rhodium Chemical compound [Rh].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O MBVAQOHBPXKYMF-LNTINUHCSA-N 0.000 description 6
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 6
- 150000001335 aliphatic alkanes Chemical class 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 6
- FJDJVBXSSLDNJB-LNTINUHCSA-N cobalt;(z)-4-hydroxypent-3-en-2-one Chemical compound [Co].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FJDJVBXSSLDNJB-LNTINUHCSA-N 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000007859 condensation product Substances 0.000 description 4
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- -1 phosphine modified rhodium Chemical class 0.000 description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 125000005587 carbonate group Chemical group 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000007700 distillative separation Methods 0.000 description 1
- CCGKOQOJPYTBIH-UHFFFAOYSA-N ethenone Chemical compound C=C=O CCGKOQOJPYTBIH-UHFFFAOYSA-N 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229960004279 formaldehyde Drugs 0.000 description 1
- 235000019256 formaldehyde Nutrition 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 230000000116 mitigating effect Effects 0.000 description 1
- GQEZCXVZFLOKMC-UHFFFAOYSA-N n-alpha-hexadecene Natural products CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 description 1
- 150000002924 oxiranes Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000011988 third-generation catalyst Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
- C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions
- 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
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
- C07C29/141—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group with hydrogen or hydrogen-containing gases
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A hydroformylation process and a separation process for a hydroformylation product, the hydroformylation process comprising: the method comprises the steps of contacting carbon monoxide, hydrogen and olefin with phosphine ligand and active metal compound for hydroformylation reaction to generate aldehyde and/or alcohol, wherein the active metal compound is organic cobalt compound or organic rhodium compound, and the liquid phase material contains alkyl modified polyvinylpyrrolidone. The hydroformylation reaction mixture is distilled and separated twice to obtain a hydroformylation product. The hydroformylation method provided by the invention has higher catalyst stability. The separation method of the hydroformylation products provided by the invention is simpler and more convenient compared with the separation method of the hydroformylation products in the prior art through twice distillation separation.
Description
Technical Field
The invention relates to the field of hydroformylation synthesis, in particular to a hydroformylation method for synthesizing aldehyde or alcohol from olefin, carbon monoxide and hydrogen and a separation method of a hydroformylation product.
Background
Hydroformylation refers to the process of adding hydrogen atoms and formyl groups simultaneously to double bonds of an olefin under the action of a catalyst to form aldehyde or alcohol with one more carbon atom than the original olefin. Has now become one of the most important homogeneous catalytic processes, with annual production levels exceeding 1200 ten thousand tons. Industrially, suitable starting olefins for the oxo process include linear and branched C2 to C17 but olefins. The hydroformylation products are mainly classified into three types according to carbon number: 1) Short chain alcohols (C3-C4) to produce solvents. Such as propanol, butanol, etc. 2) Medium chain alcohols (C5-C12) are converted into plasticizers. 3) The long chain alcohol (C13-17) is converted to a surfactant. For example, these alcohols react with ethylene oxide to give the corresponding ethoxylates, replacing the phosphorous-containing surfactants, which are believed to have a strong contaminating effect on the water body.
The metal center of the hydroformylation catalyst used in industry is cobalt or rhodium. Rhodium is far more catalytically active than cobalt, but is also extremely expensive. The initial use is that the unmodified cobalt carbonyl is used as a catalyst, the catalyst has harsh reaction conditions, the pressure is above 20MPa, the reaction temperature is 110-180 ℃, and the normal isomerism is lower. And then developing a phosphine ligand modified cobalt catalyst, wherein the reaction temperature is improved, but the pressure is greatly reduced to 5-10MPa, and the normal isomerism ratio is obviously improved. The third generation catalyst is a phosphine modified rhodium catalyst, the reaction temperature and the reaction pressure are greatly reduced, and the normal isomerism ratio is also greatly improved. The latest generation is a water-soluble rhodium catalyst, a water-oil two-phase system is used, and the separation of a catalyst solution and a product is simpler.
The hydroformylation catalyst may be gradually deactivated during operation. One reason is that loss of phosphine ligand during the reaction results in a decrease in the effective ligand concentration. The main substances which lead to deterioration of the phosphine ligands are water, carbon dioxide, ketene, alkyne and butadiene which may be present in the production plant and which can be removed by corresponding chemical processes before the reaction. On the other hand, when the ratio of phosphine to rhodium or phosphine to cobalt in the reaction system becomes small, the local temperature of the reaction is too high, and the partial pressure of CO is too high, the metal complex slowly polymerizes into polynuclear metal cluster chelates, and the metal clusters grow gradually, so that the metal clusters are deposited on the wall of the reactor or are precipitated as tiny particles. In addition, as the heavy components in the reaction system increase, impurities accumulate, etc., the solubility of the catalyst decreases slowly and the reaction efficiency decreases during operation.
CN1993311a discloses a hydroformylation process with improved stability comprising reacting one or more reactants (e.g. olefins) with carbon monoxide and hydrogen in the presence of a hydroformylation catalyst to produce a reaction product stream containing one or more products, preferably aldehydes; wherein the process is carried out in a region of the hydroformylation rate curve which is in an inverse or inverse relationship to carbon monoxide; wherein the total pressure is controlled at a predetermined target value and/or the discharge flow rate is controlled at a predetermined target value by adjusting the flow rate of the carbon monoxide-containing inlet gas, thereby preventing abrupt changes in process parameters (e.g., reaction rate, total pressure, discharge flow rate, temperature, or a combination thereof) and/or mitigating periodic changes in process parameters, thereby improving the stability of the catalyst.
CN1307143a discloses a rhodium-catalyzed process for the hydroformylation of olefins with reduced rhodium losses, which process comprises catalytically hydroformylation of olefins having from 6 to 20 carbon atoms with rhodium, then distillative separation of the output from the hydroformylation reactor into the hydroformylation product and a rhodium-containing solution, and reflux of the solution into the hydroformylation reactor, characterized in that the rhodium concentration in the refluxed rhodium-containing solution is from 20 to 150ppm. The stability of the catalytic system is improved by controlling the concentration of the catalyst metal within a suitable range.
CN1092058a discloses a process for stabilizing phosphite ligands in a homogeneous reaction mixture containing a group viii transition metal catalyst and phosphite ligands by adding 0.001 to 5wt% (based on the total weight of the reaction mixture) of epoxide to the reaction mixture to reduce ligand degradation, thereby extending catalyst run time.
US4774361 discloses a process for slowing the deactivation of rhodium catalysts by adding to the reaction system 0.1 to 5.0 wt.% of macromolecules containing amide, ketone, carbamate, urea and carbonate groups.
Nevertheless, in actual industrial operation, the deactivation of the hydroformylation catalyst during operation of the plant still needs to be slowed down as much as possible. It is therefore desirable to provide a simple and efficient method.
Disclosure of Invention
The invention aims to solve the technical problem of providing a hydroformylation method for improving the stability of a catalyst and a separation method of a hydroformylation product on the basis of the prior art.
The first aspect of the invention provides a hydroformylation method, carbon monoxide, hydrogen and olefin are contacted with phosphine ligand and active metal compound to carry out hydroformylation reaction to generate aldehyde and/or alcohol, wherein the active metal compound is organic cobalt compound or organic rhodium compound, and the reaction liquid phase material contains alkyl modified polyvinylpyrrolidone.
The second aspect of the invention provides a method for separating a hydroformylation product, wherein a mixture after the hydroformylation reaction is distilled and separated to obtain a first light component and a first heavy component, the first light component contains hydroformylation product alcohol, byproduct alkane and a small amount of aldehyde, and the first heavy component contains hydroformylation product alcohol, alkyl modified polyvinylpyrrolidone, an active metal compound and a phosphine ligand; the first light component is subjected to alkali washing and then is subjected to distillation separation, a mixture of a hydroformylation product alcohol and a byproduct alkane is obtained at the top of the tower, and a condensation product of aldehyde in the hydroformylation reaction is obtained at the bottom of the tower; the hydroformylation reaction product is prepared by the hydroformylation method.
The hydroformylation method and the separation method of the hydroformylation products provided by the invention have the beneficial effects that:
Compared with the prior art, the hydroformylation method provided by the invention has higher catalyst stability. In the prior art, the separation method of the hydroformylation reaction product comprises the steps of distilling the mixture after the reaction for one time, and hydrofining the distilled product to obtain the final product. The separation method of the hydroformylation products provided by the invention is simpler and more convenient compared with the separation method of the hydroformylation products in the prior art through twice distillation separation.
Drawings
FIG. 1 is a schematic flow chart of the hydroformylation process provided by the invention.
Wherein: 1-a reactor; 2. 3, 12-line; 4-a heat exchanger; 5-high pressure separator; 6-a product tank; 7-a liquid level regulating valve; 8-a distillation column; 9-an alkaline washing tank; 10-discharging from the top of the tower; 11-discharging from the bottom of the tower; 13-a pressure reducing valve; 14-gas meter.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The first aspect of the invention provides a hydroformylation method, carbon monoxide, hydrogen and olefin are contacted with phosphine ligand and active metal compound to carry out hydroformylation reaction to generate aldehyde and/or alcohol, wherein the active metal compound is organic cobalt compound or organic rhodium compound, and the reaction liquid phase material contains alkyl modified polyvinylpyrrolidone.
Preferably, the ratio of the amount of hydrogen to the amount of carbon monoxide species is in the range of 0.5 to 3 and the ratio of the amount of carbon monoxide to the amount of olefin species is in the range of 2 to 10.
In the method provided by the invention, the hydroformylation reaction is carried out in an organic solvent, wherein the organic solvent is at least one of C4-C16 alcohol, toluene and a hydroformylation reaction product, preferably an olefin, carbon monoxide and hydrogen hydroformylation reaction product; the phosphine ligand and the active metal compound separated from the mixture after the reaction are returned to the hydroformylation reactor for continuous use.
In the process provided by the invention, the olefin is one or more of C3-C12 olefin, preferably C6-C10 olefin.
In the method provided by the invention, the alkyl modified polyvinylpyrrolidone has the following structure:
Wherein n ranges from 100 to 1000, preferably from 300 to 600; m is 0 to 7, preferably 1 to 3.
The reaction liquid phase material also contains one or more of polyvinylpyrrolidone, polyethylene glycol and polyacrylamide.
Preferably, the mass fraction of alkyl-modified polyvinylpyrrolidone in the reaction liquid phase material is 0.1-10wt%, more preferably 0.5-5wt%; the mass fraction of polyvinylpyrrolidone is 0-5wt%, more preferably 0-2wt%; the mass fraction of polyethylene glycol is 0-10wt%, more preferably 0-5wt%; the mass fraction of polyacrylamide is 0-2wt%, more preferably 0-0.5wt%.
In the method provided by the invention, the ratio of the amount of phosphine ligand substances to the amount of active metal compound substances is r, and the r value is 1-1000. The r value is defined as follows:
Preferably, when the active metal compound is an organic cobalt compound, the mass volume concentration of cobalt in the reaction liquid phase material is 50-5000mg/L, preferably 100-2000mg/L; r is 1 to 20, preferably 1 to 10; the reaction temperature is 140-220 ℃, preferably 150-190 ℃; the reaction pressure is 5-12MPa, preferably 6-10MPa.
Preferably, when the active metal compound is an organo-rhodium compound, the mass volume concentration of rhodium in the reaction liquid phase material is 20-2000mg/L, preferably 50-1000mg/L; r is 2 to 1000, preferably 20 to 800; the reaction temperature is 40-180 ℃, preferably 60-150 ℃; the reaction pressure is 0.5-10MPa, preferably 1-8MPa.
The hydroformylation reaction is carried out in an organic solvent, preferably the organic solvent is the corresponding alcohol obtained by the hydroformylation method.
The second aspect of the invention provides a method for separating a hydroformylation product, wherein a mixture obtained after the reaction of the hydroformylation method is distilled and separated to obtain a first light component and a first heavy component, the first light component contains hydroformylation product alcohol, byproduct alkane and a small amount of aldehyde, and the first heavy component contains hydroformylation product alcohol, alkyl modified polyvinylpyrrolidone, an active metal compound and phosphine ligand; the first light component is subjected to alkali washing and then is subjected to distillation separation, a mixture of a hydroformylation product alcohol and a byproduct alkane is obtained at the top of the tower, and a condensation product of aldehyde in the hydroformylation reaction is obtained at the bottom of the tower.
After the reaction is finished, the reaction material is distilled and separated to obtain a first light component, the first light component is mixed and contacted with an aqueous solution containing potassium hydroxide and/or sodium hydroxide, an organic phase is distilled and separated after liquid-liquid separation, and the top discharge of the tower is hydroformylation product alcohol and byproduct alkane. Wherein the sum of the molar concentrations of potassium hydroxide and sodium hydroxide in the aqueous potassium hydroxide and/or sodium hydroxide solution is from 0.1 to 10 mol/l, preferably from 0.5 to 4 mol/l. The volume ratio of the first light component to the aqueous solution is 0.5-20, preferably 2-10. The contact temperature is 10-90 ℃, preferably 30-80 ℃; the contact time is 10 to 240 minutes, preferably 20 to 60 minutes.
In the present invention, the pressures involved are gauge pressures.
The hydroformylation process provided by the present invention is further described below with reference to the accompanying drawings.
FIG. 1 is a schematic flow chart of the hydroformylation method provided by the invention, as shown in FIG. 1, a certain amount of cobalt or rhodium precursor salt and ligand are added into a solvent under the protection of argon, and a set amount of alkyl modified polyvinylpyrrolidone and at least one polymer of polyvinylpyrrolidone, polyethylene glycol and polyacrylamide are added. The liquid phase material is transferred to the reactor 1 and then heated to the reaction temperature. The synthesis gas is charged to a set pressure via line 3. Then, a predetermined amount of olefin was fed into the reactor via line 2 by a plunger pump. The pressure was maintained during the reaction. The mixture after reaction is led out through a pipeline 4, cooled by a heat exchanger and enters a high-pressure separator 5, and the separated liquid phase material enters a product tank 6 through a regulating valve 7. The mixture after reaction enters a distillation tower 8, and is distilled and separated to obtain a first light component and a first heavy component. The first heavy component is alkyl modified polyvinylpyrrolidone, active metal compound and phosphine ligand and a small amount of hydroformylation product alcohol, and the mixture is returned to the reactor through a pipeline 12 as a catalyst solution for recycling. The first light component enters an alkaline washing tank 9 to be in contact reaction with sodium hydroxide aqueous solution, an organic phase is subjected to distillation separation after liquid-liquid separation, a tower top discharge 10 is a hydroformylation product alcohol and a byproduct alkane, and a tower bottom discharge 11 is a condensation product of aldehyde in the hydroformylation reaction.
The hydroformylation method and effect provided by the invention will be described below by way of examples.
Comparative examples and examples: the reagents used were all chemically pure. Cobalt acetylacetonate, n-decane, produced by alpha-epothilone; triphenylphosphine, n-octanol, n-heptene, alkyl modified polyvinylpyrrolidone and polyethylene glycol; polyacrylamide, polyvinylpyrrolidone, is manufactured by Inonoka corporation.
The conversion is 100% of the mass of olefin reacted/mass of olefin added.
Wherein the mass of the remaining olefins is obtained by the following method: after the reaction is finished, the reaction kettle is cooled to room temperature, residual synthesis gas is released, the liquid mixture is weighed, internal standard n-decane is added, and the mass of residual olefin is determined through chromatographic analysis.
Comparative example 1
The comparative example was carried out in a 500ml reactor. Firstly, cobalt acetylacetonate and triphenylphosphine are added into n-octanol serving as a solvent under the protection of argon. Then transferred to a reaction kettle, and heated to the reaction temperature of 170 ℃. And (3) charging synthesis gas to 8MPa, and activating for 2 hours. And then pumping the n-heptene by a plunger pump. The pressure was maintained during the reaction. Samples were taken every 1h for analysis of composition. The reaction time was 6h. After the reaction was completed, the mixture was cooled in an ice-water bath. The reaction material is distilled and separated for the first time to obtain light components and heavy components. Stirring the light component and 5wt% sodium hydroxide aqueous solution for 1h at 70 ℃, separating liquid from liquid, distilling and separating an organic phase to obtain light component hydroformylation products n-octanol and octane, and obtaining an aldehyde condensation product at the bottom of the tower, wherein the main component is hexadecene aldehyde.
The heavy component obtained by the first distillation and separation is used as a catalyst solution for the next circulation.
Of these, 11g of cobalt acetylacetonate, 15.6g of triphenylphosphine, 1500ml of n-octanol and 1050g of n-heptene. The conversion is the mass of olefin reacted/the mass of olefin added. The reaction results are shown in Table 1.
Comparative example 2
The procedure of comparative example 2 was the same as in comparative example 1, except that the reaction mass was added: rhodium acetylacetonate 1.5g, triphenylphosphine 152g, n-heptanol 1500ml, and hexene 1050g. The reaction temperature was 100℃and the pressure was 3MPa. The reaction results are shown in Table 1.
Example 1
The procedure of example 1 was the same as in comparative example 1, except that the reaction mass was added: 11g of cobalt acetylacetonate, 15.6g of triphenylphosphine, 50g of alkyl modified polyvinylpyrrolidone (n=300-400; m=1), 5g of polyethylene glycol, 1500ml of n-octanol and 1050g of n-heptene. The reaction temperature was 170℃and the pressure was 8MPa. The reaction results are shown in Table 1.
Example 2
The procedure of example 2 was the same as in comparative example 1, except that the reaction mass was added: 11g of cobalt acetylacetonate, 15.6g of triphenylphosphine, 100g of alkyl modified polyvinylpyrrolidone (n=100-200; m=1), 30g of polyacrylamide, 1500ml of n-octanol and 1050g of n-heptene. The temperature is 170 ℃ and the pressure is 8MPa. The reaction results are shown in Table 1.
Example 3
The procedure of example 3 was the same as in comparative example 1, except that the reaction mass was added: 11g of cobalt acetylacetonate, 15.6g of triphenylphosphine, 100g of alkyl modified polyvinylpyrrolidone (n=700-900; m=5), 30g of polyacrylamide, 1500ml of n-octanol and 1050g of n-heptene. The reaction temperature was 170℃and the pressure was 8MPa. The reaction results are shown in Table 1.
Example 4
The procedure of example 4 was as in comparative example 1, except that the reaction mass was added: 1.5g of rhodium acetylacetonate, 152g of triphenylphosphine, 100g of alkyl modified polyvinylpyrrolidone (n=700-900; m=5), 2g of polyacrylamide, 1500ml of n-heptanol and 1050g of n-hexene. The reaction temperature was 100℃and the pressure was 3MPa. The reaction results are shown in Table 1.
Example 5
The procedure of example 5 was the same as in comparative example 1, except that the reaction mass was added: 1.5g of rhodium acetylacetonate, 152g of triphenylphosphine, 100g of alkyl modified polyvinylpyrrolidone (n=700-900; m=5), 1500ml of n-heptanol and 1050g of n-hexene. The reaction temperature was 100℃and the pressure was 3MPa. The reaction results are shown in Table 1.
Example 6
The procedure of example 6 was as in comparative example 1, except that the reaction mass was added: 1.5g of rhodium acetylacetonate, 152g of triphenylphosphine, 100g of alkyl modified polyvinylpyrrolidone (n=700-900; m=5), 30g of polyvinylpyrrolidone (n=700-900), 1500ml of n-heptanol and 1050g of n-hexene. The reaction temperature was 100℃and the pressure was 3MPa. The reaction results are shown in Table 1.
Example 7
The procedure of example 7 was the same as in comparative example 1, except that the reaction mass was added: 1.5g of rhodium acetylacetonate, 152g of triphenylphosphine, 100g of alkyl modified polyvinylpyrrolidone (n=700-900; m=5), 2g of polyacrylamide, 5g of polyethylene glycol, 1500ml of n-heptanol and 1050g of n-hexene. The reaction temperature was 100℃and the pressure was 3MPa. The reaction results are shown in Table 1.
Example 8
The procedure of example 8 was as in comparative example 1, except that the reaction mass was added: 1.5g of rhodium acetylacetonate, 152g of triphenylphosphine, 500g of alkyl modified polyvinylpyrrolidone (n=700-900; m=5), 1500ml of n-heptanol and 1050g of n-hexene. The temperature is 100 ℃ and the pressure is 3MPa. The reaction results are shown in Table 1.
TABLE 1
As can be seen from the results in Table 1, the metal active compound catalysts of examples 1-8 of the hydroformylation process provided by the invention have better stability and significantly better effect.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (15)
1. The hydroformylation method is characterized in that carbon monoxide, hydrogen and olefin are contacted with phosphine ligand and active metal compound to carry out hydroformylation reaction to generate aldehyde and/or alcohol, wherein the active metal compound is organic cobalt compound or organic rhodium compound, the reaction liquid phase material contains alkyl modified polyvinylpyrrolidone, and the mass fraction of the alkyl modified polyvinylpyrrolidone in the reaction material is 0.1-10wt%;
The alkyl modified polyvinylpyrrolidone has the following structure:
wherein n is 100-1000, and m is 0-7;
The reaction liquid phase material also contains one or more of polyvinylpyrrolidone, polyethylene glycol and polyacrylamide.
2. The hydroformylation process according to claim 1, characterized in that the ratio of the amount of hydrogen to the amount of carbon monoxide species is from 0.5 to 3 and the ratio of the amount of carbon monoxide to the amount of olefin species is from 2 to 10.
3. The hydroformylation process according to claim 1, wherein the hydroformylation reaction is carried out in an organic solvent which is at least one of a C4-C16 alcohol, toluene and a hydroformylation reaction product; the phosphine ligand and the active metal compound obtained by separating the reaction product are returned to the reactor for continuous use.
4. The hydroformylation process according to claim 3, wherein said organic solvent is a hydroformylation reaction product.
5. The hydroformylation process according to claim 1 or 2, characterized in that the olefins are one or more of the C3-C12 olefins.
6. The hydroformylation process according to claim 5, wherein the olefins are one or more of C6-C10 olefins.
7. The hydroformylation process according to claim 1, wherein said alkyl-modified polyvinylpyrrolidone has a molecular structure of: n is 300-600, m is 1-3.
8. The hydroformylation process according to claim 1, characterized in that the mass fraction of alkyl-modified polyvinylpyrrolidone in the reaction mass is from 0.5 to 5% by weight.
9. The hydroformylation process according to claim 1, wherein the mass fraction of polyvinylpyrrolidone in the liquid reaction mixture is 0 to 5wt%, the mass fraction of polyethylene glycol is 0 to 10wt% and the mass fraction of polyacrylamide is 0 to 2wt%.
10. The hydroformylation process according to claim 9, wherein the mass fraction of polyvinylpyrrolidone in the liquid reaction mixture is 0to 2wt%, the mass fraction of polyethylene glycol is 0to 5wt% and the mass fraction of polyacrylamide is 0to 0.5wt%.
11. The hydroformylation process according to claim 1, characterized in that the ratio of the amount of phosphine ligand material to the amount of active metal compound material is r, r is from 1 to 1000 and the mass volume concentration of active metal compound in the reaction mass is from 10 to 5000mg/L.
12. The hydroformylation process according to claim 11, wherein, when the active metal compound is an organocobalt compound, the mass volume concentration of cobalt in the reaction mixture is 50 to 5000mg/L, the r value is 1 to 20, the reaction temperature is 140 to 220℃and the reaction pressure is 5 to 12MPa.
13. The hydroformylation process according to claim 12, characterized in that the mass volume concentration of cobalt in the reaction mass is from 100 to 2000mg/L; r is 1-10; the reaction temperature is 150-190 ℃; the reaction pressure is 6-10MPa.
14. The hydroformylation process according to claim 1, wherein, when the active metal compound is an organorhodium compound, the mass volume concentration of rhodium in the reaction mass is 20 to 2000mg/L; the r value is 2-1000, the reaction temperature is 40-180 ℃, and the reaction pressure is 0.5-10MPa.
15. The hydroformylation process according to claim 14, characterized in that the mass volume concentration in the reaction mass is from 50 to 1000mg/L; r is 20-800; the reaction temperature is 60-150 ℃; the reaction pressure is 1-8MPa.
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| US4774361A (en) * | 1986-05-20 | 1988-09-27 | Union Carbide Corporation | Transition metal complex catalyzed reactions |
| EP1154976A1 (en) * | 1999-02-26 | 2001-11-21 | Basf Aktiengesellschaft | Method for the hydroformylation of olefins |
| CN1871066A (en) * | 2003-10-23 | 2006-11-29 | 巴斯福股份公司 | Stabilization of hydroformylation catalysts based on phosphoramide ligands |
| EP3130399A1 (en) * | 2015-08-12 | 2017-02-15 | Basf Se | Method for the hydroformylation of olefins and/or alkynes in the gas phase with a mixture of hydrogen and carbon monoxide in the presence of heterogeneous catalyst |
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| US4774361A (en) * | 1986-05-20 | 1988-09-27 | Union Carbide Corporation | Transition metal complex catalyzed reactions |
| EP1154976A1 (en) * | 1999-02-26 | 2001-11-21 | Basf Aktiengesellschaft | Method for the hydroformylation of olefins |
| CN1871066A (en) * | 2003-10-23 | 2006-11-29 | 巴斯福股份公司 | Stabilization of hydroformylation catalysts based on phosphoramide ligands |
| EP3130399A1 (en) * | 2015-08-12 | 2017-02-15 | Basf Se | Method for the hydroformylation of olefins and/or alkynes in the gas phase with a mixture of hydrogen and carbon monoxide in the presence of heterogeneous catalyst |
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