CN114768884B - Immobilized catalyst for producing ethylene carbonate, preparation method and application - Google Patents
Immobilized catalyst for producing ethylene carbonate, preparation method and application Download PDFInfo
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- CN114768884B CN114768884B CN202210480632.7A CN202210480632A CN114768884B CN 114768884 B CN114768884 B CN 114768884B CN 202210480632 A CN202210480632 A CN 202210480632A CN 114768884 B CN114768884 B CN 114768884B
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- chlorine
- porous resin
- immobilized catalyst
- triphenylphosphine
- ethylene carbonate
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- 239000003622 immobilized catalyst Substances 0.000 title claims abstract description 43
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 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 82
- 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
- 239000004005 microsphere Substances 0.000 claims abstract description 56
- 239000011347 resin Substances 0.000 claims abstract description 53
- 229920005989 resin Polymers 0.000 claims abstract description 53
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 18
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 16
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 8
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 67
- 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 24
- 238000005406 washing Methods 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 14
- 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 13
- 239000001263 FEMA 3042 Substances 0.000 claims description 13
- 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 13
- 238000001914 filtration Methods 0.000 claims description 13
- 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 13
- 229940033123 tannic acid Drugs 0.000 claims description 13
- 235000015523 tannic acid Nutrition 0.000 claims description 13
- 229920002258 tannic acid Polymers 0.000 claims description 13
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 12
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 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
- 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
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical compound 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
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 8
- 239000012279 sodium borohydride Substances 0.000 claims description 8
- QKIUAMUSENSFQQ-UHFFFAOYSA-N dimethylazanide Chemical compound C[N-]C QKIUAMUSENSFQQ-UHFFFAOYSA-N 0.000 claims description 7
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims description 5
- 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
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 abstract description 13
- 230000003197 catalytic effect Effects 0.000 abstract description 10
- 150000001450 anions Chemical class 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 5
- 230000002194 synthesizing effect Effects 0.000 abstract description 3
- 230000009467 reduction Effects 0.000 abstract description 2
- 239000000543 intermediate Substances 0.000 description 20
- 239000003921 oil Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification 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
- 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
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 150000002148 esters Chemical group 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
- 229920000642 polymer Polymers 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000012048 reactive intermediate Substances 0.000 description 1
- 239000002002 slurry Substances 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
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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
- B01J31/16—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
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Abstract
The invention relates to the technical field of catalysts, and provides a preparation method of an immobilized catalyst for producing ethylene carbonate, which uses chlorine-containing porous resin microspheres as a carrier, triphenylphosphine as a main active component and dimethylformamide as a solvent, wherein the carrier comprises the following components in percentage by weight ‑ Synthesizing an immobilized catalyst by using the complex anions; the preparation method provided by the invention uses chlorine-containing porous resin microspheres as a carrier, triphenylphosphine as a main active component and dimethylformamide as a solvent, I ‑ The immobilized catalyst is synthesized by coordination anions, has higher conversion rate of raw material ethylene oxide and selectivity of product ethylene carbonate in the process of preparing ethylene carbonate by an addition method of ethylene oxide and carbon dioxide, and has no obvious reduction of catalytic performance after repeated use for a plurality of times, thus indicating that the immobilized catalyst has good catalytic performance and service life.
Description
Technical Field
The invention relates to the technical field of catalysts, in particular to an immobilized catalyst for producing ethylene carbonate, a preparation method and application thereof.
Background
Ethylene Carbonate (EC) is an excellent organic solvent that can dissolve a variety of polymers; in addition, the catalyst can be used as an organic intermediate, can replace ethylene oxide to be used for dioxygenation reaction, and is a main raw material for producing dimethyl carbonate by an ester exchange method; can also be used as raw materials for synthesizing furazolidone, water glass series slurry, fiber finishing agent and the like; in addition, the method is also applied to lithium battery electrolyte. Ethylene carbonate is also useful as a reactive intermediate in the production of lubricating oils and greases.
Ethylene oxide and carbon dioxide addition method are commonly adopted at present to prepare ethylene carbonate, the addition method is exothermic and has reduced volume, the reaction is facilitated under the conditions of low temperature and high pressure from the aspect of chemical balance, and meanwhile, the selection of a proper catalyst is the key of smooth reaction, and the reaction system is mainly a homogeneous catalysis system. The homogeneous catalytic system has good catalytic effect, but has a problem that after the reaction is finished, the catalyst is difficult to separate from the product, so that the purity of the product is influenced, and unnecessary loss of the catalyst is caused.
Disclosure of Invention
The invention provides an immobilized catalyst for producing ethylene carbonate, 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 first aspect of 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 - The immobilized catalyst is synthesized by using the complex anions.
The second aspect of the invention provides an immobilized 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, which is particularly used in 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 has at least the following advantages and beneficial effects:
the preparation method provided by the invention uses chlorine-containing porous resin microspheres as a carrier, triphenylphosphine as a main active component and dimethylformamide as a solvent, I - The immobilized catalyst is synthesized by coordination anions, has higher conversion rate of raw material ethylene oxide and selectivity of product ethylene carbonate in the process of preparing ethylene carbonate by an addition method of ethylene oxide and carbon dioxide, and has no obvious reduction of catalytic performance after repeated use for a plurality of times, thus indicating that the immobilized catalyst has good catalytic performance and service life.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and other related drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
Fig. 1 is a scanning electron microscope image of an immobilized catalyst for producing ethylene carbonate, which is 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 clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The specific embodiment 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 - The method is used for synthesizing the immobilized catalyst for coordinating anions, and specifically comprises the following steps:
s1, respectively adding chlorine-containing porous resin microspheres and triphenylphosphine into dimethylamide, and heating for reaction to obtain a chlorine-containing intermediate;
s2, washing the chlorine-containing intermediate, placing the washed chlorine-containing intermediate into a KI solution, and keeping the temperature and standing the solution to obtain the immobilized catalyst.
Further, in step S1, the chlorine-containing porous resin microspheres are, in mass ratio: triphenylphosphine: dimethylamide = 1: (0.4-0.6): (6-8).
Further, in step S2, the chlorine-containing intermediate is obtained by mass ratio: KI solution = 1: (4-6), wherein the concentration of the KI solution is 20wt%.
Further, in step S1, it includes:
s11, preparing chlorine-containing porous resin microspheres with porous structures
And sequentially adding vinylidene chloride, benzoyl peroxide, glycol dimethacrylate, toluene and white oil into deionized water, reacting at 70 ℃ for 8 hours, filtering out a solid phase, and washing to obtain the chlorine-containing porous resin microspheres.
Wherein, according to mass ratio, vinylidene chloride: benzoyl peroxide: ethylene glycol dimethacrylate: toluene: white oil = 1: (1-1.4): (0.4-0.6): (4-6): (10-12).
Wherein the particle size of the chlorine-containing porous resin microsphere is 500-550 nanometers.
Further, in step S1, further includes:
s12, loading nano iron on chlorine-containing porous resin microspheres
And (3) simultaneously placing the chlorine-containing porous resin microspheres and ferric chloride powder in ethanol, dropwise adding sodium borohydride solution under stirring, stirring and reacting for 10min, performing suction filtration, and washing to obtain the nano-iron-loaded chlorine-containing porous resin microspheres.
The surface of the porous resin microsphere containing chlorine is rough, after ferric chloride is adsorbed, the surface of the porous resin microsphere containing chlorine is rough, and the surface of the porous resin microsphere containing chlorine 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 porous resin microsphere containing chlorine is further increased, namely the specific surface area of the surface of the microsphere is increased, and the catalytic reaction efficiency is improved.
Further, in step S1, further includes:
s13, loading nano iron on triphenylphosphine
And (3) placing triphenylphosphine in ferric chloride solution, stirring for 30min, standing for 4h, filtering, and drying to obtain triphenylphosphine loaded with nano iron.
By utilizing the ligand action of triphenylphosphine and iron, the iron can be better adsorbed with the triphenylphosphine, and the triphenylphosphine can be well adsorbed on the microsphere surface due to the existence of the iron on the surface of the porous resin microsphere containing chlorine.
Further, tannic acid is also added in the step S1, and the porous resin microspheres containing chlorine are prepared according to the mass ratio: tannic acid=1: (0.5-0.7).
Through the complexing action of tannic acid and iron, triphenylphosphine can be more firmly adsorbed on the surface of the porous resin microspheres containing chlorine, so that the service life of the catalyst is effectively prolonged.
Example 1
The embodiment is used for preparing the immobilized catalyst for producing ethylene carbonate, and comprises the following steps:
s1, preparing chlorine-containing intermediate
S11, preparing chlorine-containing porous resin microspheres with porous structures
Sequentially adding vinylidene chloride, benzoyl peroxide, glycol dimethacrylate, toluene and white oil into deionized water, wherein the vinylidene chloride is prepared by the following steps of: benzoyl peroxide: ethylene glycol dimethacrylate: toluene: white oil = 1:1.2:0.5:5:11, after reacting for 8 hours at 70 ℃, filtering out a solid phase, washing and drying to obtain the chlorine-containing porous resin microsphere with the particle size of 520 nanometers.
S12, loading nano iron on chlorine-containing porous resin microspheres
Mixing porous resin microspheres containing chlorine with ferric chloride powder according to a mass ratio of 1: and 4, simultaneously placing the mixture into 500mL of ethanol, dropwise adding sodium borohydride solution (the concentration is 15 wt%) at a speed of 20 drops/min under stirring, stopping dropwise adding the sodium borohydride solution after stirring and reacting for 10min, carrying out suction filtration, and washing to obtain the nano-iron-loaded chlorine-containing porous resin microsphere.
S13, loading nano iron on triphenylphosphine
And (3) placing triphenylphosphine in ferric chloride solution (the concentration is 30 wt%) and stirring for 30min, standing for 4h, filtering and drying to obtain triphenylphosphine loaded with nano-iron.
S14, preparing chlorine-containing intermediate
Firstly, respectively adding nano-iron-loaded chlorine-containing porous resin microspheres and nano-iron-loaded triphenylphosphine into dimethylamide, heating to 50 ℃, stirring for 10 minutes, then slowly pouring tannic acid, continuously stirring in the pouring process, reacting for 30 minutes in a stirring environment, standing for 6 hours, filtering, cleaning and drying to obtain a chlorine-containing intermediate;
wherein, according to mass ratio, the chlorine-containing porous resin microsphere loaded with nano iron comprises the following components: triphenylphosphine loaded with nano iron: dimethylformamide: 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 chlorine-containing intermediate comprises the following components in percentage by mass: KI solution = 1: and 5, keeping the temperature at 35 ℃ and standing for 8 hours, and taking out, washing and drying to obtain the immobilized catalyst A1.
Example 2
The embodiment is used for preparing the immobilized catalyst for producing ethylene carbonate, and comprises the following steps:
s1, preparing chlorine-containing intermediate
S11, preparing chlorine-containing porous resin microspheres with porous structures
Sequentially adding vinylidene chloride, benzoyl peroxide, glycol dimethacrylate, toluene and white oil into deionized water, wherein the vinylidene chloride is prepared by the following steps of: benzoyl peroxide: ethylene glycol dimethacrylate: toluene: white oil = 1:1:0.4:4:10, after reacting for 8 hours at 70 ℃, filtering out a solid phase, washing and drying to obtain the chlorine-containing porous resin microsphere with the particle size of 500 nanometers.
S12, loading nano iron on chlorine-containing porous resin microspheres
Mixing porous resin microspheres containing chlorine with ferric chloride powder according to a mass ratio of 1: and 3, simultaneously placing the mixture into 500mL of ethanol, dropwise adding sodium borohydride solution (the concentration is 15 wt%) at a speed of 20 drops/min under stirring, stopping dropwise adding the sodium borohydride solution after stirring and reacting for 10min, carrying out suction filtration, and washing to obtain the nano-iron-loaded chlorine-containing porous resin microsphere.
S13, loading nano iron on triphenylphosphine
And (3) placing triphenylphosphine in ferric chloride solution (the concentration is 30 wt%) and stirring for 30min, standing for 4h, filtering and drying to obtain triphenylphosphine loaded with nano-iron.
S14, preparing chlorine-containing intermediate
Firstly, respectively adding nano-iron-loaded chlorine-containing porous resin microspheres and nano-iron-loaded triphenylphosphine into dimethylamide, heating to 50 ℃, stirring for 10 minutes, then slowly pouring tannic acid, continuously stirring in the pouring process, reacting for 30 minutes in a stirring environment, standing for 6 hours, filtering, cleaning and drying to obtain a chlorine-containing intermediate;
wherein, according to mass ratio, the chlorine-containing porous resin microsphere loaded with nano iron comprises the following components: triphenylphosphine loaded with nano iron: dimethylformamide: tannic acid=1: 0.4:6:0.5.
s2, placing the chlorine-containing intermediate obtained in the step S1 into a KI solution (the concentration is 20 wt%), wherein the chlorine-containing intermediate comprises the following components in percentage by mass: KI solution = 1:4, keeping the temperature at 35 ℃ and standing for 8 hours, and taking out, washing and drying to obtain the immobilized catalyst A2.
Example 3
The embodiment is used for preparing the immobilized catalyst for producing ethylene carbonate, and comprises the following steps:
s1, preparing chlorine-containing intermediate
S11, preparing chlorine-containing porous resin microspheres with porous structures
Sequentially adding vinylidene chloride, benzoyl peroxide, glycol dimethacrylate, toluene and white oil into deionized water, wherein the vinylidene chloride is prepared by the following steps of: benzoyl peroxide: ethylene glycol dimethacrylate: toluene: white oil = 1:1.4:0.6:6:12, after reacting for 8 hours at 70 ℃, filtering out a solid phase, washing and drying to obtain the chlorine-containing porous resin microsphere with the particle size of 550 nanometers.
S12, loading nano iron on chlorine-containing porous resin microspheres
Mixing porous resin microspheres containing chlorine with ferric chloride powder according to a mass ratio of 1: and 5, simultaneously placing the mixture into 500mL of ethanol, dropwise adding sodium borohydride solution (the concentration is 15 wt%) at a speed of 20 drops/min under stirring, stopping dropwise adding the sodium borohydride solution after stirring and reacting for 10min, carrying out suction filtration, and washing to obtain the nano-iron-loaded chlorine-containing porous resin microsphere.
S13, loading nano iron on triphenylphosphine
And (3) placing triphenylphosphine in ferric chloride solution (the concentration is 30 wt%) and stirring for 30min, standing for 4h, filtering and drying to obtain triphenylphosphine loaded with nano-iron.
S14, preparing chlorine-containing intermediate
Firstly, respectively adding nano-iron-loaded chlorine-containing porous resin microspheres and nano-iron-loaded triphenylphosphine into dimethylamide, heating to 50 ℃, stirring for 10 minutes, then slowly pouring tannic acid, continuously stirring in the pouring process, reacting for 30 minutes in a stirring environment, standing for 6 hours, filtering, cleaning and drying to obtain a chlorine-containing intermediate;
wherein, according to mass ratio, the chlorine-containing porous resin microsphere loaded with nano iron comprises the following components: triphenylphosphine loaded with nano iron: dimethylformamide: tannic acid=1: 0.6:8:0.7.
s2, placing the chlorine-containing intermediate obtained in the step S1 into a KI solution (the concentration is 20 wt%), wherein the chlorine-containing intermediate comprises the following components in percentage by mass: KI solution = 1:6, keeping the temperature at 35 ℃ and standing for 8 hours, and taking out, washing and drying to obtain the immobilized catalyst A3.
Comparative example 1
The other features were the same as in example 1 except that nano iron was not supported on the chlorine-containing porous resin microspheres, and finally an immobilized catalyst D1 was produced.
Comparative example 2
The other features were the same as in example 1 except that nano iron was not supported on triphenylphosphine, and finally an immobilized catalyst D2 was prepared.
Comparative example 3
The other features were the same as in example 1 except that tannic acid was not added, and finally an immobilized catalyst D3 was produced.
Experimental example 1
The experimental example was used for evaluating the performance of the immobilized catalyst.
10 g of the immobilized catalyst (the catalyst prepared in each of the above examples and comparative examples) was weighed and placed in a reaction kettle, the air in the kettle was replaced with carbon dioxide, 45 g of ethylene oxide was then added, carbon dioxide was charged to 1 mpa, a temperature-raising program was started, the temperature-raising rate was 2 ℃/min, carbon dioxide was charged to the reaction pressure after the temperature was raised to the reaction temperature, the temperature was lowered after the reaction for a while, the mass of the reaction mixture was weighed after purging unreacted ethylene oxide with nitrogen, and the conversion of ethylene oxide and the selectivity of ethylene carbonate were calculated, respectively, and the data are shown in table 1.
Experimental example 2
The experimental example is used for testing the service life of the immobilized catalyst.
The reaction was carried out according to the method provided in experimental example 1, after the reaction was completed, the immobilized catalyst was separated from the reaction product, and then the reaction was carried out again, and repeated 5 times, with the data shown in table 2.
TABLE 1 Performance of immobilized catalysts
| Experimental group | Conversion of ethylene oxide/% | Selectivity/% |
| 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 immobilized catalyst
As shown in the data of 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 repeated reactions. In the D1, nano iron is not loaded on the porous resin microspheres containing chlorine, so that triphenylphosphine is easy to fall off, and the catalytic performance of the catalyst is affected; d2 is not loaded with nano iron on triphenylphosphine, and the triphenylphosphine is easy to fall off, so that the catalytic performance of the catalyst is affected; d3 is not added with tannic acid, so that the adsorption force of triphenylphosphine and the chlorine-containing porous resin microspheres is weak, and the triphenylphosphine is easy to fall off, so that 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, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (5)
1. A preparation method of an immobilized catalyst for producing ethylene carbonate 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, and I - Is coordination anionsSynthesizing an immobilized catalyst;
the method comprises the following steps:
s1, respectively adding chlorine-containing porous resin microspheres and triphenylphosphine into dimethylamide, and heating for reaction to obtain a chlorine-containing intermediate;
tannic acid is also added in the step S1, and the porous resin microspheres containing chlorine are prepared according to the mass ratio: tannic acid=1: (0.5-0.7);
s2, washing the chlorine-containing intermediate, placing the washed chlorine-containing intermediate in a KI solution, and keeping the temperature and standing to obtain the immobilized catalyst;
the step S1 includes:
s11, preparing chlorine-containing porous resin microspheres with porous structures
Sequentially adding vinylidene chloride, benzoyl peroxide, glycol dimethacrylate, toluene and white oil into deionized water, reacting at 70 ℃ for 8 hours, filtering out a solid phase, and washing to obtain chlorine-containing porous resin microspheres;
s12, loading nano iron on chlorine-containing porous resin microspheres
Simultaneously placing the chlorine-containing porous resin microspheres and ferric chloride powder in ethanol, dropwise adding sodium borohydride solution under stirring, stirring and reacting for 10min, performing suction filtration, and washing to obtain nano-iron-loaded chlorine-containing porous resin microspheres;
s13, loading nano iron on triphenylphosphine
And (3) placing triphenylphosphine in ferric chloride solution, stirring for 30min, standing for 4h, filtering, and drying to obtain triphenylphosphine loaded with nano iron.
2. The method for preparing an immobilized catalyst for producing ethylene carbonate according to claim 1, wherein the porous resin microspheres contain chlorine according to mass ratio: triphenylphosphine: dimethylamide = 1: (0.4-0.6): (6-8);
the chlorine-containing intermediate comprises the following components in percentage by mass: KI solution = 1: (4-6).
3. The method for preparing an immobilized catalyst for producing ethylene carbonate according to claim 1, wherein the vinylidene chloride is prepared by the following steps: benzoyl peroxide: ethylene glycol dimethacrylate: toluene: white oil = 1: (1-1.4): (0.4-0.6): (4-6): (10-12).
4. An immobilized catalyst for producing ethylene carbonate, characterized by being produced by the method for producing an immobilized catalyst for producing ethylene carbonate according to any one of claims 1 to 3.
5. The use of an immobilized catalyst for the production of ethylene carbonate according to claim 4 for catalyzing the reaction process for the production of ethylene carbonate starting from ethylene oxide and carbon dioxide.
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