CN114478214A - Hydroformylation method and separation method of hydroformylation product - Google Patents
Hydroformylation method and separation method of hydroformylation product Download PDFInfo
- Publication number
- CN114478214A CN114478214A CN202011144073.XA CN202011144073A CN114478214A CN 114478214 A CN114478214 A CN 114478214A CN 202011144073 A CN202011144073 A CN 202011144073A CN 114478214 A CN114478214 A CN 114478214A
- Authority
- CN
- China
- Prior art keywords
- hydroformylation
- reaction
- mass
- product
- hydroformylation process
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000007037 hydroformylation reaction Methods 0.000 title claims abstract description 99
- 238000000034 method Methods 0.000 title claims abstract description 63
- 238000000926 separation method Methods 0.000 title claims abstract description 33
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 32
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 32
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 32
- 230000008569 process Effects 0.000 claims abstract description 31
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims abstract description 30
- 150000001336 alkenes Chemical class 0.000 claims abstract description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 150000002736 metal compounds Chemical class 0.000 claims abstract description 21
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 20
- 238000004821 distillation Methods 0.000 claims abstract description 20
- 239000003446 ligand Substances 0.000 claims abstract description 20
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 20
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 15
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 14
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 11
- 239000012071 phase Substances 0.000 claims abstract description 11
- 239000001257 hydrogen Substances 0.000 claims abstract description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 10
- 150000001869 cobalt compounds Chemical class 0.000 claims abstract description 6
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims abstract description 5
- 150000003284 rhodium compounds Chemical class 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 68
- 239000000047 product Substances 0.000 claims description 31
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 13
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 13
- 229910052703 rhodium Inorganic materials 0.000 claims description 12
- 239000010948 rhodium Substances 0.000 claims description 12
- 229920002401 polyacrylamide Polymers 0.000 claims description 11
- 239000002202 Polyethylene glycol Substances 0.000 claims description 9
- 229920001223 polyethylene glycol Polymers 0.000 claims description 9
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 8
- 239000006227 byproduct Substances 0.000 claims description 8
- 239000007795 chemical reaction product Substances 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 229910017052 cobalt Inorganic materials 0.000 claims description 6
- 239000010941 cobalt Substances 0.000 claims description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 239000007859 condensation product Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- -1 C12 olefins Chemical class 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 22
- 239000011541 reaction mixture Substances 0.000 abstract description 5
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract description 2
- 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
- 230000000052 comparative effect Effects 0.000 description 23
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 14
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 12
- 150000001299 aldehydes Chemical class 0.000 description 11
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 10
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- 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
- 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
- 239000007789 gas Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 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
- 230000007423 decrease Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000006317 isomerization reaction Methods 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
- 150000001298 alcohols Chemical class 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
- 239000013522 chelant Substances 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 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
- QFPVVMKZTVQDTL-UHFFFAOYSA-N (Z)-9-hexadecenal Natural products CCCCCCC=CCCCCCCCC=O QFPVVMKZTVQDTL-UHFFFAOYSA-N 0.000 description 1
- 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
- 206010024769 Local reaction Diseases 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation 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
- IUZCCOPYZPLYBX-UHFFFAOYSA-N cobalt;phosphane Chemical compound P.[Co] IUZCCOPYZPLYBX-UHFFFAOYSA-N 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000007700 distillative separation Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000012530 fluid Substances 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
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000000116 mitigating effect Effects 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
- WJIBZZVTNMAURL-UHFFFAOYSA-N phosphane;rhodium Chemical compound P.[Rh] WJIBZZVTNMAURL-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000002244 precipitate Substances 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
- 239000002994 raw material Substances 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
- 230000001105 regulatory effect Effects 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
- KLJFYXOVGVXZKT-CCEZHUSRSA-N trans-hexadec-2-enal Chemical group CCCCCCCCCCCCC\C=C\C=O KLJFYXOVGVXZKT-CCEZHUSRSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
- C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions
- 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
Abstract
A hydroformylation process and a process for the separation of a hydroformylation product, the hydroformylation process comprising: carbon monoxide, hydrogen, olefin, phosphine ligand and active metal compound are contacted to carry out hydroformylation reaction to generate aldehyde and/or alcohol, wherein the active metal compound is an organic cobalt compound or an organic rhodium compound, and the reaction liquid phase material contains alkyl modified polyvinylpyrrolidone. And the hydroformylation reaction mixture is separated by twice distillation to obtain a hydroformylation product. The hydroformylation method provided by the invention has higher catalyst stability. The separation method of the hydroformylation product provided by the invention is simpler and more convenient compared with the separation method of the hydroformylation product 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 a process of forming aldehyde or alcohol having one more carbon atom than the original olefin by adding hydrogen atom and formyl group to double bonds of olefin simultaneously with carbon monoxide and hydrogen under the action of catalyst. It has now become one of the most important homogeneous catalytic processes, with annual product volumes in excess of 1200 million tons. Commercially, suitable starting olefins for the oxo process include straight and branched chain C2 to C17 olefins. The hydroformylation products are mainly classified into three types according to carbon number: 1) short chain alcohols (C3-C4) to produce solvents. For example, propanol, butanol, etc. 2) The medium chain length alcohol (C5-C12) is converted into a plasticizer. 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, which are believed to have a strong polluting effect on water bodies, in place of the phosphorus-containing surfactants.
The hydroformylation catalyst metal centers used in industry are cobalt or rhodium. Rhodium is much more catalytically active than cobalt, but is also extremely expensive. The original catalyst is unmodified cobalt carbonyl, which has harsh reaction conditions, pressure of more than 20MPa, reaction temperature of 110 ℃ and 180 ℃, and low normal isomerization ratio. Then, the phosphine ligand modified cobalt catalyst is developed, the reaction temperature is increased, but the pressure is greatly reduced to 5-10MPa, and the normal isomerization ratio is obviously improved. The third-generation catalyst is a phosphine-modified rhodium catalyst, the reaction temperature and pressure are both greatly reduced, and the normal isomerization ratio is also greatly improved. The latest generation is water-soluble rhodium catalyst, and the separation of catalyst solution and product is simpler by using water-oil two-phase system.
The hydroformylation catalyst gradually deactivates during operation. One reason is that depletion of phosphine ligands during the reaction results in a decrease in the effective ligand concentration. The main substances which lead to the deterioration of the phosphine ligands are water, carbon dioxide, alkenones, alkynes 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 phosphine-rhodium or phosphine-cobalt ratio in the reaction system becomes small, the local reaction temperature is too high, and the CO partial pressure is too high, the metal complex compounds are slowly polymerized into the polynuclear metal cluster chelate, and the metal cluster gradually grows up, so that the metal cluster chelate is deposited on the wall of the reactor or is precipitated as tiny particles. In addition, as the heavy components in the reaction system increase, impurities accumulate, etc., the solubility of the catalyst decreases during the operation and slowly precipitates, which can also lead to a decrease in the reaction efficiency.
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 fluid containing one or more products, preferably aldehydes; wherein the process is carried out in a region of the hydroformylation rate curve which is inversely or inversely related to carbon monoxide; wherein the total pressure is controlled at a predetermined target value and/or the vent flow rate is controlled at a predetermined target value by adjusting the flow of the carbon monoxide-containing inlet gas, thereby preventing sudden changes in process parameters (e.g., reaction rate, total pressure, vent flow rate, temperature, or combinations thereof) and/or mitigating periodic changes in process parameters, thereby improving catalyst stability.
CN1307143A discloses a rhodium-catalyzed hydroformylation process of olefins having 6 to 20 carbon atoms with reduced rhodium loss, by hydroformylation of olefins catalyzed by rhodium, followed by distillative separation of the output from the hydroformylation reactor into an hydroformylation product and a rhodium-containing solution, and refluxing the solution to the hydroformylation reactor, characterized in that the rhodium-containing solution is refluxed with a rhodium concentration of 20 to 150 ppm. The stability of the catalytic system is improved by controlling the concentration of the catalyst metal in a suitable range.
CN1092058A discloses a method for stabilizing phosphite ligands in a homogeneous reaction mixture containing a group viii transition metal catalyst and phosphite ligands by adding 0.001 to 5 wt% (based on the total reaction mixture) of an epoxide to the reaction mixture to reduce the degradation of the ligands and thereby extend the catalyst cycle time.
US4774361 discloses a method of slowing the deactivation of rhodium catalysts by adding 0.1-5.0 wt% of a polymer containing amide, ketone, carbamate, urea and carbonate groups to the reaction system.
Nevertheless, in actual industrial operation, deactivation of the hydroformylation catalyst during plant operation needs to be slowed down as much as possible. It is therefore desirable to provide a simple and efficient method.
Disclosure of Invention
The technical problem to be solved by the invention is to provide 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 invention provides a hydroformylation method, wherein carbon monoxide, hydrogen, olefin, phosphine ligand and active metal compound are contacted to carry out hydroformylation reaction to generate aldehyde and/or alcohol, 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 separation method of a hydroformylation product, after hydroformylation reaction, a mixture is subjected to distillation separation to obtain a first light component and a first heavy component, wherein 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 distillation separation, a mixture of hydroformylation product alcohol and byproduct alkane is obtained at the tower top, and a condensation product of aldehyde in the hydroformylation reaction is obtained at the tower bottom; the hydroformylation reaction product is prepared by the hydroformylation method.
The hydroformylation method and the separation method of the hydroformylation product 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 is to subject the mixture after the reaction to primary distillation, and then subject the distillation product to hydrorefining to obtain the final product. The separation method of the hydroformylation product provided by the invention is simpler and more convenient compared with the separation method of the hydroformylation product in the prior art through twice distillation separation.
Drawings
FIG. 1 is a schematic flow diagram of a hydroformylation process provided by the present invention.
Wherein: 1-a reactor; 2. 3, 12-line; 4-a heat exchanger; 5-a high pressure separator; 6-a product tank; 7-liquid level regulating valve; 8-a distillation column; 9-an alkaline washing tank; 10-discharging at the top of the tower; 11-bottom discharge of the tower; 13-a pressure relief valve; 14-gas meter.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a hydroformylation method, wherein carbon monoxide, hydrogen, olefin, phosphine ligand and active metal compound are contacted to carry out hydroformylation reaction to generate aldehyde and/or alcohol, 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 carbon monoxide species is from 0.5 to 3 and the ratio of the amount of carbon monoxide to olefin species is from 2 to 10.
In the method provided by the invention, the hydroformylation reaction is carried out in an organic solvent, the organic solvent is at least one of C4-C16 alcohol, toluene and a hydroformylation reaction product, and the hydroformylation reaction product of olefin, carbon monoxide and hydrogen is preferred; after the reaction, the mixture is separated to obtain the phosphine ligand and the active metal compound which are returned to the hydroformylation reactor for continuous use.
In the method 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 100-1000, preferably 300-600; 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 the alkyl modified polyvinylpyrrolidone in the reaction liquid phase material is 0.1-10 wt%, more preferably 0.5-5 wt%; the mass fraction of polyvinylpyrrolidone is 0 to 5 wt%, more preferably 0 to 2 wt%; the mass fraction of the polyethylene glycol is 0-10 wt%, more preferably 0-5 wt%; the mass fraction of polyacrylamide is 0 to 2 wt%, more preferably 0 to 0.5 wt%.
In the method provided by the invention, the ratio of the amount of the phosphine ligand substance to the amount of the active metal compound substance is r, and the r value is 1-1000. The r values are 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 100-2000 mg/L; r has a value of 1 to 20, preferably 1 to 10; the reaction temperature is 140-220 ℃, and preferably 150-190 ℃; the reaction pressure is 5 to 12MPa, preferably 6 to 10 MPa.
Preferably, when the active metal compound is an organic rhodium compound, the mass volume concentration of rhodium in the reaction liquid phase material is 20-2000mg/L, preferably 50-1000 mg/L; r is from 2 to 1000, preferably from 20 to 800; the reaction temperature is 40-180 ℃, preferably 60-150 ℃; the reaction pressure is 0.5-10MPa, preferably 1-8 MPa.
The hydroformylation reaction is carried out in an organic solvent, and preferably, the organic solvent is corresponding alcohol obtained by a hydroformylation method.
The second aspect of the present invention provides a separation method of a hydroformylation product, wherein a mixture after a reaction in the hydroformylation method is subjected to distillation separation to obtain a first light component and a first heavy component, the first light component contains a hydroformylation product alcohol, a byproduct alkane and a small amount of aldehyde, and the first heavy component contains the hydroformylation product alcohol, an alkyl modified polyvinylpyrrolidone, an active metal compound and a phosphine ligand; the first light component is subjected to alkali washing and distillation separation, a mixture of hydroformylation product alcohol and byproduct alkane is obtained at the tower top, and a condensation product of aldehyde in the hydroformylation reaction is obtained at the tower bottom.
After the reaction is finished, the reaction material is subjected to distillation separation 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 subjected to distillation separation after liquid-liquid separation, and the hydroformylation product alcohol and the byproduct alkane are discharged from the top of the tower. Wherein the sum of the molar concentrations of potassium hydroxide and sodium hydroxide in the aqueous solution of potassium hydroxide and/or sodium hydroxide is 0.1-10 mol/l, preferably 0.5-4 mol/l. The volume ratio of the first light component to the aqueous solution is 0.5 to 20, preferably 2 to 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 are gauge pressures.
The hydroformylation process provided by the present invention is further illustrated below with reference to the accompanying drawings.
FIG. 1 is a schematic flow diagram of a hydroformylation method provided by the present 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 gas, and a certain amount of alkyl modified polyvinylpyrrolidone and at least one polymer selected from 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 pressure is charged to the set level via line 3. The reactor is then pumped with a set amount of olefin via line 2 using a plunger pump. The pressure was maintained constant during the reaction. The mixture after reaction is led out through a pipeline 4, cooled by a heat exchanger and then enters a high-pressure separator 5, and the separated liquid-phase material enters a product tank 6 through an adjusting valve 7. And the mixture after the reaction enters a distillation tower 8, and a first light component and a first heavy component are obtained through distillation and separation. The first fraction is alkyl modified polyvinylpyrrolidone, active metal compound and phosphine ligand and a small amount of hydroformylation product alcohol, which is returned to the reactor as catalyst solution via line 12 for recycling. The first light component enters an alkaline washing tank 9, is in contact reaction with a sodium hydroxide aqueous solution, is subjected to liquid-liquid separation, and then is subjected to distillation separation on an organic phase, wherein a material 10 discharged from the top of the tower is a hydroformylation product alcohol and a byproduct alkane, and a material 11 discharged from the bottom of the tower is a condensation product of aldehyde in the hydroformylation reaction.
The hydroformylation process and effects provided by the present invention will be described below by way of examples.
Comparative examples and examples: all reagents used were chemically pure. Cobalt acetylacetonate and n-decane were produced from alpha-aesar; triphenylphosphine, n-octanol, n-heptene, alkyl modified polyvinylpyrrolidone, polyethylene glycol; polyacrylamide and polyvinylpyrrolidone are both produced by the company Inokay.
Conversion is the mass of olefins reacted/mass of olefins charged 100%.
Wherein the mass of the residual olefin is obtained by the following method: after the reaction is finished, cooling the reaction kettle to room temperature, releasing the residual synthesis gas, weighing the liquid mixture, adding the internal standard n-decane, and determining the mass of the residual olefin through chromatographic analysis.
Comparative example 1
The comparative example was carried out in a 500ml reaction kettle. Firstly, cobalt acetylacetonate and triphenylphosphine are added into n-octanol serving as a solvent under the protection of argon. Then transferring the mixture into a reaction kettle, and raising the temperature to 170 ℃. The pressure of the synthesis gas is charged to 8MPa, and the activation is carried out for 2 h. Then pumping n-heptene by a plunger pump. The pressure was maintained constant during the reaction. Samples were taken every 1h for composition analysis. The reaction time was 6 h. After the reaction was completed, the reaction mixture was cooled in an ice-water bath. And (3) carrying out primary distillation and separation on the reaction materials to obtain light components and heavy components. Stirring the light components and 5 wt% of sodium hydroxide aqueous solution at 70 ℃ for 1h, carrying out liquid-liquid separation, then carrying out distillation separation on an organic phase to obtain light component hydroformylation products, namely n-octanol and octane, and obtaining a condensation product of aldehyde at the bottom of the tower, wherein the main component is hexadecenal.
And the heavy component obtained by the first distillation separation is used as a catalyst solution to be recycled in the next step.
Wherein, the raw materials include 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/mass of olefin added. The reaction results are shown in Table 1.
Comparative example 2
Comparative example 2 the procedure of comparative example 1 is the same as comparative example 1 except that the reaction mass is charged with: rhodium acetylacetonate 1.5g, triphenylphosphine 152g, n-heptanol 1500ml, n-hexene 1050 g. The reaction temperature is 100 ℃ and the pressure is 3 MPa. The reaction results are shown in Table 1.
Example 1
The procedure of example 1 is the same as in comparative example 1, except that in comparative example 1: 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 is 170 ℃ and the pressure is 8 MPa. The reaction results are shown in Table 1.
Example 2
The procedure of example 2 is the same as in comparative example 1, except that in comparative example 1: 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 8 MPa. The reaction results are shown in Table 1.
Example 3
The procedure of example 3 is the same as in comparative example 1, except that in comparative example 1: 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 is 170 ℃ and the pressure is 8 MPa. The reaction results are shown in Table 1.
Example 4
The procedure of example 4 is the same as in comparative example 1, except that in comparative example 1: 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 is 100 ℃ and the pressure is 3 MPa. The reaction results are shown in Table 1.
Example 5
The procedure of example 5 is the same as in comparative example 1 except that in comparative example 1: 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 is 100 ℃ and the pressure is 3 MPa. The reaction results are shown in Table 1.
Example 6
The procedure of example 6 is the same as in comparative example 1, except that in comparative example 1: rhodium acetylacetonate 1.5g, triphenylphosphine 152g, alkyl modified polyvinylpyrrolidone (n: 700-900; m: 5)100g, polyvinylpyrrolidone (n: 700-900) 30g, n-heptanol 1500ml, n-hexylene 1050 g. The reaction temperature is 100 ℃ and the pressure is 3 MPa. The reaction results are shown in Table 1.
Example 7
The procedure of example 7 is the same as in comparative example 1, except that in comparative example 1: 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 is 100 ℃ and the pressure is 3 MPa. The reaction results are shown in Table 1.
Example 8
The procedure of example 8 is the same as in comparative example 1 except that in comparative example 1: 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 3 MPa. The reaction results are shown in Table 1.
TABLE 1
It can be seen from the results in table 1 that the metal active compound catalysts of examples 1 to 8 using the hydroformylation process provided by the present invention have better stability and significantly better effect.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including various technical features being combined in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (19)
1. A hydroformylation method is characterized in that carbon monoxide, hydrogen, olefin, phosphine ligand and active metal compound are contacted to carry out hydroformylation reaction to generate aldehyde and/or alcohol, wherein the active metal compound is an organic cobalt compound or an organic rhodium compound, and the reaction liquid phase material contains alkyl modified polyvinylpyrrolidone.
2. A hydroformylation process according to claim 1 wherein the ratio of the amount of hydrogen to carbon monoxide is from 0.5 to 3 and the ratio of the amount of carbon monoxide to olefinic species is from 2 to 10.
3. The hydroformylation process of claim 1, wherein the hydroformylation reaction is carried out in an organic solvent, the organic solvent being at least one of a C4-C16 alcohol, toluene and a hydroformylation reaction product, preferably a hydroformylation reaction product of an olefin and carbon monoxide; the phosphine ligand and the active metal compound obtained by separating the reaction product are returned to the reactor for continuous use.
4. A hydroformylation process according to claim 1 or claim 2 wherein the olefin is one or more of C3 to C12 olefins.
5. The hydroformylation process of claim 4 wherein the olefin is one or more of C6 to C10 olefins.
6. A hydroformylation process according to claim 1 or 2, wherein the alkyl-modified polyvinylpyrrolidone has the following structure:
7. The hydroformylation process according to claim 6, wherein the molecular structure of the alkyl-modified polyvinylpyrrolidone is: n is 300-600, and m is 1-3.
8. A hydroformylation process according to claim 6 or 7, wherein the mass fraction of the alkyl-modified polyvinylpyrrolidone in the reaction mass is from 0.1 to 10% by weight.
9. A hydroformylation process according to claim 8, wherein the mass fraction of the alkyl-modified polyvinylpyrrolidone in the reaction mass is from 0.5 to 5% by weight.
10. The hydroformylation process of claim 6 wherein the reaction liquid feed further comprises one or more of polyvinylpyrrolidone, polyethylene glycol and polyacrylamide.
11. The hydroformylation process according to claim 10, wherein the mass fraction of polyvinylpyrrolidone, the mass fraction of polyethylene glycol and the mass fraction of polyacrylamide in the reaction liquid phase are 0 to 5 wt%, 0 to 10 wt% and 0 to 2 wt%, respectively.
12. The hydroformylation process according to claim 11, wherein the mass fraction of polyvinylpyrrolidone, the mass fraction of polyethylene glycol and the mass fraction of polyacrylamide in the reaction liquid phase are 0 to 2 wt%, 0 to 5 wt% and 0 to 0.5 wt%, respectively.
13. A hydroformylation process according to claim 1, wherein the ratio of the amount of phosphine ligand species to the amount of active metal compound species is r, the value of r is from 1 to 1000 and the mass volume concentration of active metal compound in the reaction mass is from 10 to 5000 mg/L.
14. The hydroformylation process as claimed in claim 13, wherein, when the active metal compound is an organic cobalt compound, the mass volume concentration of cobalt in the reaction mass is from 50 to 5000mg/L, the r value is from 1 to 20, the reaction temperature is from 140 ℃ to 220 ℃ and the reaction pressure is from 5 to 12 MPa.
15. The hydroformylation process as claimed in claim 14, wherein the mass volume concentration of cobalt in the reaction mass is 100-2000 mg/L; r is 1-10; the reaction temperature is 150-190 ℃; the reaction pressure is 6-10 MPa.
16. The hydroformylation process of claim 13 wherein, when the active metal compound is an organorhodium compound, the mass volume concentration of rhodium in the reaction mass is from 20 to 2000 mg/L; r value is 2-1000, reaction temperature is 40-180 deg.C, and reaction pressure is 0.5-10 MPa.
17. A hydroformylation process according to claim 16, wherein the mass volume concentration in the reaction mass is from 50 to 1000 mg/L; r is 20-800; the reaction temperature is 60-150 ℃; the reaction pressure is 1-8 MPa.
18. A separation method of hydroformylation products, the mixture is separated by distillation after the reaction of the hydroformylation method of any one of claims 1 to 17 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, active metal compound and phosphine ligand; the first light component is subjected to alkali washing and distillation separation, a mixture of hydroformylation product alcohol and byproduct alkane is obtained at the tower top, and a condensation product of aldehyde in the hydroformylation reaction is obtained at the tower bottom.
19. The separation process of a hydroformylation product according to claim 18, wherein the first light fraction is contacted with an aqueous solution of potassium hydroxide and/or sodium hydroxide in which the sum of molar concentrations of potassium hydroxide and sodium hydroxide is 0.1 to 10 mol/liter, at 10 to 90 ℃ for 10 to 240 minutes while mixing, and the volume ratio of the first light fraction to the aqueous solution is 0.5 to 20.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011144073.XA CN114478214B (en) | 2020-10-23 | Hydroformylation method and separation method of hydroformylation product |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011144073.XA CN114478214B (en) | 2020-10-23 | Hydroformylation method and separation method of hydroformylation product |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114478214A true CN114478214A (en) | 2022-05-13 |
| CN114478214B CN114478214B (en) | 2024-05-17 |
Family
ID=
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Non-Patent Citations (1)
| Title |
|---|
| 张雪华 等: "均相催化CO2/H2 还原羰基化合成高值化学品研究进展", 《物理化学学报》, vol. 37, no. 5, pages 2007052 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1229318C (en) | Method for carrying out heterogeneous catalytic reaction, especially hydroformylation | |
| CN1227204C (en) | Hydroformylation process of olefin | |
| US4447661A (en) | Process for producing an alcohol by hydroformylation | |
| CN109937090B (en) | Method for processing hydroformylation catalyst solutions | |
| CN100400490C (en) | Method for producing tricyclodecandialdehyde | |
| CA1268776A (en) | Rhodium catalysts and methods of preparation and use thereof | |
| CN104203884A (en) | Passivation of a homegeneous hydrogenation catalyst for the production of ethylene glycol | |
| CN101565353B (en) | Preparation method for 2-propyl enanthol | |
| CN100355712C (en) | Process for the preparation of methanol | |
| CN109789404A (en) | The method of hydrogenating organic compounds in the presence of CO and catalyst fixed bed comprising integral catalyzer formed body | |
| CN112898140B (en) | Method for preparing aldehyde based on internal olefin catalyzed by phosphoramidite phosphine ligand | |
| SK2693A3 (en) | Method of improving of catalitic activity | |
| CA2313199C (en) | Process for the production of n-propanol | |
| JPH04234331A (en) | Process for producing 1,3-diol from epoxide | |
| TWI727267B (en) | Producing bdo via hydroformylation of allyl alcohol made from glycerin | |
| CN114478214A (en) | Hydroformylation method and separation method of hydroformylation product | |
| CN109020791A (en) | A method of alcohol is prepared using the olefin hydroformylation of Co catalysts Direct Regeneration reuse | |
| CN114478214B (en) | Hydroformylation method and separation method of hydroformylation product | |
| CN114426469A (en) | Method for preparing alcohol and aldehyde by olefin hydroformylation | |
| KR101291015B1 (en) | Reactor for the hydroformylation of olefin and method for the hydroformylation using the same | |
| CN113874382A (en) | Highly linear selective ligands for hydroformylation of allyl alcohols | |
| US5093297A (en) | Polystyrene immobilized rhodium complex catalyst for the hydroformylation of olefins | |
| US5091546A (en) | Novel rhodium recovery | |
| CN114522738A (en) | Method for preparing 1, 3-propylene glycol from 3-acetoxy propionaldehyde through one-step hydrogenation | |
| KR20030005058A (en) | Preparation of aldehydes |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant |