CN107497494B - Catalyst composition for synthesizing methyl propionate from ethylene and synthesis method thereof - Google Patents
Catalyst composition for synthesizing methyl propionate from ethylene and synthesis method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 86
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 239000005977 Ethylene Substances 0.000 title claims abstract description 64
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 229940017219 methyl propionate Drugs 0.000 title claims abstract description 49
- 239000000203 mixture Substances 0.000 title claims abstract description 37
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 31
- 238000001308 synthesis method Methods 0.000 title description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 72
- 238000006243 chemical reaction Methods 0.000 claims abstract description 61
- 238000000034 method Methods 0.000 claims abstract description 27
- 239000002904 solvent Substances 0.000 claims abstract description 25
- 238000005810 carbonylation reaction Methods 0.000 claims abstract description 21
- 150000002903 organophosphorus compounds Chemical class 0.000 claims abstract description 21
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 17
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 16
- 230000002378 acidificating effect Effects 0.000 claims abstract description 12
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims abstract description 11
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 30
- 239000002253 acid Substances 0.000 claims description 22
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 15
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 14
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 230000035484 reaction time Effects 0.000 claims description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 7
- 229910001868 water Inorganic materials 0.000 claims description 7
- ISFYBNLVHLGKMB-UHFFFAOYSA-N tris(3,4-dimethoxyphenyl)phosphane Chemical compound COC=1C=C(C=CC=1OC)P(C1=CC(=C(C=C1)OC)OC)C1=CC(=C(C=C1)OC)OC ISFYBNLVHLGKMB-UHFFFAOYSA-N 0.000 claims description 5
- MRUDNSFOFOQZDA-UHFFFAOYSA-N 2,6-dichlorobenzoic acid Chemical compound OC(=O)C1=C(Cl)C=CC=C1Cl MRUDNSFOFOQZDA-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 239000000654 additive Substances 0.000 claims description 4
- 230000000996 additive effect Effects 0.000 claims description 4
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 claims description 4
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 4
- 235000011007 phosphoric acid Nutrition 0.000 claims description 4
- 229960004889 salicylic acid Drugs 0.000 claims description 4
- 239000003446 ligand Substances 0.000 claims description 3
- 229940092714 benzenesulfonic acid Drugs 0.000 claims description 2
- 150000001728 carbonyl compounds Chemical class 0.000 claims 3
- 229940032330 sulfuric acid Drugs 0.000 claims 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims 1
- 229910000510 noble metal Inorganic materials 0.000 abstract description 24
- 230000006315 carbonylation Effects 0.000 abstract description 6
- 150000002736 metal compounds Chemical class 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 239000007788 liquid Substances 0.000 description 9
- 238000003756 stirring Methods 0.000 description 8
- FFRBMBIXVSCUFS-UHFFFAOYSA-N 2,4-dinitro-1-naphthol Chemical group C1=CC=C2C(O)=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 FFRBMBIXVSCUFS-UHFFFAOYSA-N 0.000 description 6
- 238000007789 sealing Methods 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 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
- 230000000694 effects Effects 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- XAOGXQMKWQFZEM-UHFFFAOYSA-N isoamyl propanoate Chemical compound CCC(=O)OCCC(C)C XAOGXQMKWQFZEM-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- -1 phosphine compound Chemical class 0.000 description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 2
- 235000019260 propionic acid Nutrition 0.000 description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 239000001117 sulphuric acid Substances 0.000 description 2
- 235000011149 sulphuric acid Nutrition 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- QGLVWTFUWVTDEQ-UHFFFAOYSA-N 2-chloro-3-methoxyphenol Chemical compound COC1=CC=CC(O)=C1Cl QGLVWTFUWVTDEQ-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 238000005882 aldol condensation reaction Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical group 0.000 description 1
- 229940117927 ethylene oxide Drugs 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical class [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 description 1
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
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- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/19—Catalysts containing parts with different compositions
-
- 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
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
-
- 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
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2213—At least two complexing oxygen atoms present in an at least bidentate or bridging ligand
-
- 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
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/36—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates
- C07C67/38—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates by addition to an unsaturated carbon-to-carbon bond
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/845—Cobalt
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- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/128—Halogens; Compounds thereof with iron group metals or platinum group metals
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- 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
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0255—Phosphorus containing compounds
- B01J31/0267—Phosphines or phosphonium compounds, i.e. phosphorus bonded to at least one carbon atom, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, the other atoms bonded to phosphorus being either carbon or hydrogen
- B01J31/0268—Phosphonium compounds, i.e. phosphine with an additional hydrogen or carbon atom bonded to phosphorous so as to result in a formal positive charge on phosphorous
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
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- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention relates to a catalyst composition for synthesizing methyl propionate from ethylene, which comprises a non-noble metal compound main catalyst shown in a general formula (I), an organic phosphorus compound, an optional acidic auxiliary agent and an optional solvent. The invention also relates to a method for synthesizing methyl propionate from ethylene, methanol and carbon monoxide through a carbonyl combination reaction in the presence of the catalyst composition. The catalyst composition provided by the invention has the characteristics of high conversion rate, good selectivity and long service life when used for synthesizing methyl propionate from ethylene, has good catalytic activity and selectivity at a lower temperature and a lower pressure, can efficiently catalyze carbonylation of ethylene and methanol to synthesize methyl propionate, has a reaction result of ethylene, and has a highest yield of 93% of methyl propionate, and a good commercial value. [ Co (X)a](BF4)2·(6‑b)H2O(I)。
Description
Technical Field
The invention belongs to the technical field of organic chemical products synthesized by ethylene carbonylation, and particularly relates to a catalyst composition for synthesizing methyl propionate by ethylene and a synthesis method thereof.
Background
Methyl propionate is a colorless and transparent organic liquid, is widely used as a solvent for high-grade food and cosmetics, and can also be used as an excellent additive, preservative or spice for partial food and feed. Methyl propionate can be subjected to aldol condensation reaction with formaldehyde to generate an important chemical synthesis raw material Methyl Methacrylate (MMA), and various products such as acrylic acid, propionic acid and propionate (benzyl propionate, isoamylpropionate and the like) can also be prepared through saponification reaction, hydrolysis reaction and ester exchange reaction, so that the development of a synthesis process of methyl propionate is beneficial to the progress and development of the process technologies such as propionic acid, propionate and the like.
Most of catalyst systems used for synthesizing methyl propionate by carbonylation reaction are noble metal complex systems, and palladium (II) salt and tridentate phosphine compound are used as main active components, for example, a palladium (II) compound, aryl substituted phosphine and acid system are involved in patent CN87110635 of SHELL company, and are used for carbonylation reaction of ethylene and methanol; in chinese patent CN103319337, a composite catalyst system with palladium acetate as a main catalyst and metal ions such as cobalt, nickel or ruthenium as an auxiliary catalyst is adopted. The catalyst system has the characteristics of taking noble metal palladium as a main active component, mild reaction condition, complete conversion and high selectivity. However, the use of expensive noble metals results in catalyst costs that represent a significant portion of the overall production costs, which are high.
Currently, non-noble metal catalyst systems for the synthesis of methyl propionate by carbonylation have also attracted extensive academic attention. Literature [ r.f.heck, j.a.m.chem.soc.1963, 85; w.keim.j.mol.catal.,1989,54(1) ] shows that ruthenium, nickel, cobalt, etc. complex catalysts are active in the oxo synthesis of methyl propionate from carbon monoxide/methanol/ethylene. However, the non-noble metal catalyst systems have the defects of harsh reaction conditions, low conversion rate and poor selectivity, and basically have no commercial application prospect.
Therefore, there is a need to develop a catalyst composition for synthesizing methyl propionate from ethylene with low production cost and high efficiency, and a synthesis method thereof.
Disclosure of Invention
The technical problem to be solved by the present invention is to provide a catalyst composition for synthesizing methyl propionate from ethylene, which is a non-noble metal catalyst composition, and comprises a non-noble metal compound main catalyst shown in general formula (I), an organic phosphorus compound, an optional acidic auxiliary agent, and an optional solvent. The invention also provides a method for synthesizing methyl propionate by ethylene, which overcomes the defects of harsh reaction conditions, low conversion rate and poor selectivity of a non-noble metal catalyst system, avoids using expensive noble metals, greatly reduces the catalyst cost and increases the process added value.
To this end, the invention provides a catalyst composition for synthesizing methyl propionate from ethylene, which comprises a catalyst, an optional acidic auxiliary agent and an optional solvent; wherein the catalyst comprises a main catalyst and an organophosphorus compound.
In some embodiments of the invention, the mass ratio of the main catalyst, the organic phosphorus compound, the acidic auxiliary agent and the solvent is 1 (0.05-20.0): 0-3.0): 0-20.0; preferably 1 (0.35-10.26): (0.23-2.5): 0.56-20.0).
According to the invention, the main catalyst is a compound shown in a general formula (I);
[Co(X)a](BF4)2·(6-b)H2O (I)
wherein a is more than or equal to 0 and less than or equal to 6; b is more than or equal to 0 and less than or equal to 6; x is a ligand capable of coordinating with Co; preferably, X comprises Tetrahydrofuran (THF) and/or CH3CN。
In some embodiments of the invention, the compound of formula (I) comprises [ Co (THF) ]6](BF4)2、[Co(CH3CN)6](BF4)2And Co (BF)4)2·6H2One or more of O.
In other embodiments of the present invention, the organophosphorus compound includes triphenylphosphine and/or tris (3, 4-dimethoxyphenyl) phosphine.
In some embodiments of the invention, the acidic adjuvant is an acid; preferably the acid comprises one or more of benzene sulphonic acid, methyl benzene sulphonic acid, sulphuric acid, salicylic acid, orthophosphoric acid and 2, 6-dichlorobenzoic acid.
In other embodiments of the present invention, the solvent comprises water (H)2O), Tetrahydrofuran (THF) and acetonitrile (CH)3CN) is selected.
In a second aspect, the invention provides a method for synthesizing methyl propionate from ethylene, which is to synthesize methyl propionate by the carbonylation reaction of ethylene with methanol and carbon monoxide in the presence of the catalyst composition according to the first aspect of the invention.
According to the invention, the catalyst composition comprises, based on the weight of methanol:
in some preferred embodiments of the present invention, the catalyst composition comprises, based on the weight of methanol:
in some embodiments of the invention, the reaction pressure of the carbonylation reaction is from 1.5 to 8.0 MPa; preferably, the reaction pressure of the carbonyl combination reaction is 4.0-6.0 MPa; more preferably, the reaction pressure of the carbonylation reaction is 5.0 to 6.0 MPa.
In other embodiments of the invention, the reaction temperature of the carbonylation reaction is from 70 ℃ to 110 ℃; the reaction temperature of the carbonylation reaction is preferably 80 to 90 ℃.
In other embodiments of the present invention, the reaction time of the carbonylation reaction is 3-5 hours; the reaction time of the carbonyl combination reaction is preferably 3 to 4 hours.
In some embodiments of the invention, the molar ratio of carbon monoxide to ethylene is (1-5): 1; preferably, the molar ratio of carbon monoxide to ethylene is (1-2): 1; more preferably, the molar ratio of carbon monoxide to ethylene is (1-1.5): 1.
Detailed Description
In order that the present invention may be more readily understood, the following detailed description of the invention is given by way of example only, and is not intended to limit the scope of the invention.
In view of the disadvantage of high cost of the existing noble metal catalyst system, and the disadvantage of harsh reaction conditions, low conversion rate and poor selectivity of the existing non-noble metal catalyst system, the inventor of the invention has conducted extensive and intensive research on the catalyst composition for synthesizing methyl propionate from ethylene, and found that the non-noble metal catalyst composition comprising the non-noble metal compound main catalyst shown in the general formula (I), the organic phosphorus compound, the optional acidic auxiliary agent and the optional solvent can overcome the disadvantages of harsh reaction conditions, low conversion rate and poor selectivity of the non-noble metal catalyst system, and simultaneously avoid using expensive noble metals and overcome the disadvantage of high cost of the noble metal catalyst system. The catalyst composition is used for synthesizing methyl propionate from ethylene, has the characteristics of high conversion rate, good selectivity and long service life, has good catalytic activity and selectivity at lower temperature and lower pressure, and can efficiently catalyze carbonylation of ethylene and methanol to synthesize methyl propionate. The present invention has been made based on the above findings.
Therefore, the catalyst composition for synthesizing methyl propionate from ethylene according to the first aspect of the present invention comprises a catalyst, an optional acidic auxiliary agent, and an optional solvent; wherein the catalyst comprises a main catalyst and an organophosphorus compound.
In the catalyst composition, the mass ratio of the main catalyst, the organic phosphorus compound, the acid auxiliary agent and the solvent is 1 (0.05-20.0): (0-3.0): 0-20.0); preferably 1 (0.35-10.26): (0.23-2.5): 0.56-20.0); more preferably 1 (0.77-1.58): (0.23-1.13): 0.56-10.0); further preferred are 1 (1.0-1.14): (0.25-0.5): 1.11-4.0).
In the catalyst composition, the main catalyst is a compound shown in a general formula (I);
[Co(X)a](BF4)2·(6-b)H2O (I)
wherein a is more than or equal to 0 and less than or equal to 6; b is more than or equal to 0 and less than or equal to 6; x is a ligand capable of coordinating with Co; preferably, X comprises Tetrahydrofuran (THF) and/or CH3CN。
In the above catalyst composition, the compound represented by the general formula (I) includes [ Co (THF) ]6](BF4)2、[Co(CH3CN)6](BF4)2And Co (BF)4)2·6H2One or more of O.
In the above catalyst composition, the organophosphorus compound includes triphenylphosphine and/or tris (3, 4-dimethoxyphenyl) phosphine.
In the catalyst composition, the acid auxiliary agent is an acid; preferably the acid comprises one or more of benzene sulphonic acid, methyl benzene sulphonic acid, sulphuric acid, salicylic acid, orthophosphoric acid and 2, 6-dichlorobenzoic acid.
In the invention, the acid auxiliary agent is preferably an acid with larger steric hindrance, because the acid with larger steric hindrance is favorable for the close combination of the complex formed by the main catalyst of the compound shown in the general formula (I) and the organic phosphorus compound and reactants in the carbonylation reaction process, thereby being favorable for improving the reaction efficiency.
In the above catalyst composition, the solvent comprises water (H)2O), Tetrahydrofuran (THF) and acetonitrile (CH)3CN) is selected.
In the process for synthesizing methyl propionate from ethylene according to the second aspect of the present invention, ethylene is subjected to a carbonylation reaction with methanol and carbon monoxide in the presence of the catalyst composition according to the first aspect of the present invention to synthesize methyl propionate.
In the method for synthesizing methyl propionate from ethylene, the content of the main catalyst is 0.5wt% -10.0wt% based on the weight of methanol; preferably, the content of the main catalyst is 0.5-4.5 wt%; more preferably, the content of the main catalyst is 1.0 wt% to 4.5 wt%; further preferably, the content of the main catalyst is 2.5wt% to 4.5 wt%.
In the method for synthesizing methyl propionate by ethylene, the content of the organophosphorus compound is 0.5wt% to 10.0wt% based on the weight of the methanol; preferably, the content of the organophosphorus compound is 1.58 to 5.13 wt%; more preferably, the content of the organophosphorus compound is 1.93% by weight to 4.9% by weight.
In the above method for synthesizing methyl propionate from ethylene, the acidic auxiliary agent is an optional added component; the content of the acid additive is less than or equal to 1.5wt% based on the weight of the methanol; preferably, the content of the acidic auxiliary agent is 1.03-1.25 wt%; more preferably, the content of the acid auxiliary agent is 1.13 wt% to 1.25 wt%.
In the above method for synthesizing methyl propionate from ethylene, the solvent is an optional added component; the content of the solvent is less than or equal to 10.0wt% based on the weight of the methanol; preferably, the content of the solvent is 2.5wt% to 10.0 wt%; more preferably, the solvent is present in an amount of 5.0 wt% to 10.0 wt%.
In the method for synthesizing methyl propionate from ethylene, the reaction pressure of the carbonyl combination reaction is 1.5-8.0 MPa; preferably, the reaction pressure of the carbonyl combination reaction is 4.0-6.0 MPa; more preferably, the reaction pressure of the carbonylation reaction is 5.0 to 6.0 MPa.
In the method for synthesizing methyl propionate from ethylene, the reaction temperature of the carbonyl combination reaction is 70-110 ℃; the reaction temperature of the carbonylation reaction is preferably 80 to 90 ℃.
In the method for synthesizing methyl propionate from ethylene, the reaction time of the carbonyl combination reaction is 3-5 h; the reaction time of the carbonyl combination reaction is preferably 3 to 4 hours; more preferably, the reaction time of the carbonyl combination reaction is 4 hours.
In the above method for synthesizing methyl propionate from ethylene, the molar ratio of carbon monoxide to ethylene (i.e. n (CO): n (C)2H2) Is (1-5) 1; preferably, the molar ratio of carbon monoxide to ethylene is (1-2): 1; more preferably, the molar ratio of carbon monoxide to ethylene is (1-1.5): 1; it is further preferred that the molar ratio of carbon monoxide to ethylene is 1: 1.
In some embodiments of the present invention, the step of synthesizing methyl propionate from ethylene comprises: a certain amount of methanol, a main catalyst, an organic phosphorus compound, an optional acid auxiliary agent and an optional solvent are weighed into a 1.5L autoclave, and the autoclave is closed. Then replacing the air in the autoclave with 1.0MPa nitrogen for three times, introducing mixed gas of ethylene and carbon monoxide with a certain proportion relationship into the autoclave under the stirring condition for replacement for 5min, wherein the stirring speed is 400r/min, gradually increasing the pressure until the reaction pressure is 1.5-8.0MPa, and simultaneously heating the reactor to the reaction temperature of 70-110 ℃. After a certain period of reaction, liquid samples were taken for chromatographic analysis.
The catalyst used in the present invention can be prepared from commercially available starting materials.
The term "water" as used herein refers to deionized water unless otherwise specified.
The term "optional" as used herein means either with or without, and with or without the addition of.
Components in the scope of "≦" definitions in the present invention refer to optional or optional added components. For example, "the content of the acid builder is 1.5 wt%" means that the acid builder is an optional added component and the amount thereof added is 0. ltoreq. the content of the acid builder 1.5 wt%. As another example, "the content of the solvent is 10.0 wt%", means that the solvent is an optional added component, and the amount thereof added is 0. ltoreq. solvent.ltoreq.10.0 wt%.
The inventor of the invention researches and discovers that a non-noble metal compound shown in a general formula (I) is used as a main catalyst, the non-noble metal compound can form a complex with proper coordination and combination with an organophosphorus compound, and a non-noble metal catalyst composition containing the complex can show high reaction activity and selectivity in the carbonylation reaction of synthesizing methyl propionate from ethylene.
The addition of the solvent and the acid auxiliary agent can further improve the activity and selectivity of the catalyst for synthesizing methyl propionate by ethylene carbonylation.
The catalyst composition for synthesizing methyl propionate from ethylene provided by the invention adopts the catalyst composition of the non-noble metal compound main catalyst shown in the general formula (I), can overcome the defects of harsh reaction conditions, low conversion rate and poor selectivity of a non-noble metal catalyst system, simultaneously avoids using expensive noble metal, greatly reduces the catalyst cost (the catalyst cost is only less than 10% of that of a catalyst taking noble metal palladium as a main active component), and increases the process added value. The catalytic composition is used for synthesizing methyl propionate from ethylene, has the characteristics of high conversion rate, good selectivity and long service life, has good catalytic activity and selectivity at lower temperature and lower pressure, can efficiently catalyze carbonylation of ethylene and methanol to synthesize methyl propionate, has a reaction result of ethylene, can reach a maximum yield of 93 percent of methyl propionate, and has good commercial value.
Examples
Example 1
400g of methanol and Co (BF) are added into a 1.5L high-pressure reaction kettle4)2·6H2And O2 g and triphenylphosphine 2g are sealed. According to the formula n (CO): n (C)2H2) Introducing CO and ethylene at the ratio of 1.5:1, stirring at the speed of 400r/min, the reaction temperature of 80 ℃, the reaction pressure of 5.0MPa and the reaction time of 4 h. The selectivity of methyl propionate is 87% in terms of ethylene, and the residue is golden yellow transparent liquid.
Example 2
400g of methanol and Co (BF) are added into a 1.5L high-pressure reaction kettle4)2·6H2O10 g, triphenylphosphine 7.7g, benzenesulfonic acid 5g and distilled water 40g, and then sealing. According to the formula n (CO): n (C)2H2) Introducing CO and ethylene at the ratio of 1:1, stirring at the speed of 400r/min, the reaction temperature of 90 ℃, the reaction pressure of 5.0MPa and the reaction time of 4 h. The selectivity to methyl propionate was 93% in terms of ethylene, and the bottoms were golden yellow transparent liquids.
Example 3
Into a 1.5L autoclave were charged 400g of methanol, [ Co (CH) ]3CN)6](BF4)24g, 6.33g of tris (3, 4-dimethoxyphenyl) phosphine, 4.5g of salicylic acid and 40g of distilled water, and then sealing. According to the formula n (CO): n (C)2H2) Introducing CO and ethylene at a ratio of 2:1, stirring at 400r/min, reacting at 80 ℃ under 4.0MPa for 4 h. The selectivity of methyl propionate is 86% in terms of ethylene, and the residue is golden yellow transparent liquid.
Example 4
Into a 1.5L autoclave were charged 400g of methanol, [ Co (THF) ]6](BF4)218g, 20.5g of tris (3, 4-dimethoxyphenyl) phosphine, 4.5g of orthophosphoric acid and 20g of distilled water, and then sealing. According to the formula n (CO): n (C)2H2) Introducing CO and ethylene at a ratio of 2:1, stirring at 400r/min, reacting at 90 ℃ under 6.0MPa for 4 h. The selectivity of methyl propionate is 91% in terms of ethylene, and the residue is golden yellow transparent liquid.
Example 5
Into a 1.5L autoclave were charged 400g of methanol, [ Co (THF) ]6](BF4)218g of triphenylphosphine, 19.6g of 2, 6-dichlorobenzoic acid, 4.1g of CH3CN10 g later and sealing. According to the formula n (CO): n (C)2H2) Introducing CO and ethylene at a ratio of 2:1, stirring at 400r/min, reacting at 90 ℃ under 6.0MPa for 4 h. The selectivity of methyl propionate is 90% calculated by ethylene, and the kettle liquid is golden yellow transparent liquid.
Comparative example 1
To a 1.5L autoclave were added 400g of methanol, Co (OAC)2·4H2O4 g, triphenylphosphine 4.22g and distilled water 24g, and then sealing. According to the formula n (CO): n (C)2H2) Introducing CO and ethylene at the ratio of 1:1, stirring at the speed of 400r/min, the reaction temperature of 80 ℃, the reaction pressure of 4.0MPa and the reaction time of 4 h. The selectivity to methyl propionate was 61% based on ethylene, and the bottoms were golden yellow translucent liquids, with some precipitation.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (15)
1. A catalyst composition for synthesizing methyl propionate by ethylene comprises a catalyst, an optional acidic auxiliary agent and an optional solvent; the catalyst comprises a main catalyst and an organic phosphorus compound; the mass ratio of the main catalyst, the organic phosphorus compound, the acid auxiliary agent and the solvent is 1 (0.05-20.0) to (0-3.0) to (0-20.0); the main catalyst is a compound shown in a general formula (I);
[Co(X)a](BF4)2·(6-b)H2O （I）
wherein a is more than or equal to 0 and less than or equal to 6; b is more than or equal to 0 and less than or equal to 6; x is a ligand capable of coordinating with Co;
the organophosphorus compound comprises triphenylphosphine and/or tri (3, 4-dimethoxyphenyl) phosphine; the acidic auxiliary agent is acid.
2. The catalyst composition of claim 1, wherein the mass ratio of the main catalyst, the organic phosphorus compound, the acidic assistant and the solvent is 1 (0.35-10.26): 0.23-2.5): 0.56-20.0.
3. The catalyst composition of claim 1,
the X comprises tetrahydrofuran and/or CH3CN。
4. The catalyst composition according to any one of claims 1 to 3, wherein the compound of formula (I) comprises [ Co (THF)6](BF4)2、[Co(CH3CN)6](BF4)2And Co (BF)4)2·6H2One or more of O.
5. The catalyst composition of any one of claims 1-3, wherein the solvent comprises one or more of water, tetrahydrofuran, and acetonitrile.
6. The catalyst composition of claim 1, wherein the acid comprises one or more of benzene sulfonic acid, methyl benzene sulfonic acid, sulfuric acid, salicylic acid, orthophosphoric acid, and 2, 6-dichlorobenzoic acid.
7. A process for synthesizing methyl propionate from ethylene by the oxo reaction of ethylene with methanol and carbon monoxide in the presence of a catalyst composition as claimed in any one of claims 1 to 6.
8. The process of claim 7, wherein the catalyst composition comprises, based on the weight of methanol:
component a, 0.5wt% -10.0wt% of main catalyst;
component b, 0.5 to 10.0 weight percent of organic phosphorus compound;
component c, the acid additive is less than or equal to 1.5 wt%;
the component d is less than or equal to 10.0wt% of solvent.
9. The process of claim 8, wherein the catalyst composition comprises, based on the weight of methanol:
component a, 0.5wt% -4.5wt% of main catalyst;
component b, organic phosphorus compound 1.58wt% -5.13 wt%;
component c, 1.03-1.25 wt% of acid additive;
component d, solvent 2.5wt% -10.0 wt%.
10. The method according to any one of claims 7 to 9,
the reaction pressure of the carbonyl combination reaction is 1.5-8.0 MPa; the reaction temperature of the carbonyl compound reaction is 70-110 ℃; the reaction time of the carbonyl compound reaction is 3-5 h.
11. The method according to claim 10, wherein the reaction pressure of the carbonylation reaction is 4.0 to 6.0 MPa; the reaction temperature of the carbonyl combination reaction is 80-90 ℃; the reaction time of the carbonyl compound reaction is 3-4 h.
12. The method according to any one of claims 7 to 9, wherein the reaction pressure of the carbonylation reaction is 5.0 to 6.0 MPa.
13. The process according to any one of claims 7 to 9, wherein the molar ratio of carbon monoxide to ethylene is (1-5): 1.
14. The process of claim 13, wherein the molar ratio of carbon monoxide to ethylene is (1-2): 1.
15. The process of claim 14, wherein the molar ratio of carbon monoxide to ethylene is (1-1.5): 1.
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| EP0105704A1 (en) * | 1982-09-30 | 1984-04-18 | The British Petroleum Company p.l.c. | Process for the production of carboxylic acid esters and/or carboxylic acid |
| CN103319337A (en) * | 2013-06-28 | 2013-09-25 | 西南化工研究设计院有限公司 | Method for synthesizing methyl propionate by ethylene |
| CN103387490A (en) * | 2012-05-09 | 2013-11-13 | 中国科学院兰州化学物理研究所 | Method for synthesizing phenylacetic acid by carbonylation of methylbenzene |
| CN105541610A (en) * | 2016-01-13 | 2016-05-04 | 河北工业大学 | Method for synthesizing methyl propionate with carbon dioxide and ethylene |
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| EP0105704A1 (en) * | 1982-09-30 | 1984-04-18 | The British Petroleum Company p.l.c. | Process for the production of carboxylic acid esters and/or carboxylic acid |
| CN103387490A (en) * | 2012-05-09 | 2013-11-13 | 中国科学院兰州化学物理研究所 | Method for synthesizing phenylacetic acid by carbonylation of methylbenzene |
| CN103319337A (en) * | 2013-06-28 | 2013-09-25 | 西南化工研究设计院有限公司 | Method for synthesizing methyl propionate by ethylene |
| CN105541610A (en) * | 2016-01-13 | 2016-05-04 | 河北工业大学 | Method for synthesizing methyl propionate with carbon dioxide and ethylene |
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