CN106694036A - Method for preparing immobilized ionic liquid catalyst - Google Patents
Method for preparing immobilized ionic liquid catalyst Download PDFInfo
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- CN106694036A CN106694036A CN201611003854.0A CN201611003854A CN106694036A CN 106694036 A CN106694036 A CN 106694036A CN 201611003854 A CN201611003854 A CN 201611003854A CN 106694036 A CN106694036 A CN 106694036A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—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
- B01J31/0278—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 containing nitrogen as cationic centre
- B01J31/0285—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 containing nitrogen as cationic centre also containing elements or functional groups covered by B01J31/0201 - B01J31/0274
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
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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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/49—Esterification or transesterification
Abstract
The invention discloses a method for preparing an immobilized ionic liquid catalyst. The method comprises the following steps: (1) mixing 1,3-propane sultone with ethyl acetate, mixing an organic amine solution with the mixture in a dropwise adding manner, and carrying out a reaction with stirring, so as to synthesize an ionic liquid intermediate; (2) subjecting an organic constituent, i.e., the ionic liquid intermediate and an inorganic constituent, i.e., an acidic aqueous solution to a reaction with oil-bath heating, so as to obtain acidic ionic liquid; and (3) subjecting an aqueous solution of the acidic ionic liquid and an alcoholic solution of ethyl orthosilicate to a reaction in oil bath in an acidic environment, carrying out aging after the reaction ends, and carrying out roasting, thereby obtaining the immobilized ionic liquid catalyst. The catalyst prepared by the method for preparing the immobilized ionic liquid catalyst, disclosed by the invention, is applied to the catalytic synthesis of esters, particularly selective ester compounds, is efficient and is good in selectivity, light in environmental pollution and good in repeatability.
Description
Technical field
The present invention relates to esters preparing technical field, and in particular to a kind of immobilized ionic-liquid catalyst and its preparation side
The application of method and the catalyst in catalytic hydroxy acid esterifying reaction.
Background technology
Ester type compound is important fine chemicals, is widely used in the industries such as food, spices, cosmetics.Traditional ester
The industrial production of class material is main with inorganic acids such as the concentrated sulfuric acids as catalyst, by separations, neutralization, washing, drying, rectifying, divides
Completed from operations such as purifying.The shortcoming of the method is many technical process, and catalyst is not readily separated, and product loss is big, of poor quality, pair sets
Standby seriously corroded, post processing is complicated, and environmental pollution is serious.
Ionic liquid, also referred to as ionic liquid at room temperature, are composed entirely of ions and have conventional organic molten different from other
It is the special nature of agent, such as fixedness, heat-flash stability, designability, nontoxic, easy to be recycled thus green by the world
The extensive concern of colour chemistry research.In recent years, to ionic liquid commercial Application in terms of correlative study just deepen continuously, and
There is relatively broad application in field of environment-friendly organic synthesis.But ionic liquid application there is also its own problem, such as consumption
Greatly, it is expensive, cause the raising of its cost；And the existence form of liquid not only makes product separate difficulty, big viscosity also makes
Obtain ionic liquid recovery loss larger, further increase cost.
Supported ionic liquids open frontier for the commercial Application of ionic liquid.Will be from by chemically and physically method
Sub- fluid load is on solid carrier.Make supported ionic liquid with carrier material high-specific surface area and ionic liquid
High catalytic activity, not only improves the utilization rate of ionic liquid, and drastically reduce the area the consumption of ionic liquid, significantly reduces
Cost, and be easy to the separation of product and the recovery of ionic liquid, more realizing that fixed bed continuous prodution is provided may.
The content of the invention
The invention provides a kind of preparation method and applications of immobilized ionic-liquid catalyst, the catalyst is used to urge
The particularly selective ester type compound of esters is combined to, efficient, the good, environmental pollution of selectivity is small, Repeatability is good.
A kind of preparation method of immobilized ionic-liquid catalyst, comprises the following steps：
（1）PS is mixed with ethyl acetate, Amine Solutions are mixed with by dropwise addition mode, stirring is anti-
Should, synthesize ionic liquid intermediate；
（2）The organic component ionic liquid intermediate reacts to obtain acidic ionic liquid with inorganic component aqueous acid in oil bath heating
Body；
（3）The acidic ion liquid aqueous solution and tetraethyl orthosilicate alcoholic solution after sour environment reacts in oil bath and terminates,
Ageing, roasting obtains final product the immobilized ionic-liquid catalyst.
Ionic liquid is the new greenization reagent of a class, in addition to solvent or catalyst as reaction, is being greatly improved
On the premise of the conversion ratio and selectivity of reaction so that reaction condition becomes gentle.It is particularly with sulfonic group with ionic liquid
Ionic liquid, except outer with stronger acidity, in catalytic reaction " from separation "（self-seperation）Performance makes it
Application receive much attention.Acidic ion liquid is immobilized overcome the liquid acids such as sulfuric acid, hydrochloric acid corrosivity it is strong, it is difficult reclaim lack
Point, while reducing the recovery loss that big viscosity is brought when acidic ion liquid is used.
Many for the harshness of catalytic reaction condition present in selective esterification course of reaction, side reaction, selectivity is low and anti-
The problem that speed is slow is answered, has developed a kind of immobilized ionic-liquid catalyst.
Based on the reason for it is its high activity that solid-state nmr analysis and research show highly acid and three-dimensional effect, the present invention uses 1,
3-N-morpholinopropanesulfonic acid lactone, organic amine prepare organic ion liquid intermediate for raw material, the intermediate respectively with various strong acid knots
Acidic ion liquid is closed to obtain, recycles sol-gal process to be prepared into immobilized ionic-liquid catalyst, each group divides it in catalyst
Between mutually cooperate with, highly acid and three-dimensional effect make the catalyst activity that the present invention prepares and stability all significantly carry
Height, with good activity during to catalysis preparation esterification, conversion ratio prepares laurate more than 90% particularly with catalysis
During monoglyceride, conversion ratio in 45min up to more than 90%, the selectivity of monoglyceride more than 80%, the equal recoverable of catalyst,
After repeating to test 5 times, determine yield and float within 5%.
Preferably, the organic amine is N- methylimidazoles, pyridine, triethylamine, DMA, N, N- dimethyl
The intermediate that benzylamine, methenamine etc. are prepared with 1,3- propane sultones corresponds to N- methylimidazole propyl sulfonic acids ammonium, pyrrole
Pyridine propyl sulfonic acid ammonium, triethyl group propyl sulfonic acid ammonium, N, N- dimethylphenylpropyls ichthyodin, N, N- dimethyl benzyl propyl sulfonic acids
Ammonium salt, tetrapropyl sulfonic group hexa-methylene ammonium salt；The acid is sulfuric acid, hydrochloric acid, phosphoric acid, p-methyl benzenesulfonic acid, trifluoroacetic acid.Using
The catalyst that the combination is prepared its catalysis prepares ethyl laurate yield more than 90%, prepares the conversion of Glycerol Monolaurate
Rate more than 90%, the selectivity more than 80% of monoesters.
It is further preferred that the organic amine is N, N- dimethyl benzylamines and N- methylimidazoles；The acid is sulfuric acid, salt
Acid.
Most preferably, the organic amine is N, N- dimethyl benzylamines；The acid is sulfuric acid, under the optimal material combination
Ethyl laurate yield more than 90% during the catalyst esterification for preparing, the conversion ratio of Glycerol Monolaurate is 90%
More than, monoesters selectivity more than 80%.
Preferably, step（1）Described in the amount ratio of material of PS and organic amine be 1:1.
Further preferably, step（2）Intermediate ion liquid intermediate is 1 with the amount ratio of the material of sulfuric acid:1.
Most preferably, step（3）Middle sulfate ion content liquid accounts for 20%.
In the present invention by above-mentioned organic amine with it is various acid proportioning it is preferred, immobilized content it is preferred, prepare
Catalyst activity is significantly improved, and reduces the usage amount of ionic liquid；Reaction disperses to suspend during the course of the reaction after terminating
Catalyst cooling after be layered, catalysis activity stabilization, catalytic effect keeps good.
Preferably, step（1）The temperature of middle oil bath reaction is 40 ~ 80 DEG C, and the time is 1 ~ 5h；Step（2）Middle oil bath is anti-
The temperature answered is 70 ~ 110 DEG C, and the time is 18 ~ 30h.Step（3）Step（3）The temperature of middle oil bath reaction is 50-100 DEG C, time
It is 18-30h；
It is further preferred that step（1）The temperature of middle oil bath reaction is 50 DEG C, and the time is 2h；Step（2）The temperature of middle oil bath reaction
It is 90 DEG C to spend, and the time is 24h.Step（3）The temperature of reaction is 60 DEG C, and the time is 12h.
Post-processing step described in catalyst preparation process is：Place reaction liquid into culture dish evaporate into it is dry, at 100 DEG C
Overnight dry, 5h is calcined for 200 DEG C in collection residue placement Muffle furnace, it is final to obtain described product.
Compared with prior art, the present invention has the advantages that：
The present invention with PS, organic amine with various strong acid as raw material prepares ionic-liquid catalyst, and consolidated
Loadization, the solid-supported catalyst for obtaining is applied to selective esterification reaction, the association of operation simplicity, stereoeffect and Radiation grafting
Same-action makes catalyst show that preferable catalysis activity, selectivity of product are high, recovery is convenient, it is good to recycle performance.This hair
Bright outstanding advantages are that ionic liquid usage amount is low, catalysis activity is good, selectivity is high, the reaction time greatly shortens, it is simple to post-process,
Recycle performance good, belong to Green Chemistry.
Specific embodiment
In order to better illustrate technical scheme, the present invention is further elaborated on reference to embodiment.
It is raw materials used in following examples to be commercial goods.
Embodiment 1
With 20% load N, as a example by N- dimethyl benzyl propyl sulfonic acid base ammonium hydrogen sulfate ionic liquids, the preparation method of catalyst is such as
Under：
（1）By 1,3- propane sultones and ethyl acetate（Raw material mixed with solvent before this, and ethyl acetate is solvent, is then dripped again
Plus the ethyl acetate solution of another raw material）Mixing, N, the acetic acid of N- dimethyl benzylamines are added dropwise under room temperature condition to mixed solution
Ethyl ester solution, intensification stirring reaction, reaction cools down suction filtration after terminating, and washs, and is vacuum dried to obtain white solid N, N- dimethylbenzyl
Base propyl sulfonic acid ammonium（DMBPSH）；The quality of ethyl acetate is about 2 ~ 3 times of PS, the N of addition, N- dimethyl
Benzylamine is 1 with the amount ratio of 1,3- propane sultone materials:1, oil bath reaction temperature is 50 DEG C, and the reaction time is 2h.
（2）N is weighed, N- dimethyl benzyl propyl sulfonic acid ammoniums are dissolved in distilled water, the concentrated sulfuric acid, stirring is added dropwise to reaction system
After reaction terminates, washing reaction thing removes water to obtain faint yellow ionic liquid（[DMBPSH]HSO4）；N, N- dimethyl benzyl propyl group sulphur
Sour ammonium（DMBPSH）It is 1 with the amount ratio of sulfuric acid material:1, oil bath reaction temperature is 90 DEG C, the h of reaction time 24.
（3）By ethanol, tetraethyl orthosilicate and step（2）Gained ionic liquid forms mixing in 15 ~ 30min of stirring under normal temperature
Solution；Appropriate concentrated hydrochloric acid is added dropwise makes reaction be in acid condition, and reaction system is positioned in oil bath, is stirred overnight.
The amount of ethanol is about 4-5 times of tetraethyl orthosilicate, and tetraethyl orthosilicate is 8 with the amount ratio of the material of ionic liquid:2,
Oil bath reaction temperature is 60 DEG C, and the reaction time is 24h.
（4）After stirring reaction terminates, place reaction liquid into culture dish and evaporate into dry, overnight dried at 100 DEG C, collect surplus
5h is calcined in excess placement Muffle furnace for 200 DEG C, it is final to obtain described product [DMBPSH] HSO4/SG（Silica gel）.
Respectively with hydrochloric acid（HCl）, p-methyl benzenesulfonic acid（PTSA）, phosphoric acid（H3PO4）, trifluoroacetic acid（CF3COOH）Replace with
Upper step（2）Middle sulfuric acid, with N- methylimidazole propyl sulfonic acid ammoniums（MIMPSH）, pyridylpropyl ichthyodin（PPSH）, triethyl group third
Base ichthyodin（TEAPSH）, N, N- dimethylphenylpropyl ichthyodins（DMPPSH）, tetrapropyl sulfonic group hexa-methylene ammonium salt
（Tshx）Replace above step（1）In organic amine, prepare the different ionic liquid catalyst of silica gel load：[DMBPSH]
HSO4、[DMBPSH]HCl、[DMBPSH]PTSA、[DMBPSH]H2PO4、[DMBPSH]CF3COO、[DMPPSH]HSO4、
[TEAPSH]HSO4、[MIMPSH]HSO4、[PPSH]HSO4、[Tshx][HSO4]4By the above-mentioned different ionic liquid for preparing
Catalyst is used to catalyze and synthesize high-grade aliphatic ester in following examples.
Embodiment 2-11
In to the there-necked flask equipped with constant pressure funnel and 100 mL of reflux condensing tube, laurate 10.0g, ethanol are sequentially added
18.4g, 20% supported catalyst 0.40g, are placed on heating response 3.0h in 90 DEG C of oil baths.Reaction is cooled down after terminating, catalysis
Agent and reaction system are layered, and product suction filtration separates solid catalyst, through ether washing, dry after can be directly used for it is next time anti-
Should.Excessive ethanol is evaporated off.Vacuum distillation obtains ethyl laurate, and gas-chromatography carries out purity detecting.
From the variety classes supported catalyst prepared in embodiment 1, operated by examples detailed above, obtain esterification result
As shown in table 1.
Table 1
| Catalyst type | Yield/% | Purity/% |
| [DMBPSH]HSO4/SG | 95.3 | 99.5 |
| [DMBPSH]HCl/SG | 92.5 | 98.0 |
| [DMBPSH]PTSA/SG | 91.3 | 98.2 |
| [DMBPSH]H2PO4/SG | 90.7 | 99.3 |
| [DMBPSH]CF3COO/SG | 90.1 | 99.1 |
| [DMPPSH]HSO4/SG | 93.8 | 98.4 |
| [TEAPSH]HSO4/SG | 94.2 | 98.9 |
| [MIMPSH]HSO4/SG | 94.8 | 98.5 |
| [PPSH]HSO4/SG | 93.6 | 98.2 |
| [Tshx][HSO4]4/SG | 94.5 | 99.2 |
Embodiment 12-24
In there-necked flask to 100 mL equipped with reflux condensing tube, laurate 10g, glycerine 18.4g, catalyst are sequentially added
0.20g, is placed on heating response 45min in 150 DEG C of oil baths.Reaction is cooled down after terminating, and catalyst is layered with reaction system,
Product suction filtration separates solid catalyst, and next secondary response is can be directly used for after ether washing, drying.Gas-chromatography is to reaction
Conversion ratio and Glycerol Monolaurate yield are analyzed.
Continue esterification from the different loads ionic-liquid catalyst prepared in embodiment 1, obtain laurate list sweet
Ester esterification result is as shown in table 2.
Table 2
| Catalyst type | Conversion ratio/% | Yield/% |
| 5%[DMBPSH]HSO4/SG | 81.3 | 69.1 |
| 10%[DMBPSH]HSO4/SG | 90.1 | 73.7 |
| 20%[DMBPSH]HSO4/SG | 95.3 | 80.3 |
| 30%[DMBPSH]HSO4/SG | 96.5 | 79.5 |
| 20% [DMBPSH]HCl/SG | 93.1 | 76.8 |
| 20% [DMBPSH]PTSA/SG | 92.3 | 75.5 |
| 20% [DMBPSH]H2PO4/SG | 90.7 | 74.8 |
| 20% [DMBPSH]CF3COO/SG | 90.1 | 72.5 |
| 20% [DMPPSH]HSO4/SG | 93.7 | 78.2 |
| 20% [TEAPSH]HSO4/SG | 94.5 | 78.6 |
| 20% [MIMPSH]HSO4/SG | 94.6 | 79.6 |
| 20% [PPSH]HSO4/SG | 93.9 | 78.3 |
| 20% [Tshx][HSO4]4/SG | 95.1 | 78.5 |
Embodiment 25-29
In there-necked flask to 100 mL equipped with reflux condensing tube, laurate 10g, catalyst 0.2g are sequentially added, be placed on
Heating response 45min in 150 DEG C of oil baths, reaction is cooled down after terminating, and catalyst is layered with reaction system, and product suction filtration separates solid
Body catalyst, next secondary response is can be directly used for after ether washing, drying.Gas-chromatography is to reaction conversion ratio and laurate
Monoglyceride yield is analyzed.It is as shown in table 3 that change glycerine obtains esterification result with the amount ratio of bay acid substance.
Table 3
| The amount ratio of alcohol acid substance | Conversion ratio/% | Yield/% |
| 2 : 1 | 84.7 | 69.3 |
| 3 : 1 | 90.1 | 78.6 |
| 4 : 1 | 95.3 | 80.3 |
| 5 : 1 | 95.6 | 79.0 |
| 6 : 1 | 96.2 | 77.1 |
Embodiment 30-34
In there-necked flask to 100 mL equipped with reflux condensing tube, laurate 10g, glycerine 18.4g, catalyst are sequentially added
0.20g, is placed on heating response 45min in oil bath, and reaction is cooled down after terminating, and catalyst is layered with reaction system, and product is taken out
Filter separates solid catalyst, and next secondary response is can be directly used for after ether washing, drying.Gas-chromatography is to reaction conversion ratio
And Glycerol Monolaurate yield is analyzed.It is as shown in table 4 that change differential responses temperature obtains esterification result.
Table 4
| Reaction temperature/DEG C | Conversion ratio/% | Yield/% |
| 130 | 81.2 | 72.9 |
| 140 | 94.3 | 82.6 |
| 150 | 95.3 | 80.3 |
| 160 | 95.8 | 73.4 |
| 170 | 98.0 | 68.8 |
More than reaction terminate after, the equal recoverable of catalyst, repeat experiment five times after, determine yield float 5 % with
It is interior.
Show that catalyst prepared by which just shows preferably during relatively low ionic liquid usage amount by above example card
Catalysis activity and monoglyceride selectivity high, and the reaction time greatly shortens, to post-process easy, pollution few, belongs to greenization
Work technology.
Certainly, those of ordinary skill in the art is it should be appreciated that the embodiment of the above is intended merely to explanation originally
Invention, and limitation of the invention is not intended as, as long as in essential scope of the invention, the change to embodiment described above
Change, modification will all fall in the range of claims of the present invention.
Claims (10)
1. a kind of preparation method of immobilized ionic-liquid catalyst, it is characterised in that comprise the following steps：
（1）1-1.5 is compared by the amount of material in ethyl acetate as raw material with organic amine, PS:1 synthesis ionic liquid
Body intermediate；
（2）The step（1）Gained ionic liquid intermediate and inorganic component aqueous acid in oil bath heating react it is acid from
Sub- liquid；
（3）The acidic ion liquid and tetraethyl orthosilicate alcoholic solution after sour environment react in oil bath and terminates, ageing, sky
200 DEG C of roastings obtain final product the immobilized ionic-liquid catalyst during atmosphere is enclosed.
2. the preparation method of immobilized ionic-liquid catalyst according to claim 1, it is characterised in that the organic amine is
N- methylimidazoles, pyridine, triethylamine, N, accelerine, N, any one in N- dimethyl benzylamines or methenamine.
3. the preparation method of immobilized ionic-liquid catalyst according to claim 1, it is characterised in that step（2）In nothing
The acid of machine component is any one inorganic acid in sulfuric acid, hydrochloric acid, phosphoric acid, p-methyl benzenesulfonic acid or trifluoroacetic acid.
4. the preparation method of immobilized ionic-liquid catalyst according to claim 1, it is characterised in that step（2）In from
Sub- liquid intermediate is 1 with the amount ratio of the material of inorganic component acid:1.
5. the preparation method of immobilized ionic-liquid catalyst according to claim 1, it is characterised in that step（3）Middle acid
The amount content of property ionic liquid material is accounted for：5%-30%.
6. the preparation method of immobilized ionic-liquid catalyst according to claim 5, it is characterised in that step（3）Middle acid
The amount content of property ionic liquid material accounts for 20%.
7. the preparation method of immobilized ionic-liquid catalyst according to claim 1, it is characterised in that step（3）Middle acid
It is hydrochloric acid to change used acid, any one in nitric acid, oxalic acid, citric acid or ascorbic acid.
8. the preparation method of immobilized ionic-liquid catalyst according to claim 1, it is characterised in that step（1）Middle oil
The temperature for bathing reaction is 40 ~ 80 DEG C, and the time is 2 ~ 10h；Step（2）The temperature of middle oil bath reaction is 70 ~ 110 DEG C, the time is 18 ~
30h;Step（3）Oil bath reaction temperature is 50 ~ 100 DEG C in middle oil bath, and mixing time is 18-30h.
9. the preparation method of immobilized ionic-liquid catalyst according to claim 1, it is characterised in that step（1）Middle institute
It is 1 that PS is stated with the amount ratio of the material of organic amine:1.
10. what a kind of preparation method as described in claim 1 ~ 9 any claim was prepared is immobilized ionic liquid-catalyzed
Agent.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108558891A (en) * | 2018-05-11 | 2018-09-21 | 浙江工业大学 | A kind of supported on silica-gel multinuclear sulfonic group acidic ion liquid and application |
| CN108906021A (en) * | 2018-06-01 | 2018-11-30 | 浙江利欧环保科技有限公司 | A kind of thorium doping tripolite loading Catalyzed by p-Toluenesulfonic Acid agent and its preparation method and application |
| CN108911977A (en) * | 2018-06-12 | 2018-11-30 | 浙江工业大学 | A kind of method that supported on silica-gel multi-sulfonic functional ion liquid catalyzes and synthesizes isopropyl palmitate |
| CN110331001A (en) * | 2019-07-11 | 2019-10-15 | 福建师范大学福清分校 | The preparation method and applications of the immobilized ionic liquid of ferrous metals organic backbone |
| CN110918124A (en) * | 2019-12-12 | 2020-03-27 | 福建师范大学福清分校 | Preparation method and application of iron-based MOFs immobilized ionic liquid |
| CN111072559A (en) * | 2019-12-15 | 2020-04-28 | 浙江工商大学 | Construction and application of 2, 6-dibromopyridine oxidation system |
| CN112570022A (en) * | 2020-12-10 | 2021-03-30 | 浙江工商大学 | Magnetic substance immobilized organic-inorganic hybrid material catalyst and preparation and application thereof |
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2016
- 2016-11-15 CN CN201611003854.0A patent/CN106694036A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| 梁丽亚: ""固载化酸性离子液体催化酯化反应研究"", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108558891A (en) * | 2018-05-11 | 2018-09-21 | 浙江工业大学 | A kind of supported on silica-gel multinuclear sulfonic group acidic ion liquid and application |
| CN108906021A (en) * | 2018-06-01 | 2018-11-30 | 浙江利欧环保科技有限公司 | A kind of thorium doping tripolite loading Catalyzed by p-Toluenesulfonic Acid agent and its preparation method and application |
| CN108906021B (en) * | 2018-06-01 | 2021-05-18 | 浙江利欧环保科技有限公司 | Thorium-doped diatomite-loaded p-toluenesulfonic acid catalyst and preparation method and application thereof |
| CN108911977A (en) * | 2018-06-12 | 2018-11-30 | 浙江工业大学 | A kind of method that supported on silica-gel multi-sulfonic functional ion liquid catalyzes and synthesizes isopropyl palmitate |
| CN110331001A (en) * | 2019-07-11 | 2019-10-15 | 福建师范大学福清分校 | The preparation method and applications of the immobilized ionic liquid of ferrous metals organic backbone |
| CN110918124A (en) * | 2019-12-12 | 2020-03-27 | 福建师范大学福清分校 | Preparation method and application of iron-based MOFs immobilized ionic liquid |
| CN111072559A (en) * | 2019-12-15 | 2020-04-28 | 浙江工商大学 | Construction and application of 2, 6-dibromopyridine oxidation system |
| CN111072559B (en) * | 2019-12-15 | 2021-06-18 | 浙江工商大学 | Construction and application of 2, 6-dibromopyridine oxidation system |
| CN112570022A (en) * | 2020-12-10 | 2021-03-30 | 浙江工商大学 | Magnetic substance immobilized organic-inorganic hybrid material catalyst and preparation and application thereof |
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