CN106268939B - A kind of supported ionic liquids carrier, preparation method and applications - Google Patents
A kind of supported ionic liquids carrier, preparation method and applications Download PDFInfo
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- CN106268939B CN106268939B CN201610648192.6A CN201610648192A CN106268939B CN 106268939 B CN106268939 B CN 106268939B CN 201610648192 A CN201610648192 A CN 201610648192A CN 106268939 B CN106268939 B CN 106268939B
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- ionic liquids
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- carried catalyst
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- 239000002608 ionic liquid Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title abstract description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000003054 catalyst Substances 0.000 claims abstract description 31
- 239000010881 fly ash Substances 0.000 claims abstract description 15
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000741 silica gel Substances 0.000 claims abstract description 13
- 229910002027 silica gel Inorganic materials 0.000 claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 11
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 8
- 239000007822 coupling agent Substances 0.000 claims abstract description 6
- 239000007787 solid Substances 0.000 claims abstract 2
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 claims description 7
- 229910052740 iodine Inorganic materials 0.000 claims description 6
- 239000011630 iodine Substances 0.000 claims description 6
- 239000003849 aromatic solvent Substances 0.000 claims description 5
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical group CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 230000036571 hydration Effects 0.000 claims description 3
- 238000006703 hydration reaction Methods 0.000 claims description 3
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 150000002460 imidazoles Chemical class 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 13
- 238000010992 reflux Methods 0.000 abstract description 10
- 238000006243 chemical reaction Methods 0.000 abstract description 7
- 230000008569 process Effects 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 150000001555 benzenes Chemical class 0.000 abstract description 2
- 239000000969 carrier Substances 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 230000001681 protective effect Effects 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000000047 product Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000013598 vector Substances 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000007306 functionalization reaction Methods 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- KAIPKTYOBMEXRR-UHFFFAOYSA-N 1-butyl-3-methyl-2h-imidazole Chemical compound CCCCN1CN(C)C=C1 KAIPKTYOBMEXRR-UHFFFAOYSA-N 0.000 description 1
- REACWASHYHDPSQ-UHFFFAOYSA-N 1-butylpyridin-1-ium Chemical compound CCCC[N+]1=CC=CC=C1 REACWASHYHDPSQ-UHFFFAOYSA-N 0.000 description 1
- ZKYGURGLVHDMAB-UHFFFAOYSA-N CN1C=NC=C1.[I] Chemical compound CN1C=NC=C1.[I] ZKYGURGLVHDMAB-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000005496 phosphonium group Chemical group 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0272—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255
- B01J31/0275—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255 also containing elements or functional groups covered by B01J31/0201 - B01J31/0269
-
- 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
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0292—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature immobilised on a substrate
- B01J31/0295—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature immobilised on a substrate by covalent attachment to the substrate, e.g. silica
-
- 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
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
- C07C29/10—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of ethers, including cyclic ethers, e.g. oxiranes
- C07C29/103—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of ethers, including cyclic ethers, e.g. oxiranes of cyclic ethers
- C07C29/106—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of ethers, including cyclic ethers, e.g. oxiranes of cyclic ethers of oxiranes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of supported ionic liquids carriers, preparation method and applications, and support material flyash and silica gel and coupling agent are placed in benzene or substituted benzene, certain time is stirred at reflux, after reaction stops, it is filtered, washed, revolving obtains the carrier to powdered.Carrier solid-loaded ionic-liquid is obtained into carried catalyst, is used for catalytically synthesizing glycol.Preparation method of the present invention is simple, and using special ionic liquid when preparation, obtained carried catalyst has good catalytic and stability, reduce the water ratio of product, the production method of the carrier is simple simultaneously, and use process is environmentally protective, reduces the cost of industrialization preparing ethylene glycol.
Description
Technical field
The present invention relates to chemical catalysis field more particularly to a kind of supported ionic liquids carrier, preparation method and its answer
With.
Technical background
In recent years during industrial catalytically synthesizing glycol, spread out using elemental silver, resin and alkali metal or alkali metal
Biology is used as catalyst synthesizing glycol, but these catalyst are respectively present at high price, synthesis difficulty and environmental pollution
The disadvantages of serious, to solve problems, invent a kind of high-quality catalyst is very important for being catalyzed ethylene glycol.
Ionic liquid is one of the green chemical industry functional material developed in recent years, since it is with non-volatile, vapour pressure is close
Zero, the advantages that non-ignitable, receives increasingly extensive concern.Due to the anions and canons structure of ionic liquid can carry out it is artificial
Design can introduce one or more functional groups using this designability in its anions and canons and assign ionic liquid and have
There are certain special function or characteristic, that is, form functionalized ion liquid, to make it in catalysis, separation, environmental improvement
Equal numerous areas have preferable application prospect, currently have sizeable proportion to concentrate in this regard the research of ionic liquid.
But such viscosity of il is larger, and resistance to mass tranfer is big, affects its application prospect.
Synthesize that ionic liquid solid-state material with functionalization will very good solution be above-mentioned asks if can design
Topic, and there is theoretical and practical significance.By that on different carriers, ionic liquid can be overcome to exist ionic liquid supported
Mass transfer problem in practical application keeps it more stable, and specific surface is bigger, and the separation, recycling after use are also easy to accomplish,
It will be more advantageous in terms of industrial continuous application.
But for current carrier mainly based on zeolite, molecular sieve, relative price is expensive, and finding one kind can be as a kind of new
Carrier substitute become a kind of development trend.
Summary of the invention
For the defects in the prior art and insufficient, for the present invention by finding new carrier raw material, utilization is simple and fast
Method it is further modified, and then propose a kind of preparation method of immobilized ionic liquid carrier of acidity.
To solve the above problems, the technical scheme adopted by the invention is as follows:
A kind of supported ionic liquids carrier is consolidated what is obtained after support material, coupling agent and aromatic solvent mixed processing
Body substance is supported ionic liquids carrier；The support material includes flyash and silica gel.
Specifically, by quality than based on, the flyash: silica gel=0.9~0.7:0.1~0.3.
More specifically, the partial size of the flyash is 0.5~50 μm.
In addition, the aromatic solvent is benzene or substituted benzene.
Again specifically, 12~48h of reflux is mixed in support material, coupling agent and aromatic solvent, using filter, washing
With revolving to it is powdered to obtain the final product.
The supported ionic liquids carrier is used for the application of immobilized 1,3- methylimidazole iodine.
Carried catalyst is obtained after immobilized 1, the 3- methylimidazole iodine of the supported ionic liquids carrier, which urges
Agent is used for direct hydration method catalytically synthesizing glycol.
The ratio that the supported ionic liquids carrier and 1,3- methylimidazole iodine are 1:2 in mass ratio is mixed
Conjunction forms carried catalyst.
Compared with prior art, the invention has the following advantages:
1) while ensure that catalytic effect, life is greatly saved using flyash and silica gel as carrier in the present invention
Produce cost.
2) operating method of the invention is simple and quick, can simultaneously serve as the carrier of immobilized ionic liquid from it is different from
Sub- liquid combines, and is used for organic synthesis field as catalyst.
3) present invention solves existing catalyst there are the problems such as at high price, synthesis is difficult and environmental pollution is serious, accords with
Close the theory of Green Chemistry.
Detailed description of the invention
Fig. 1 is the modified-image for changing support material type synthetic vectors specific surface area；
The modified-image of Fig. 2 feed change proportion synthetic vectors specific surface area；
Fig. 3 changes the modified-image for being stirred at reflux time synthetic vectors specific surface area；
The water ratio proccessing result and its blank control of Fig. 4 catalyst variety classes alcohol；
The present invention is illustrated below in conjunction with specification drawings and specific embodiments.
Specific embodiment
Further illustrate the present invention below by the detailed construction and example of specific embodiment, but the present invention and unlimited
In following embodiments, under the range for not departing from the front and back objective, change is included in technical scope of the invention.
Embodiment 1:
A kind of immobilized ionic liquid carrier of acidity is manufactured with the following method: in mass ratio by flyash: silicon
Glue=(0.9:0.1) mixture and aminopropyl triethoxysilane (KH550) are placed in toluene, are stirred at reflux for 24 hours, reaction stops
After only, filtering, deionized water washing, and rotate under conditions of 60 DEG C to powdered, after being modified carrier.Later by institute
The carrier obtained analyzes its specific surface area using full-automatic specific surface area analysis instrument, and resulting specific surface area is 389m2/g。
Embodiment 2:
A kind of immobilized ionic liquid carrier of acidity is manufactured with the following method: in mass ratio by zeolite: silica gel
The mixture and aminopropyl triethoxysilane (KH550) of=(0.9:0.1) is placed in toluene, is stirred at reflux for 24 hours, and reaction stops
Afterwards, filtering, deionized water washing, and rotate under conditions of 60 DEG C to powdered, after being modified carrier.Later by gained
Carrier its specific surface area is analyzed using full-automatic specific surface area analysis instrument, resulting specific surface area be 79m2/g。
Embodiment 3:
A kind of immobilized ionic liquid carrier of acidity is manufactured with the following method: in mass ratio by montmorillonite: silicon
Glue=(0.9:0.1) mixture and coupling agent aminopropyl triethoxysilane (KH550) are placed in toluene, are stirred at reflux for 24 hours,
After reaction stops, filtering wash with the deionized water of heat, and rotated to powdered, after being modified under conditions of 60 DEG C
Carrier.Resulting carrier analyzes its specific surface area using full-automatic specific surface area analysis instrument later, it is resulting to compare table
Area is 153m2/g。
The Comparative result of embodiment 1-3 is specifically shown in Fig. 1, it is known that in one timing of other conditions, change the type of support material,
The specific surface area of the carrier eventually formed is different, and when support material is flyash and silica gel, effect is preferable.
Embodiment 4:
The present embodiment is unlike the first embodiment: the mass ratio of flyash and silica gel is 0.8:0.2.
Embodiment 5:
The present embodiment is unlike the first embodiment: the mass ratio of flyash and silica gel is 0.7:0.3.
Embodiment 6:
The present embodiment is unlike the first embodiment: the mass ratio of flyash and silica gel is 0.6:0.4.
The specific surface area result of the carrier of embodiment 4-6 is shown in Fig. 2, it is known that in the timing of other conditions one, change flyash with
The specific surface area of the proportion of silica gel, the carrier eventually formed is different, when in flyash: silica gel=0.9:0.1~0.7:0.3
When range, specific surface area is larger, is conducive to the application of carrier.
Embodiment 7:
The present embodiment is unlike the first embodiment: being stirred at reflux the time is 12h.
Embodiment 8:
The present embodiment is unlike the first embodiment: being stirred at reflux the time is 48h.
Embodiment 9:
The present embodiment is unlike the first embodiment: being stirred at reflux the time is 6h.
The specific surface area of the carrier of embodiment 7-9 is shown in Fig. 3, it is known that in the timing of other conditions one, change be stirred at reflux when
Between, the specific surface area of the carrier eventually formed is different, when being in the range of 12~48h in return time, specific surface
Product is larger, is conducive to the application of carrier.
Embodiment 10:
(alkyl replaces miaow to the carrier that embodiment 1 is prepared with functionalization ionized liquids 1,3- methylimidazole iodine
Oxazolinium ion) it is mixed in the ratio of 1:2, and 3h is stirred at room temperature on magnetic stirring apparatus, form powdered carried catalyst.
Embodiment 11:
The present embodiment is as different from Example 10: ionized liquids be 1- butyl -3- methylimidazole (alkyl quaternary phosphonium from
Son), form the carried catalyst of colloidal.
Embodiment 12:
The present embodiment is as different from Example 10: ionized liquids be chlorination 1- butyl-pyridinium (alkyl substituted pyridines from
Son), form thick carried catalyst.
By the result of embodiment 10-12 it is found that changing the type of ionic liquid in one timing of other conditions, eventually forming
Carried catalyst state it is different, when ionic liquid type is 1,3- methylimidazole iodine, the carried catalyst of synthesis is
Powdered substance, good dispersion when as catalyst application, easily participates in final catalysis reaction.
Embodiment 13:
Ethylene oxide and water are added in reaction kettle according to molar ratio 20:1, is reacted 1 hour at 120 DEG C, controls other
Reaction condition is suitable for putting into the carried catalyst of embodiment 10 and ethylene oxide mass ratio in 1:8 ratio, resulting product second
The water ratio of glycol is 3.4.
Embodiment 14:
As different from Example 13, carried catalyst is the carried catalyst in embodiment 11 to the present embodiment, resulting
The water ratio of glycol product is 15.9.
Embodiment 15:
As different from Example 13, carried catalyst is the carried catalyst in embodiment 12 to the present embodiment, resulting
The water ratio 32.1 of glycol product.
By the experimental result of embodiment 13-15 it is found that changing and being urged made from different ionic liquid in one timing of other conditions
The water ratio of agent type, the ethylene glycol finally catalyzed and synthesized is different, when catalyst is that (alkyl replaces 1,3- methylimidazole iodine
Imidazol ion) it is powdered made from ionic liquid when, catalytic effect is best.
Embodiment 16:
The carried catalyst that embodiment 10 is prepared is applied to ethylene oxide direct hydration method catalytically synthesizing glycol
Process industry in, the ethylene glycol after being catalyzed and synthesized measures the water ratio of product.And do the blank that catalyst is not added
Control.
Embodiment 17:
The carried catalyst that embodiment 10 is prepared is applied in the process industry of methane oxidation synthesizing methanol, is obtained
Methanol after catalyzing and synthesizing measures the water ratio of product.And do the blank control that catalyst is not added.
Embodiment 18:
The carried catalyst that embodiment 10 is prepared is applied to ethylene synthase to catalyze and synthesize in the process industry of butanol,
Butanol after being catalyzed and synthesized measures the water ratio of product.And do the blank control that catalyst is not added.
The result of embodiment 16-18 is shown in Fig. 4, it is known that the carried catalyst in embodiment 10 is merely able to catalysis ethylene glycol, tool
There is specificity, the effect not improved is catalyzed and synthesized to other alcohols.
Claims (6)
1. a kind of supported ionic liquids carrier, which is characterized in that support material, coupling agent and aromatic solvent to be mixed back
12~48h is flowed, using filter, washing and revolving to powdered, obtained solid matter is supported ionic liquids carrier；
The support material includes flyash and silica gel；It counts in mass ratio, the flyash: silica gel=0.9~0.7:0.1
~0.3；
The coupling agent is aminopropyl triethoxysilane.
2. supported ionic liquids carrier as described in claim 1, which is characterized in that the partial size of the flyash is 0.5
~50 μm.
3. supported ionic liquids carrier as described in claim 1, which is characterized in that the aromatic solvent is benzene or benzene
Homologue.
4. the application that supported ionic liquids carrier described in claim 1,2 or 3 is used for immobilized 1,3- methylimidazole iodine.
5. application as claimed in claim 4, which is characterized in that immobilized 1, the 3- dimethyl of the supported ionic liquids carrier
Carried catalyst is obtained after imidazoles iodine, which is used for direct hydration method catalytically synthesizing glycol.
6. application as claimed in claim 5, which is characterized in that carry supported ionic liquids described in claim 1,2 or 3
Body and 1,3- methylimidazole iodine are that the ratio of 1:2 carries out being mixed to form carried catalyst in mass ratio.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610648192.6A CN106268939B (en) | 2016-08-09 | 2016-08-09 | A kind of supported ionic liquids carrier, preparation method and applications |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610648192.6A CN106268939B (en) | 2016-08-09 | 2016-08-09 | A kind of supported ionic liquids carrier, preparation method and applications |
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| Publication Number | Publication Date |
|---|---|
| CN106268939A CN106268939A (en) | 2017-01-04 |
| CN106268939B true CN106268939B (en) | 2018-12-28 |
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| CN102040473A (en) * | 2009-10-13 | 2011-05-04 | 中国石油化工股份有限公司 | Method for producing ethylene glycol |
| CN102513064A (en) * | 2011-12-23 | 2012-06-27 | 广东工业大学 | Preparation method and application of ionic liquid bonded silica adsorbent |
| CN102698812A (en) * | 2012-06-04 | 2012-10-03 | 大连理工大学 | Solid super acid-ionic liquid composite solid supported catalyst and preparation method thereof |
| CN103638970A (en) * | 2013-12-31 | 2014-03-19 | 海南大学 | Ion liquid catalyst and preparation method thereof as well as preparation method of cyclic carbonate |
| CN104525252A (en) * | 2014-11-26 | 2015-04-22 | 绍兴文理学院 | Immobilized ionic liquid solid acid catalyst and preparation method thereof |
| CN105536758A (en) * | 2016-02-26 | 2016-05-04 | 济南大学 | Preparation method of floatable type recoverable photocatalyst based on single-crystal titanium dioxide |
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102040473A (en) * | 2009-10-13 | 2011-05-04 | 中国石油化工股份有限公司 | Method for producing ethylene glycol |
| CN102513064A (en) * | 2011-12-23 | 2012-06-27 | 广东工业大学 | Preparation method and application of ionic liquid bonded silica adsorbent |
| CN102698812A (en) * | 2012-06-04 | 2012-10-03 | 大连理工大学 | Solid super acid-ionic liquid composite solid supported catalyst and preparation method thereof |
| CN103638970A (en) * | 2013-12-31 | 2014-03-19 | 海南大学 | Ion liquid catalyst and preparation method thereof as well as preparation method of cyclic carbonate |
| CN104525252A (en) * | 2014-11-26 | 2015-04-22 | 绍兴文理学院 | Immobilized ionic liquid solid acid catalyst and preparation method thereof |
| CN105536758A (en) * | 2016-02-26 | 2016-05-04 | 济南大学 | Preparation method of floatable type recoverable photocatalyst based on single-crystal titanium dioxide |
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