CN112174791A - Method for separating catalyst in preparation of aldehyde by olefin hydroformylation - Google Patents
Method for separating catalyst in preparation of aldehyde by olefin hydroformylation Download PDFInfo
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- CN112174791A CN112174791A CN202011204335.7A CN202011204335A CN112174791A CN 112174791 A CN112174791 A CN 112174791A CN 202011204335 A CN202011204335 A CN 202011204335A CN 112174791 A CN112174791 A CN 112174791A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 94
- 238000007037 hydroformylation reaction Methods 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims abstract description 33
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 16
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 title claims abstract description 15
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000000926 separation method Methods 0.000 claims abstract description 206
- 239000007788 liquid Substances 0.000 claims abstract description 132
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 109
- 238000006243 chemical reaction Methods 0.000 claims abstract description 49
- 239000012530 fluid Substances 0.000 claims abstract description 48
- 238000011282 treatment Methods 0.000 claims abstract description 42
- 239000011259 mixed solution Substances 0.000 claims abstract description 32
- 239000012074 organic phase Substances 0.000 claims abstract description 13
- 239000012535 impurity Substances 0.000 claims description 24
- 239000003446 ligand Substances 0.000 claims description 19
- 239000000243 solution Substances 0.000 claims description 18
- 239000008346 aqueous phase Substances 0.000 claims description 12
- 239000012528 membrane Substances 0.000 claims description 12
- 238000001704 evaporation Methods 0.000 claims description 10
- 230000008020 evaporation Effects 0.000 claims description 10
- 238000002425 crystallisation Methods 0.000 claims description 7
- 230000008025 crystallization Effects 0.000 claims description 7
- 239000012266 salt solution Substances 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 4
- 239000013505 freshwater Substances 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- 239000002351 wastewater Substances 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 10
- VURFVHCLMJOLKN-UHFFFAOYSA-N diphosphane Chemical compound PP VURFVHCLMJOLKN-UHFFFAOYSA-N 0.000 description 10
- 239000002904 solvent Substances 0.000 description 8
- 238000000605 extraction Methods 0.000 description 7
- 239000012071 phase Substances 0.000 description 6
- 238000007792 addition Methods 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 4
- -1 i.e. Chemical class 0.000 description 4
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 3
- 235000019799 monosodium phosphate Nutrition 0.000 description 3
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- LNQFKNCJGVGEGA-UHFFFAOYSA-N [Rh+6].[O-]P([O-])[O-].[O-]P([O-])[O-] Chemical compound [Rh+6].[O-]P([O-])[O-].[O-]P([O-])[O-] LNQFKNCJGVGEGA-UHFFFAOYSA-N 0.000 description 2
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 2
- 239000012455 biphasic mixture Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- BDDWSAASCFBVBK-UHFFFAOYSA-N rhodium;triphenylphosphane Chemical compound [Rh].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 BDDWSAASCFBVBK-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 1
- AKNUHUCEWALCOI-UHFFFAOYSA-N N-ethyldiethanolamine Chemical compound OCCN(CC)CCO AKNUHUCEWALCOI-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical compound CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 description 1
- NKQYVXQKXPHGCV-UHFFFAOYSA-N [Rh+4].[O-]P([O-])OP([O-])[O-] Chemical compound [Rh+4].[O-]P([O-])OP([O-])[O-] NKQYVXQKXPHGCV-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 1
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- ZJIPHXXDPROMEF-UHFFFAOYSA-N dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O ZJIPHXXDPROMEF-UHFFFAOYSA-N 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 1
- 235000019837 monoammonium phosphate Nutrition 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 description 1
- 229940039790 sodium oxalate Drugs 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/40—Regeneration or reactivation
- B01J31/4015—Regeneration or reactivation of catalysts containing metals
- B01J31/4053—Regeneration or reactivation of catalysts containing metals with recovery of phosphorous catalyst system constituents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/40—Regeneration or reactivation
- B01J31/4015—Regeneration or reactivation of catalysts containing metals
- B01J31/4061—Regeneration or reactivation of catalysts containing metals involving membrane separation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/40—Regeneration or reactivation
- B01J31/4015—Regeneration or reactivation of catalysts containing metals
- B01J31/4076—Regeneration or reactivation of catalysts containing metals involving electrochemical processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
- B01J38/50—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using organic liquids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
- B01J38/50—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using organic liquids
- B01J38/52—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using organic liquids oxygen-containing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
- B01J38/64—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using alkaline material; using salts
-
- 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
-
- 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
- C07C45/786—Separation; Purification; Stabilisation; Use of additives by membrane separation process, e.g. pervaporation, perstraction, reverse osmosis
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
- C07C45/80—Separation; Purification; Stabilisation; Use of additives by liquid-liquid treatment
-
- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
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- Engineering & Computer Science (AREA)
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- Water Supply & Treatment (AREA)
- Electrochemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a method for separating a catalyst in preparation of aldehyde by olefin hydroformylation, which comprises the following steps: separating the reaction fluid containing the hydroformylation catalyst to obtain an organic phase containing the catalyst; the separation treatment is that the reaction fluid contacts with the separation liquid for 2 times and then contacts with water except water in the separation liquid for 1 time, and the contact of the separation liquid is continuous contact; the 1 st separation liquid contact is the contact by adopting fresh separation liquid; and the 2 nd separation liquid contact is carried out by adopting a mixed solution consisting of the separation liquid after the 1 st contact and water obtained after the water contact. By redesigning the catalytic separation method, adopting a specific separation liquid contact process and finally treating water, the high-efficiency separation of the catalyst is realized, the discharge of waste water is obviously reduced, the service life and the service performance of the catalyst are improved, and the addition of the catalyst in the subsequent production process can be obviously reduced.
Description
Technical Field
The invention relates to the field of separation, in particular to a method for separating a catalyst in preparation of aldehyde by hydroformylation of olefin.
Background
Currently, hydroformylation of olefins provides a way to produce high value-added products from olefins, i.e., olefins and syngas (CO, H)2) Producing aldehydes by using hydroformylation catalyst, the hydroformylation catalyst is mostly metalAnd organophosphorus ligand complexes, with the evolution of the hydroformylation process, the hydroformylation catalysts are also updated from cobalt catalysts, rhodium-triphenylphosphine catalysts to rhodium-bisphosphite catalysts.
The rhodium-triphenylphosphine catalyst is more stable than the rhodium-diphosphite catalyst, extraction and the like are not needed in the process flow, and the diphosphite ligand is decomposed in the catalytic reaction process although the activity is better, so that a by-product which is toxic to the catalyst is generated, and the decomposition and inactivation of the catalyst ligand are accelerated.
For example, CN111320532A discloses a method for removing acid by extraction from an olefin hydroformylation product stream, in which an effluent of a hydroformylation reaction liquid is separated into a first organic phase and a first aqueous phase in a first purification zone, and the aqueous phase is gasified and then the vapor and the first organic phase are sent to a second purification zone to remove acidic substances. However, this method involves contacting water vapor with an organic phase, the water vapor temperature is high, and a part of the hydroformylation catalyst, particularly the currently used rhodium-bisphosphite ligand catalyst, is easily decomposed at a high temperature, and this method may result in accelerating the decomposition of the catalyst and increasing the loss of the catalyst.
CN111099980A discloses an extraction method for recovering high boiling point aldehyde product and catalyst from hydroformylation product solution, comprising the following steps: (a) contacting the non-aqueous hydroformylation product solution with an aqueous extraction solvent to form a biphasic mixture, wherein the aqueous extraction solvent comprises at least one polyol, at least one primary alcohol, and water, and wherein the non-aqueous hydroformylation product solution comprises a high boiling aldehyde compound, a hydroformylation catalyst, and a non-aqueous hydroformylation solvent; and (b) separating the biphasic mixture of step (a) to obtain: (i) a non-aqueous hydroformylation solvent layer comprising the hydroformylation catalyst and the non-aqueous hydroformylation solvent; and (ii) an aqueous extraction solvent layer containing the high-boiling aldehyde compound and the aqueous extraction solvent. Various problems associated with the separation of high boiling aldehyde products from a hydroformylation product liquid containing a hydroformylation catalyst are solved while also reducing the formation of acetal compounds, particularly the amount of acetal formed.
Disclosure of Invention
In view of the problems in the prior art, the invention aims to provide a separation method of a catalyst in aldehyde preparation through olefin hydroformylation, which can realize high-efficiency separation of the catalyst, remarkably reduce the discharge of waste water, save resources, improve the service life and the service performance of the catalyst, and simultaneously remarkably reduce the addition amount of the catalyst in the subsequent production process.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a separation method of a catalyst in preparation of aldehyde by olefin hydroformylation, which comprises the following steps: separating the reaction fluid containing the hydroformylation catalyst to obtain an organic phase containing the catalyst;
the separation treatment is that the reaction fluid contacts with the separation liquid for 2 times and then contacts with water except water in the separation liquid for 1 time, and the contact of the separation liquid is continuous contact;
the 1 st separation liquid contact is the contact by adopting fresh separation liquid;
and the 2 nd separation liquid contact is carried out by adopting a mixed solution consisting of the separation liquid after the 1 st contact and water obtained after the water contact.
According to the invention, through redesigning the catalytic separation method, adopting a specific separation and contact process, adopting separation liquid contact and mixed solution contact, and then adopting water for final treatment, the high-efficiency separation of the catalyst is realized, meanwhile, the discharge of wastewater is obviously reduced, the wastewater is basically not discharged outside through the internal circulation of the process, the resources are saved, the service life and the service performance of the catalyst are improved, and meanwhile, the addition amount of the catalyst in the subsequent production process can be obviously reduced.
In a preferred embodiment of the present invention, the separation treatment is performed at least 3 times, and may be performed, for example, 3 times, 4 times, 5 times, 6 times, 7 times, 8 times, 9 times, or 10 times, but is not limited to the recited values, and other values not recited in the range are also applicable.
Preferably, the solute content of the separation liquid in the mixed solution is 5 to 30% by mass, for example, 5%, 8%, 10%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, or 25%, but not limited to the above-mentioned values, and other values not listed in this range are also applicable.
In the invention, multiple separation treatments are adopted, and the mutual promotion effect between different separation liquid contacts and water contacts is utilized, so that the separation of the catalyst is further strengthened, and the service life of the catalyst is prolonged.
As a preferred embodiment of the present invention, the catalyst comprises a metal-organophosphorus ligand complex and an organophosphorus ligand, which are known hydroformylation catalysts to those skilled in the art, such as rhodium, cobalt or other noble metal, organophosphorus monophosphine, diphosphine, triphosphon ligands or combinations thereof, which are homogeneous catalysts, dissolved in a solvent.
The separation liquid is 1 or the combination of at least 2 of weak acid metal salt solution, fatty salt solution or organic amine solution.
In the present invention, the weak acid metal salt solution is carbonate, bicarbonate, borate, citrate, phosphate, hydrogen phosphate, or acetate, and preferably sodium bicarbonate, potassium carbonate, disodium hydrogen phosphate, sodium dihydrogen phosphate, or ammonium dihydrogen phosphate, or the like.
In the invention, the fatty salt solution is maleate or fumarate.
In the present invention, the organic amine solution is triethanolamine, methyldiethanolamine, ethyldiethanolamine, tris (2-hydroxypropyl) amine, or an ethoxylate of these.
Preferably, the mass fraction of solute in the separation liquid is not less than 0.01%, and may be, for example, 0.01%, 0.05%, 0.1%, 0.5%, 1%, 5%, 10%, 20%, 30%, 40%, 50%, or 60%, but is not limited to the recited values, and other values not recited in the range are also applicable.
Preferably, the pH of the separation liquid is 6 to 8, and may be, for example, 6, 6.1, 6.2, 6.3, 6.4, 6.5, 6.6, 6.7, 6.8, 6.9, 7, 7.1, 7.2, 7.3, 7.4, 7.5, 7.6, 7.7, 7.8, 7.9 or 8, etc., but is not limited to the values recited, and other values not recited in this range are also applicable.
In a preferred embodiment of the present invention, the mass of the separation liquid in the 1 st contact is not less than 0.05% of the mass of the reaction fluid, and may be, for example, 0.05%, 0.1%, 0.5%, 1%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, or 50%, but is not limited to the above-mentioned values, and other values not listed in the above-mentioned range are also applicable.
Preferably, the mass of the mixed solution in the 2 nd separation liquid contact is 1 to 10% of the mass of the reaction fluid, and may be, for example, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, or 10%, but is not limited to the above-mentioned values, and other values not listed in this range are also applicable.
In a preferred embodiment of the present invention, the amount of water used in the water contact is not less than 0.05% by mass of the reaction fluid, and may be, for example, 0.05%, 0.1%, 0.5%, 1%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, or 50%, but is not limited to the above-mentioned values, and other values not listed in this range are also applicable.
As a preferred technical solution of the present invention, the water contact also results in an aqueous phase; the aqueous phase is returned to the water contact process after impurity removal.
In a preferred embodiment of the present invention, the impurity removal process includes at least 2 combinations of membrane separation, evaporation, electrophoretic separation, and crystallization, and the combinations may be a combination of membrane separation and evaporation, a combination of evaporation and electrophoretic separation, or a combination of crystallization and membrane separation, but the combinations are not limited to the listed combinations, and other combinations not listed are also applicable within the scope of the combinations.
As a preferred embodiment of the invention, the membrane separation comprises a single-stage and/or multi-stage membrane separation.
Preferably, the evaporation comprises single and/or multi-stage evaporation.
As a preferable technical scheme of the invention, the process of returning the water phase to the water contact after impurity removal treatment comprises the steps of returning the water after impurity removal to the water contact independently and/or returning the water after impurity removal to the water contact after mixing the water after impurity removal and fresh water.
As a preferred embodiment of the present invention, the separation method comprises: separating the reaction fluid containing the hydroformylation catalyst to obtain an organic phase containing the catalyst;
the separation treatment is that the reaction fluid contacts with the separation liquid for 2 times and then contacts with water except water in the separation liquid for 1 time, and the contact of the separation liquid is continuous contact;
the 1 st separation liquid contact is the contact by adopting fresh separation liquid;
the 2 nd separation liquid contact is carried out by adopting a mixed solution consisting of the separation liquid after the 1 st contact and water obtained after the water contact;
the separation treatment is carried out at least 3 times;
the mass fraction of solute in the separation liquid is more than or equal to 0.01 percent;
the pH value of the separation liquid is 6-8;
the mass of the separation liquid in the separation liquid contact is more than or equal to 0.05 percent of the mass of the reaction fluid;
the amount of water in the water contact is more than or equal to 0.05 percent of the mass of the reaction fluid.
In the present invention, the reaction fluid may be contacted with the separation liquid, the mixed solution and water in a single vessel or in a plurality of vessels in series by countercurrent contact. If the reaction is carried out in a reactor, the reaction fluid is introduced from the bottom of the apparatus, the separating liquid is introduced from the top, the mixed solution is introduced at a position higher than the separating liquid, and the water is introduced at a position higher than the mixed solution. If a plurality of continuous reactors are adopted, the reaction fluid only needs to pass through three reactors in sequence.
The fresh separation liquid is prepared separation liquid, but not recycled separation liquid, and the water used in the water contact can be fresh water (deionized water or tap water) or circulating water with less other impurities in the process.
Compared with the prior art, the invention at least has the following beneficial effects:
in the invention, through redesigning the catalytic separation method, adopting a specific separation treatment process, adopting the separation liquid treatment and the mixed solution treatment, and then adopting water for final treatment, the high-efficiency separation of the catalyst is realized, simultaneously, the discharge of waste water is obviously reduced, the resources are saved, the service life and the service performance of the catalyst are improved, and the addition of the catalyst in the circulating process is reduced.
Detailed Description
To better illustrate the invention and to facilitate the understanding of the technical solutions thereof, typical but non-limiting examples of the invention are as follows:
example 1
This example provides a method for separating a catalyst from an aldehyde produced by hydroformylation of an olefin, the method comprising: separating the reaction fluid containing the hydroformylation catalyst to obtain an organic phase containing the catalyst;
the separation treatment is that the reaction fluid contacts with the separation liquid for 2 times and then contacts with water except water in the separation liquid for 1 time, and the contact of the separation liquid is continuous contact;
the 1 st separation liquid contact is the contact by adopting fresh separation liquid;
the 2 nd separation liquid contact is carried out by adopting a mixed solution consisting of the separation liquid after the 1 st contact and water obtained after the water contact; the solute of the separation solution in the mixed solution is 20% by mass;
the separation treatment was carried out 3 times;
the catalyst is a rhodium-organophosphorus ligand complex and a diphosphine organophosphorus ligand;
the separation liquid is disodium hydrogen phosphate, the mass fraction of solutes in the separation liquid is 10%, and the pH of the separation liquid is 6;
the mass of the separation liquid in the 1 st separation liquid contact is 10% of the mass of the reaction fluid;
the mass of the mixed solution in the 2 nd separation liquid contact is 7% of the mass of the reaction fluid;
the amount of water used in the water contact is 15% of the mass of the reaction fluid;
said aqueous contacting also resulting in an aqueous phase; the process of returning the water phase to the water contact after impurity removal treatment is to independently return water after impurity removal to the water contact, and the impurity removal treatment adopts membrane separation and evaporation.
The consumption quota of hydroformylation catalyst per ton of product produced is detailed in table 1.
Example 2
This example provides a method for separating catalyst in the preparation of aldehyde by hydroformylation of olefin,
the separation method comprises the following steps: separating the reaction fluid containing the hydroformylation catalyst to obtain an organic phase containing the catalyst;
the separation treatment is that the reaction fluid contacts with the separation liquid for 2 times and then contacts with water except water in the separation liquid for 1 time, and the contact of the separation liquid is continuous contact;
the 1 st separation liquid contact is the contact by adopting fresh separation liquid;
the 2 nd separation liquid contact is carried out by adopting a mixed solution consisting of the separation liquid after the 1 st contact and water obtained after the water contact; the solute of the separation solution in the mixed solution is 15% by mass;
the separation treatment was carried out 4 times;
the catalyst is a rhodium-organophosphorus ligand complex and a diphosphine organophosphorus ligand;
the separation solution is a mixed solution of sodium dihydrogen phosphate and disodium hydrogen phosphate (the mass ratio of the sodium dihydrogen phosphate to the disodium hydrogen phosphate is 1:1), the mass fraction of solutes in the separation solution is 10%, and the pH of the separation solution is 6.3;
the mass of the separation liquid in the 1 st separation liquid contact is 15% of the mass of the reaction fluid;
the mass of the mixed solution in the 2 nd separation liquid contact is 2% of the mass of the reaction fluid;
the amount of the water in the water contact is more than or equal to 5% of the mass of the reaction fluid;
said aqueous contacting also resulting in an aqueous phase; the process of returning the water phase to the water contact after impurity removal treatment is to mix the water after impurity removal and fresh water and then return the water to the water contact, and the impurity removal treatment is evaporation and crystallization.
The consumption quota of hydroformylation catalyst per ton of product produced is detailed in table 1.
Example 3
This example provides a method for separating catalyst in the preparation of aldehyde by hydroformylation of olefin,
the separation method comprises the following steps: separating the reaction fluid containing the hydroformylation catalyst to obtain an organic phase containing the catalyst;
the separation treatment is that the reaction fluid contacts with the separation liquid for 2 times and then contacts with water except water in the separation liquid for 1 time, and the contact of the separation liquid is continuous contact;
the 1 st separation liquid contact is the contact by adopting fresh separation liquid;
the 2 nd separation liquid contact is carried out by adopting a mixed solution consisting of the separation liquid after the 1 st contact and water obtained after the water contact; the solute of the separation solution in the mixed solution is 25% by mass;
the separation treatment was carried out 6 times;
the catalyst is a rhodium-organophosphorus ligand complex and a diphosphine organophosphorus ligand;
the separation liquid is maleate, the mass fraction of solute in the separation liquid is 0.7%, and the pH of the separation liquid is 6.5;
the mass of the separation liquid in the 1 st separation liquid contact is 10% of the mass of the reaction fluid;
the mass of the mixed solution in the 2 nd separation liquid contact is 5% of the mass of the reaction fluid;
the amount of water used in the water contact is 15% of the mass of the reaction fluid;
said aqueous contacting also resulting in an aqueous phase; the process of returning the water phase to the water contact after impurity removal treatment is to independently return water after impurity removal to the water contact, and the impurity removal treatment is membrane separation and crystallization.
The consumption quota of hydroformylation catalyst per ton of product produced is detailed in table 1.
Example 4
This example provides a method for separating catalyst in the preparation of aldehyde by hydroformylation of olefin,
the separation method comprises the following steps: separating the reaction fluid containing the hydroformylation catalyst to obtain an organic phase containing the catalyst;
the separation treatment is that the reaction fluid contacts with the separation liquid for 2 times and then contacts with water except water in the separation liquid for 1 time, and the contact of the separation liquid is continuous contact;
the 1 st separation liquid contact is the contact by adopting fresh separation liquid;
the 2 nd separation liquid contact is carried out by adopting a mixed solution consisting of the separation liquid after the 1 st contact and water obtained after the water contact; the solute of the separation solution in the mixed solution is 22% by mass;
the separation treatment was carried out 5 times;
the catalyst is a rhodium-organophosphorus ligand complex and a diphosphine organophosphorus ligand;
the separation liquid is sodium citrate, the mass fraction of solute in the separation liquid is 30%, and the pH value of the separation liquid is 8;
the mass of the separation liquid in the 1 st separation liquid contact is 5% of the mass of the reaction fluid;
the mass of the mixed solution in the 2 nd separation liquid contact is 10% of the mass of the reaction fluid;
the amount of water used in the water contact is 9% of the mass of the reaction fluid;
said aqueous contacting also resulting in an aqueous phase; the process of returning the water phase to the water contact after impurity removal treatment is to independently return water after impurity removal to the water contact, and the impurity removal treatment is membrane separation and crystallization.
The consumption quota of hydroformylation catalyst per ton of product produced is detailed in table 1.
Example 5
This example provides a method for separating catalyst in the preparation of aldehyde by hydroformylation of olefin,
the separation method comprises the following steps: separating the reaction fluid containing the hydroformylation catalyst to obtain an organic phase containing the catalyst;
the separation treatment is that the reaction fluid contacts with the separation liquid for 2 times and then contacts with water except water in the separation liquid for 1 time, and the contact of the separation liquid is continuous contact;
the 1 st separation liquid contact is the contact by adopting fresh separation liquid;
the 2 nd separation liquid contact is carried out by adopting a mixed solution consisting of the separation liquid after the 1 st contact and water obtained after the water contact; the solute of the separation solution in the mixed solution is 17% by mass;
the separation treatment was carried out 3 times;
the catalyst is a rhodium-organophosphorus ligand complex and a triphosphonium organophosphorus ligand;
the separation liquid is sodium oxalate, the mass fraction of solute in the separation liquid is 11%, and the pH value of the separation liquid is 8;
the mass of the separation liquid in the 1 st separation liquid contact is 22% of the mass of the reaction fluid;
the mass of the mixed solution in the 2 nd separation liquid contact is 1% of the mass of the reaction fluid;
the amount of water used in the water contact is 13% of the mass of the reaction fluid;
said aqueous contacting also resulting in an aqueous phase; the process of returning the water phase to the water contact after impurity removal treatment is to independently return water after impurity removal to the water contact, and the impurity removal treatment is membrane separation and crystallization.
The consumption quota of hydroformylation catalyst per ton of product produced is detailed in table 1.
Comparative example 1
The only difference from example 1 is that no water contact is made and the consumption rating of hydroformylation catalyst per ton of product produced is detailed in table 1.
Comparative example 2
The only difference from example 1 is that no second liquid separation contact is made and the consumption rate per ton of product hydroformylation catalyst produced is detailed in table 1.
Comparative example 3
The only difference from example 1 is that the first liquid-separation contact is not carried out and the consumption rating of the hydroformylation catalyst per ton of product produced is specified in Table 1.
Comparative example 4
The only difference from example 1 is that the mixed solution in the 2 nd separator contact was not replaced with fresh separator and the consumption rating of hydroformylation catalyst per ton of product produced is detailed in table 1.
Comparative example 5
The only difference from example 1 is that the separation treatment was carried out 2 times and the consumption rating of the hydroformylation catalyst per ton of product produced is detailed in table 1.
Comparative example 6
The only difference from example 1 is that the separation treatment was carried out 1 time and the consumption rating of the hydroformylation catalyst per ton of product produced is detailed in table 1.
TABLE 1 consumption quota and reduction in catalyst make-up in examples and comparative examples
In the invention, certain catalyst needs to be supplemented due to the loss of the catalyst and the decay of the service life in continuous operation, and the supplement reduction rate of the catalyst is calculated by adopting the following formula:
the replenishment reduction rate of the catalyst (the amount of the catalyst required to be replenished in the continuous operation process of the invention-the replenishment amount of the catalyst when only the separation liquid is contacted)/the replenishment amount of the catalyst when only the separation liquid is contacted;
when the amount of the catalyst to be added when only the separated liquid is contacted is selected in the calculation of the reduction ratio in examples 1 to 5 and comparative examples 1 to 6, the contacting conditions are the same as those in examples 1 to 5 and comparative examples 1 to 6, respectively.
According to the results of the above examples and comparative examples, in the present invention, the separation treatment is adopted by redesigning the catalytic separation method, and further, after the separation liquid is contacted with the mixed solution, the final treatment is carried out by using water, so that the high-efficiency separation of the catalyst is realized, the discharge of the waste water is also significantly reduced, the resources are saved, and the service life and the service performance of the catalyst are improved.
The applicant declares that the present invention illustrates the detailed structural features of the present invention through the above embodiments, but the present invention is not limited to the above detailed structural features, that is, it does not mean that the present invention must be implemented depending on the above detailed structural features. It should be understood by those skilled in the art that any modifications of the present invention, equivalent substitutions of selected components of the present invention, additions of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (10)
1. A method for separating a catalyst in aldehyde preparation through olefin hydroformylation is characterized by comprising the following steps: separating the reaction fluid containing the hydroformylation catalyst to obtain an organic phase containing the catalyst;
the separation treatment is that the reaction fluid contacts with the separation liquid for 2 times and then contacts with water except water in the separation liquid for 1 time, and the contact of the separation liquid is continuous contact;
the 1 st separation liquid contact is the contact by adopting fresh separation liquid;
and the 2 nd separation liquid contact is carried out by adopting a mixed solution consisting of the separation liquid after the 1 st contact and water obtained after the water contact.
2. The separation method according to claim 1, wherein the separation treatment is performed at least 3 times;
preferably, the solute of the separation solution in the mixed solution is 5-30% by mass.
3. The separation process of claim 1, wherein the catalyst comprises a metal-organophosphorus ligand complex and an organophosphorus ligand;
preferably, the separation liquid is 1 or a combination of at least 2 of weak acid metal salt solution, fatty salt solution or organic amine solution;
preferably, the mass fraction of the solute in the separation liquid is more than or equal to 0.01 percent;
preferably, the pH of the separation liquid is 6 to 8.
4. The separation process according to any one of claims 1 to 3, wherein the mass of the separated liquid in the 1 st contact is 0.05% or more of the mass of the reaction fluid;
preferably, the mass of the mixed solution in the 2 nd separation liquid contact is 1-10% of the mass of the reaction fluid.
5. The separation process according to any one of claims 1 to 4, wherein the amount of water in the water contact is 0.05% or more by mass of the reaction fluid.
6. The separation process of any one of claims 1 to 5, wherein the aqueous contacting further results in an aqueous phase; the aqueous phase is returned to the water contact process after impurity removal.
7. The separation method of claim 6, wherein the impurity removal treatment comprises a combination of at least 2 of membrane separation, evaporation, electrophoretic separation, or crystallization.
8. The separation process of claim 7, wherein the membrane separation comprises single and/or multi-stage membrane separation;
preferably, the evaporation comprises single and/or multi-stage evaporation.
9. A separation process according to any one of claims 6 to 7, wherein the reject treatment of the aqueous phase back to water contact comprises returning the reject water to water contact separately and/or mixing the reject water with fresh water and returning to water contact.
10. The separation method of any one of claims 1 to 9, wherein the separation method comprises: separating the reaction fluid containing the hydroformylation catalyst to obtain an organic phase containing the catalyst;
the separation treatment is that the reaction fluid contacts with the separation liquid for 2 times and then contacts with water except water in the separation liquid for 1 time, and the contact of the separation liquid is continuous contact;
the 1 st separation liquid contact is the contact by adopting fresh separation liquid;
the 2 nd separation liquid contact is carried out by adopting a mixed solution consisting of the separation liquid after the 1 st contact and water obtained after the water contact;
the separation treatment is carried out at least 3 times;
the mass fraction of solute in the separation liquid is more than or equal to 0.01 percent;
the pH value of the separation liquid is 6-8;
the mass of the separation liquid in the separation liquid contact is more than or equal to 0.05 percent of the mass of the reaction fluid;
the amount of water in the water contact is more than or equal to 0.05 percent of the mass of the reaction fluid.
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|---|---|---|---|---|
| US5741945A (en) * | 1995-12-06 | 1998-04-21 | Union Carbide Chemicals & Plastics Technology Corporation | Processes employing indicator ligands |
| CN103402961A (en) * | 2010-11-12 | 2013-11-20 | 陶氏技术投资有限公司 | Mitigation of fouling in hydroformylation processes by water addition |
| CN107469862A (en) * | 2017-08-22 | 2017-12-15 | 中海油炼油化工科学研究院（北京）有限公司 | A kind of two step counter-current extraction purification process of rhodium/biphosphinate catalyst |
| CN111320537A (en) * | 2019-10-28 | 2020-06-23 | 中国海洋石油集团有限公司 | Purification method of olefin hydroformylation product stream |
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2020
- 2020-11-02 CN CN202011204335.7A patent/CN112174791A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5741945A (en) * | 1995-12-06 | 1998-04-21 | Union Carbide Chemicals & Plastics Technology Corporation | Processes employing indicator ligands |
| CN103402961A (en) * | 2010-11-12 | 2013-11-20 | 陶氏技术投资有限公司 | Mitigation of fouling in hydroformylation processes by water addition |
| CN107469862A (en) * | 2017-08-22 | 2017-12-15 | 中海油炼油化工科学研究院（北京）有限公司 | A kind of two step counter-current extraction purification process of rhodium/biphosphinate catalyst |
| CN111320537A (en) * | 2019-10-28 | 2020-06-23 | 中国海洋石油集团有限公司 | Purification method of olefin hydroformylation product stream |
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