CN114768884A - Immobilized catalyst for ethylene carbonate production, preparation method and application - Google Patents
Immobilized catalyst for ethylene carbonate production, preparation method and application Download PDFInfo
- Publication number
- CN114768884A CN114768884A CN202210480632.7A CN202210480632A CN114768884A CN 114768884 A CN114768884 A CN 114768884A CN 202210480632 A CN202210480632 A CN 202210480632A CN 114768884 A CN114768884 A CN 114768884A
- Authority
- CN
- China
- Prior art keywords
- chlorine
- ethylene carbonate
- porous resin
- resin microspheres
- triphenylphosphine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003622 immobilized catalyst Substances 0.000 title claims abstract description 38
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 76
- 239000000460 chlorine Substances 0.000 claims abstract description 76
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 76
- 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 abstract description 76
- 239000004005 microsphere Substances 0.000 claims abstract description 57
- 239000011347 resin Substances 0.000 claims abstract description 53
- 229920005989 resin Polymers 0.000 claims abstract description 53
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- 239000003054 catalyst Substances 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 18
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 15
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims abstract description 13
- 150000001450 anions Chemical class 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 64
- 229910052742 iron Inorganic materials 0.000 claims description 40
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 22
- 238000005406 washing Methods 0.000 claims description 15
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 13
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 claims description 12
- 239000001263 FEMA 3042 Substances 0.000 claims description 12
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 claims description 12
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 claims description 12
- 229940033123 tannic acid Drugs 0.000 claims description 12
- 235000015523 tannic acid Nutrition 0.000 claims description 12
- 229920002258 tannic acid Polymers 0.000 claims description 12
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 claims description 10
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims description 10
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 10
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 10
- QKIUAMUSENSFQQ-UHFFFAOYSA-N dimethylazanide Chemical compound C[N-]C QKIUAMUSENSFQQ-UHFFFAOYSA-N 0.000 claims description 10
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 10
- 238000011068 loading method Methods 0.000 claims description 10
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 8
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 8
- 239000012279 sodium borohydride Substances 0.000 claims description 8
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 7
- 239000001569 carbon dioxide Substances 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 239000007790 solid phase Substances 0.000 claims description 5
- 238000000967 suction filtration Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 10
- 239000002994 raw material Substances 0.000 abstract description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract 1
- 229910052799 carbon Inorganic materials 0.000 abstract 1
- 239000000543 intermediate Substances 0.000 description 20
- 239000003921 oil Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 6
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000011038 discontinuous diafiltration by volume reduction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- PLHJDBGFXBMTGZ-WEVVVXLNSA-N furazolidone Chemical compound O1C([N+](=O)[O-])=CC=C1\C=N\N1C(=O)OCC1 PLHJDBGFXBMTGZ-WEVVVXLNSA-N 0.000 description 1
- 229960001625 furazolidone Drugs 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 230000003100 immobilizing effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000012048 reactive intermediate Substances 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical class [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 229920001864 tannin Polymers 0.000 description 1
- 235000018553 tannin Nutrition 0.000 description 1
- 239000001648 tannin Substances 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
Images
Classifications
-
- 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
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
-
- 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
- B01J31/0269—Phosphorus containing compounds on mineral substrates
-
- 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
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/069—Hybrid organic-inorganic polymers, e.g. silica derivatized with organic groups
-
- 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
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D317/34—Oxygen atoms
- C07D317/36—Alkylene carbonates; Substituted alkylene carbonates
- C07D317/38—Ethylene carbonate
-
- 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
- B01J2531/842—Iron
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention relates to the technical field of catalysts, and provides a preparation method of an immobilized catalyst for producing ethylene carbonate‑Synthesizing the immobilized catalyst for coordinating anions; the preparation method provided by the invention takes chlorine-containing porous resin microspheres as a carrier, triphenylphosphine as a main active component, dimethylformamide as a solvent, and I‑For coordinating anions, immobilized catalysts are synthesized in the presence of ethylene oxide and dioxideIn the reaction process of preparing the ethylene carbonate by the carbon addition method, the conversion rate of the raw material ethylene oxide and the selectivity of the product ethylene carbonate are high, and after repeated use, the catalytic performance of the catalyst is not obviously reduced, which indicates that the immobilized catalyst has good catalytic performance and long service life.
Description
Technical Field
The invention relates to the technical field of catalysts, and particularly relates to an immobilized catalyst for producing ethylene carbonate, a preparation method and application.
Background
Ethylene Carbonate (EC) is an organic solvent with excellent performance and can dissolve various polymers; in addition, the product can be used as an organic intermediate to replace ethylene oxide for a dioxygenation reaction and is a main raw material for producing dimethyl carbonate by a transesterification method; can also be used as raw materials for synthesizing furazolidone, water glass series sizing agent, fiber finishing agent and the like; in addition, the electrolyte is also applied to lithium battery electrolytes. Ethylene carbonate is also useful as a reactive intermediate in the production of lubricating oils and greases.
Ethylene oxide and carbon dioxide are commonly used for preparing ethylene carbonate at present by an addition method, the addition method is a reaction with heat release and volume reduction, from the aspect of chemical balance, the low-temperature and high-pressure conditions are favorable for the reaction, and meanwhile, the selection of a proper catalyst is the key for the smooth proceeding of the reaction, and the system of the reaction is mainly a homogeneous catalysis system. Homogeneous catalytic systems have good catalytic performance, but have a problem that the catalyst and the product are difficult to separate after the reaction is finished, which affects the purity of the product on one hand and causes unnecessary loss of the catalyst on the other hand.
Disclosure of Invention
The invention provides an immobilized catalyst for ethylene carbonate production, a preparation method and application thereof, and the problem that the catalyst and a product are difficult to separate is effectively solved by immobilizing the catalyst.
The invention provides a preparation method of an immobilized catalyst for producing ethylene carbonate, which takes chlorine-containing porous resin microspheres as a carrier, triphenylphosphine as a main active component, dimethylformamide as a solvent, and I-Synthesizing the immobilized catalyst for coordinating anions.
The invention provides a supported catalyst for producing ethylene carbonate, which is prepared by the preparation method.
The third aspect of the invention provides an application of the immobilized catalyst for producing ethylene carbonate, in particular to a reaction process for preparing ethylene carbonate by using ethylene oxide and carbon dioxide as raw materials.
The technical scheme of the embodiment of the invention at least has the following advantages and beneficial effects:
the preparation method provided by the invention takes chlorine-containing porous resin microspheres as a carrier, triphenylphosphine as a main active component, dimethylformamide as a solvent, and I-The immobilized catalyst is synthesized for coordinating anions, the conversion rate of the raw material ethylene oxide and the selectivity of the product ethylene carbonate are higher in the reaction process of preparing the ethylene carbonate by the addition method of the ethylene oxide and the carbon dioxide, and the catalytic performance of the catalyst is not obviously reduced after the immobilized catalyst is repeatedly used for many times, which shows that the immobilized catalyst has good catalytic performance and long service life.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and those skilled in the art can also obtain other related drawings based on the drawings without inventive efforts.
Fig. 1 is a scanning electron microscope image of an immobilized catalyst for ethylene carbonate production provided in example 1 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The specific embodiment provides a preparation method of an immobilized catalyst for producing ethylene carbonate, which takes chlorine-containing porous resin microspheres as carriersTriphenyl phosphine as main active component and dimethyl formamide as solvent, I-The method for synthesizing the immobilized catalyst for coordinating anions specifically comprises the following steps:
s1, respectively adding the chlorine-containing porous resin microspheres and triphenylphosphine into dimethyl amide, and heating for reaction to obtain a chlorine-containing intermediate;
and S2, washing the chlorine-containing intermediate, placing the chlorine-containing intermediate into a KI solution, and keeping the temperature and standing to obtain the immobilized catalyst.
Further, in step S1, the chlorine-containing porous resin microspheres are: triphenylphosphine: dimethylamide ═ 1: (0.4-0.6): (6-8).
Further, in step S2, the chlorine-containing intermediate: KI solution 1: (4-6), wherein the concentration of the KI solution is 20 wt%.
Further, step S1 includes:
s11 preparation of chlorine-containing porous resin microspheres with porous structures
And sequentially adding vinylidene chloride, benzoyl peroxide, ethylene glycol dimethacrylate, toluene and white oil into deionized water, reacting for 8 hours at 70 ℃, filtering out a solid phase, and washing to obtain the chlorine-containing porous resin microspheres.
Wherein, according to the mass ratio, the vinylidene chloride: benzoyl peroxide: ethylene glycol dimethacrylate: toluene: white oil 1: (1-1.4): (0.4-0.6): (4-6): (10-12).
Wherein the grain diameter of the chlorine-containing porous resin microspheres is 500-550 nanometers.
Further, step S1 includes:
s12, loading nano iron on chlorine-containing porous resin microspheres
And simultaneously placing the chlorine-containing porous resin microspheres and iron chloride powder into ethanol, dropwise adding a sodium borohydride solution while stirring, reacting for 10min, carrying out suction filtration, and washing to obtain the nano-iron-loaded chlorine-containing porous resin microspheres.
The surface of the chlorine-containing porous resin microsphere is rough, after ferric chloride is adsorbed, the surface of the chlorine-containing porous resin microsphere is rough, and the chlorine-containing porous resin microsphere is adsorbed on the surface of the microsphere after the ferric chloride is reduced into nano zero-valent iron, so that the surface roughness of the chlorine-containing porous resin microsphere is further increased, namely the specific surface area of the surface of the microsphere is increased, and the catalytic reaction efficiency is favorably improved.
Further, step S1 includes:
s13, loading nano iron on triphenylphosphine
And (3) placing triphenylphosphine into an iron chloride solution, stirring for 30min, standing for 4h, filtering, and drying to obtain the triphenylphosphine loaded with nano iron.
The iron can be better adsorbed with the triphenylphosphine by utilizing the ligand action of the triphenylphosphine and the iron, and the triphenylphosphine can be well adsorbed on the surfaces of the chlorine-containing porous resin microspheres due to the existence of the iron on the surfaces of the chlorine-containing porous resin microspheres.
Further, tannic acid is added in step S1, and the chlorine-containing porous resin microspheres are added in a mass ratio of: tannic acid 1: (0.5-0.7).
Through the complexation of the tannic acid and the iron, the triphenylphosphine can be more stably adsorbed on the surface of the chlorine-containing porous resin microsphere, so that the service life of the catalyst is effectively prolonged.
Example 1
The preparation method of the immobilized catalyst for producing the ethylene carbonate comprises the following steps:
s1 preparation of chlorine-containing intermediate
S11, preparing chlorine-containing porous resin microspheres with porous structures
Sequentially adding vinylidene chloride, benzoyl peroxide, ethylene glycol dimethacrylate, toluene and white oil into deionized water, wherein the mass ratio of the vinylidene chloride: benzoyl peroxide: ethylene glycol dimethacrylate: toluene: white oil 1: 1.2: 0.5: 5: 11, reacting at 70 ℃ for 8 hours, filtering out a solid phase, washing and drying to obtain the chlorine-containing porous resin microspheres with the particle size of 520 nanometers.
S12, loading nano iron on chlorine-containing porous resin microspheres
Mixing chlorine-containing porous resin microspheres with ferric chloride powder according to a mass ratio of 1: and 4, simultaneously placing the microspheres in 500mL of ethanol, dropwise adding a sodium borohydride solution (with the concentration of 15 wt%) at the rate of 20 drops/minute while stirring, stirring and reacting for 10min, stopping dropwise adding the sodium borohydride solution, performing suction filtration, and washing to obtain the chlorine-containing porous resin microspheres loaded with nano-iron.
S13, loading nano iron on triphenylphosphine
And (2) placing triphenylphosphine into an iron chloride solution (with the concentration of 30 wt%), stirring for 30min, standing for 4h, filtering, and drying to obtain the triphenylphosphine loaded with nano-iron.
S14 preparation of chlorine-containing intermediate
Firstly, respectively adding chlorine-containing porous resin microspheres loaded with nano-iron and triphenylphosphine loaded with nano-iron into dimethyl amide, heating to 50 ℃, stirring for 10 minutes, then slowly pouring tannic acid, continuously stirring in the pouring process, reacting for 30 minutes under a stirring environment, standing for 6 hours, filtering, cleaning and drying to obtain a chlorine-containing intermediate;
wherein, the chlorine-containing porous resin microspheres loaded with nano iron are calculated according to the mass ratio: triphenylphosphine loaded with nano-iron: dimethyl amide: tannic acid ═ 1: 0.5: 7: 0.6.
s2, placing the chlorine-containing intermediate obtained in the step S1 into a KI solution (the concentration is 20 wt%), wherein the mass ratio of the chlorine-containing intermediate: KI solution 1: and 5, keeping the temperature at 35 ℃ and standing for 8 hours, taking out, washing and drying to obtain the immobilized catalyst A1.
Example 2
The preparation method of the immobilized catalyst for producing the ethylene carbonate comprises the following steps:
s1 preparation of chlorine-containing intermediate
S11 preparation of chlorine-containing porous resin microspheres with porous structures
Sequentially adding vinylidene chloride, benzoyl peroxide, ethylene glycol dimethacrylate, toluene and white oil into deionized water, wherein the mass ratio of the vinylidene chloride: benzoyl peroxide: ethylene glycol dimethacrylate: toluene: white oil 1: 1: 0.4: 4: 10, reacting at 70 ℃ for 8 hours, filtering out a solid phase, washing and drying to obtain the chlorine-containing porous resin microspheres with the particle size of 500 nanometers.
S12, loading nano iron on chlorine-containing porous resin microspheres
Mixing chlorine-containing porous resin microspheres with ferric chloride powder according to a mass ratio of 1: 3, simultaneously placing the mixture into 500mL of ethanol, dropwise adding a sodium borohydride solution (with the concentration of 15 wt%) at the rate of 20 drops/minute while stirring, stirring and reacting for 10min, stopping dropwise adding the sodium borohydride solution, carrying out suction filtration, and washing to obtain the chlorine-containing porous resin microspheres loaded with nano-iron.
S13, loading nano iron on triphenylphosphine
And (2) placing triphenylphosphine into an iron chloride solution (with the concentration of 30 wt%), stirring for 30min, standing for 4h, filtering, and drying to obtain the triphenylphosphine loaded with nano-iron.
S14 preparation of chlorine-containing intermediate
Firstly, respectively adding chlorine-containing porous resin microspheres loaded with nano-iron and triphenylphosphine loaded with nano-iron into dimethyl amide, heating to 50 ℃, stirring for 10 minutes, then slowly pouring tannic acid, continuously stirring in the pouring process, reacting for 30 minutes under a stirring environment, standing for 6 hours, filtering, cleaning and drying to obtain a chlorine-containing intermediate;
wherein, according to the mass ratio, the chlorine-containing porous resin microspheres loaded with nano iron: triphenylphosphine loaded with nano-iron: dimethyl amide: tannic acid ═ 1: 0.4: 6: 0.5.
s2, placing the chlorine-containing intermediate obtained in the step S1 into a KI solution (with the concentration of 20 wt%), wherein the mass ratio of the chlorine-containing intermediate: KI solution 1: and 4, keeping the temperature at 35 ℃ and standing for 8 hours, taking out, washing and drying to obtain the immobilized catalyst A2.
Example 3
The preparation method of the immobilized catalyst for producing the ethylene carbonate comprises the following steps:
s1 preparation of chlorine-containing intermediate
S11, preparing chlorine-containing porous resin microspheres with porous structures
Sequentially adding vinylidene chloride, benzoyl peroxide, ethylene glycol dimethacrylate, toluene and white oil into deionized water, wherein the mass ratio of the vinylidene chloride: benzoyl peroxide: ethylene glycol dimethacrylate: toluene: white oil 1: 1.4: 0.6: 6: 12, reacting at 70 ℃ for 8h, filtering out a solid phase, washing and drying to obtain the chlorine-containing porous resin microspheres with the particle size of 550 nanometers.
S12, loading nano iron on the chlorine-containing porous resin microspheres
Mixing chlorine-containing porous resin microspheres and iron chloride powder according to a mass ratio of 1: and 5, simultaneously placing the microspheres in 500mL of ethanol, dropwise adding a sodium borohydride solution (with the concentration of 15 wt%) at the rate of 20 drops/min while stirring, stirring and reacting for 10min, stopping dropwise adding the sodium borohydride solution, performing suction filtration, and washing to obtain the chlorine-containing porous resin microspheres loaded with nano-iron.
S13, loading nano iron on triphenylphosphine
And (3) placing triphenylphosphine into an iron chloride solution (with the concentration of 30 wt%), stirring for 30min, standing for 4h, filtering, and drying to obtain the triphenylphosphine loaded with nano-iron.
S14 preparation of chlorine-containing intermediate
Firstly, respectively adding chlorine-containing porous resin microspheres loaded with nano iron and triphenylphosphine loaded with nano iron into dimethyl amide, heating to 50 ℃, stirring for 10 minutes, then slowly pouring tannic acid, continuously stirring in the pouring process, reacting for 30 minutes under a stirring environment, standing for 6 hours, filtering, cleaning and drying to obtain a chlorine-containing intermediate;
wherein, the chlorine-containing porous resin microspheres loaded with nano iron are calculated according to the mass ratio: triphenylphosphine loaded with nano-iron: dimethyl amide: tannic acid 1: 0.6: 8: 0.7.
s2, placing the chlorine-containing intermediate obtained in the step S1 into a KI solution (with the concentration of 20 wt%), wherein the mass ratio of the chlorine-containing intermediate: KI solution 1: and 6, keeping the temperature at 35 ℃ and standing for 8 hours, taking out the mixture, washing and drying to obtain the immobilized catalyst A3.
Comparative example 1
The remaining characteristics were the same as in example 1, except that no nano-iron was supported on the chlorine-containing porous resin microspheres, and finally, supported catalyst D1 was obtained.
Comparative example 2
The remaining characteristics were the same as in example 1, except that nano-iron was not supported on triphenylphosphine, and finally, supported catalyst D2 was obtained.
Comparative example 3
The remaining characteristics were the same as in example 1, except that tannic acid was not added, and finally, an immobilized catalyst D3 was obtained.
Experimental example 1
This experimental example was used to evaluate the performance of the supported catalyst.
Weighing 10 g of immobilized catalyst (the catalyst prepared in each example and the comparative example) and placing the catalyst in a reaction kettle, replacing air in the kettle with carbon dioxide, then adding 45 g of ethylene oxide, filling carbon dioxide to 1 MPa, starting a temperature rise program, wherein the temperature rise speed is 2 ℃/min, filling carbon dioxide to the reaction pressure after raising the temperature to the reaction temperature, cooling after reacting for a period of time, blowing unreacted ethylene oxide with nitrogen, weighing the mass of the reaction mixture, and respectively calculating the conversion rate of ethylene oxide and the selectivity of ethylene carbonate, wherein the data are shown in Table 1.
Experimental example 2
This experimental example was used to test the service life of the immobilized catalyst.
The reaction was carried out in the same manner as in example 1, and after completion of the reaction, the supported catalyst was separated from the reaction product, and the reaction was repeated 5 times, and the data are shown in Table 2.
TABLE 1 Properties of the Supported catalysts
Experimental group | Conversion of ethylene oxide/%) | Selectivity of ethylene carbonate/%) |
A1 | 98.8 | 99.9 |
A2 | 98.7 | 99.9 |
A3 | 98.8 | 99.9 |
D1 | 98.1 | 99.5 |
D2 | 98.6 | 99.8 |
D3 | 98.7 | 99.9 |
TABLE 2 service life of the immobilized catalyst
As can be seen from the data in Table 1, the immobilized catalyst prepared by the method provided by the invention has good catalytic performance, the conversion rate of ethylene oxide can reach more than 98.7%, and the selectivity of ethylene carbonate can reach 99.9%.
As can be seen from the data in Table 2, the immobilized catalyst prepared by the method provided by the invention has a longer service life, and the performance of the catalyst is not obviously reduced after 5 times of repeated reactions. D1 is not loaded with nano iron on the chlorine-containing porous resin microspheres, so that triphenylphosphine is easy to fall off, and the catalytic performance of the catalyst is influenced; d2 is easy to fall off because nano iron is not loaded on triphenylphosphine, thereby affecting the catalytic performance of the catalyst; d3 has weak adsorption force of triphenylphosphine and chlorine-containing porous resin microspheres due to no tannin, so that triphenylphosphine is easy to fall off, and the catalytic performance is reduced.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and various modifications and changes will occur to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of an immobilized catalyst for ethylene carbonate production is characterized in that chlorine-containing porous resin microspheres are used as a carrier, triphenylphosphine is used as a main active component, dimethylformamide is used as a solvent, I-Synthesizing the immobilized catalyst for coordinating anions.
2. The method for preparing an immobilized catalyst for ethylene carbonate production according to claim 1, comprising the steps of:
s1, respectively adding the chlorine-containing porous resin microspheres and triphenylphosphine into dimethyl amide, and heating for reaction to obtain a chlorine-containing intermediate;
and S2, washing the chlorine-containing intermediate, placing the chlorine-containing intermediate into a KI solution, and keeping the temperature and standing to obtain the immobilized catalyst.
3. The method for preparing the supported catalyst for ethylene carbonate production according to claim 2, wherein the chlorine-containing porous resin microspheres are prepared by, by mass: triphenylphosphine: dimethylamide ═ 1: (0.4-0.6): (6-8);
according to the mass ratio, the chlorine-containing intermediate: KI solution 1: (4-6).
4. The method of claim 2, wherein step S1 includes:
s11 preparation of chlorine-containing porous resin microspheres with porous structures
And sequentially adding vinylidene chloride, benzoyl peroxide, ethylene glycol dimethacrylate, toluene and white oil into deionized water, reacting for 8 hours at 70 ℃, filtering out a solid phase, and washing to obtain the chlorine-containing porous resin microspheres.
5. The method for preparing an immobilized catalyst for ethylene carbonate production according to claim 4, wherein the molar ratio of vinylidene chloride: benzoyl peroxide: ethylene glycol dimethacrylate: toluene: white oil 1: (1-1.4): (0.4-0.6): (4-6): (10-12).
6. The method of claim 2, wherein step S1 further comprises:
s12, loading nano iron on the chlorine-containing porous resin microspheres
And simultaneously placing the chlorine-containing porous resin microspheres and the iron chloride powder into ethanol, dropwise adding a sodium borohydride solution while stirring, reacting for 10min, performing suction filtration, and washing to obtain the nano-iron-loaded chlorine-containing porous resin microspheres.
7. The method of claim 6, wherein step S1 further comprises:
s13, loading nano iron on triphenylphosphine
And (3) placing triphenylphosphine into an iron chloride solution, stirring for 30min, standing for 4h, filtering, and drying to obtain the triphenylphosphine loaded with nano iron.
8. The method for preparing an immobilized catalyst for ethylene carbonate production according to claim 7, wherein tannic acid is further added in step S1, and the chlorine-containing porous resin microspheres are added in the following weight ratio: tannic acid 1: (0.5-0.7).
9. An immobilized catalyst for producing ethylene carbonate, which is obtained by the method for producing an immobilized catalyst for producing ethylene carbonate according to any one of claims 1 to 8.
10. The use of the supported catalyst for ethylene carbonate production according to claim 9 for catalyzing a reaction process for producing ethylene carbonate from ethylene oxide and carbon dioxide.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210480632.7A CN114768884B (en) | 2022-05-05 | 2022-05-05 | Immobilized catalyst for producing ethylene carbonate, preparation method and application |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210480632.7A CN114768884B (en) | 2022-05-05 | 2022-05-05 | Immobilized catalyst for producing ethylene carbonate, preparation method and application |
Publications (2)
Publication Number | Publication Date |
---|---|
CN114768884A true CN114768884A (en) | 2022-07-22 |
CN114768884B CN114768884B (en) | 2023-06-30 |
Family
ID=82435144
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202210480632.7A Active CN114768884B (en) | 2022-05-05 | 2022-05-05 | Immobilized catalyst for producing ethylene carbonate, preparation method and application |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN114768884B (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115417941A (en) * | 2022-08-30 | 2022-12-02 | 浙江工业大学 | Catalyst suitable for ozone decomposition in atmospheric environment and application thereof |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101312937A (en) * | 2005-11-23 | 2008-11-26 | 巴斯夫欧洲公司 | Process for preparing vinyl carboxylates |
CN101613339A (en) * | 2009-07-27 | 2009-12-30 | 广西壮族自治区化工研究院 | The method of synthesizing ethylene carbonate and catalyzer |
CN103030624A (en) * | 2011-09-30 | 2013-04-10 | 中国石油化工股份有限公司 | Method for preparing vinyl carbonate by epoxy ethane and carbon dioxide |
CN105440007A (en) * | 2014-09-25 | 2016-03-30 | 中国石油化工股份有限公司 | Method for synthesizing ethylene carbonate |
US20200094237A1 (en) * | 2017-06-23 | 2020-03-26 | N.E. Chemcat Corporation | Method for producing palladium-gold loaded catalyst for vinyl acetate synthesis |
-
2022
- 2022-05-05 CN CN202210480632.7A patent/CN114768884B/en active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101312937A (en) * | 2005-11-23 | 2008-11-26 | 巴斯夫欧洲公司 | Process for preparing vinyl carboxylates |
CN101613339A (en) * | 2009-07-27 | 2009-12-30 | 广西壮族自治区化工研究院 | The method of synthesizing ethylene carbonate and catalyzer |
CN103030624A (en) * | 2011-09-30 | 2013-04-10 | 中国石油化工股份有限公司 | Method for preparing vinyl carbonate by epoxy ethane and carbon dioxide |
CN105440007A (en) * | 2014-09-25 | 2016-03-30 | 中国石油化工股份有限公司 | Method for synthesizing ethylene carbonate |
US20200094237A1 (en) * | 2017-06-23 | 2020-03-26 | N.E. Chemcat Corporation | Method for producing palladium-gold loaded catalyst for vinyl acetate synthesis |
Non-Patent Citations (1)
Title |
---|
陈梁锋等: "高效负载型季鏻盐催化合成碳酸乙烯酯", 石油化工 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115417941A (en) * | 2022-08-30 | 2022-12-02 | 浙江工业大学 | Catalyst suitable for ozone decomposition in atmospheric environment and application thereof |
CN115417941B (en) * | 2022-08-30 | 2024-01-30 | 浙江工业大学 | Catalyst applicable to ozonolysis in atmospheric environment and application thereof |
Also Published As
Publication number | Publication date |
---|---|
CN114768884B (en) | 2023-06-30 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN111871466B (en) | Node-supported metal cluster catalyst in metal organic framework structure and preparation method and application thereof | |
CN114768884B (en) | Immobilized catalyst for producing ethylene carbonate, preparation method and application | |
CN111686730A (en) | Preparation method and application of catalyst for synthesizing 2-phenylimidazole by Debus method | |
CN109046442B (en) | Hierarchical pore molecular sieve supported platinum-iron bimetallic catalyst and preparation and application thereof | |
KR20180035718A (en) | Catalyst for dehydrogenation reaction of formate and hydrogenation reaction of bicarbonate and method of manufactuirng the same | |
CN116621701A (en) | Solid base catalyst, preparation method thereof and synthesis method of methyl methacrylate | |
CN114789065A (en) | Production process of vinylene carbonate and catalyst for production | |
CN113842919A (en) | Catalyst for carbon dioxide hydrogenation methanation reaction and preparation method and application thereof | |
CN114130416A (en) | Preparation method of carbon-supported multi-metal catalyst and application of carbon-supported multi-metal catalyst in N-alkylation reaction | |
CN110656104B (en) | GA @ GOx hybrid nanoflower and preparation method and application thereof | |
CN113617394A (en) | Supported catalyst for preparing morpholine and preparation method thereof | |
CN108636440B (en) | Catalyst for preparing 1, 3-propylene glycol by hydrogenation of glycerol aqueous solution and preparation method thereof | |
CN114870864B (en) | Ferrite supported noble metal ruthenium catalyst and preparation method and application thereof | |
CN111821985B (en) | Copper-based catalyst, preparation method and application | |
CN114773180B (en) | Synthetic method and catalyst for preparing 3-hydroxybutyric acid by selective oxidation of 1, 3-butanediol | |
CN113042025B (en) | Non-metal porous carbon material catalyst prepared by taking saccharides as raw materials and preparation method and application thereof | |
CN115121248B (en) | Ruthenium-supported metal oxide catalyst and preparation method and application thereof | |
CN110479377B (en) | Catalyst for reaction of 4-iodonitrobenzene and phenylacetylene | |
CN114950503B (en) | Preparation method and application of regenerated acid catalyst | |
CN114733550B (en) | Production process of ethylene carbonate and catalyst for production | |
CN111659395B (en) | Preparation method and application of foamed iron-based catalyst with high all-olefin selectivity | |
CN115138365B (en) | Hydrogenation catalyst, preparation method and application thereof | |
CN114768784B (en) | Preparation method and application of flaky alumina-carbon composite material | |
CN112495447B (en) | Catalyst composition for synthesizing methyl methacrylate | |
CN115709067B (en) | Metal hydrogel solid catalyst and preparation method and application thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |