CN105289731A - Immobilized polyacid catalyst as well as preparation method and application thereof - Google Patents

Immobilized polyacid catalyst as well as preparation method and application thereof Download PDF

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Publication number
CN105289731A
CN105289731A CN201510880671.6A CN201510880671A CN105289731A CN 105289731 A CN105289731 A CN 105289731A CN 201510880671 A CN201510880671 A CN 201510880671A CN 105289731 A CN105289731 A CN 105289731A
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polyacid
acid
catalyst
poms
immobilized
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单春燕
张云黔
陶朱
梁正云
魏娴
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Guizhou University
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Guizhou University
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    • 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

Abstract

The invention relates to novel solid polyacid catalyst formed by immobilizing polyacid on a Q[6]-POMs self-assembly formed by using the self-assembling effect of cucurbit urils (Q[6] with phosphomolybdic acid, phosphotungstic acid and silicotungstic acid polyacid POMs. The self-assembly is difficult to dissolve in water, acid, alkaline solution and organic solvent and can maintain the original structure and performance of the cucurbit urils and polyacid. In the ester synthetic reaction, the original catalytic performance of the polyacid immobilized by Q[6] is kept; moreover, due to the characteristics such as simple preparation, stable performance, convenience use, easy recycling and reusability, the novel solid polyacid catalyst is environmentally friendly, economical and practical and has potential application prospect and economic benefit.

Description

A kind of immobilized polyacid Catalysts and its preparation method and application
Technical field
The present invention is chemical catalyst and Synthesis and applications technical field, specifically a kind of immobilized polyacid Catalysts and its preparation method and application.
Background technology
Polyacid (Polyoxometalates, be abbreviated as POMs) the class polyoxy acid (salt) that is made up of by oxygen atom ligand bridging by certain structure many metallic atoms (as Mo, W, V, Nb, Ta etc.) and hetero atom (as P, Si, Fe, Co etc.), there is very high catalytic activity, it not only has acidity, and there is oxidation-reduction quality, be a kind of multifunctional novel catalyst.In catalytic reaction, effect is preferably structure with Keggin heteropoly acid at present, and its general structure of polyoxoanion with Keggin-type structure is [XM 12o 40] n-(X=P, Si, Ge, As etc., M=Mo, W etc.), such as phosphotungstic acid, silico-tungstic acid, phosphomolybdic acid etc.Because polyacid is water-soluble fabulous, be difficult to when using as catalyst reclaim, add use cost, also certain pollution is caused to environment.
In order to solve defect when polyacid catalyst uses, at present main by polyacid load on some porous carriers such as active carbon, silica, molecular sieve, kaolin and diatomite, form solid catalyst, or polyacid is made multi-acid salt, so that reclaim.But above method also exists, and preparation is loaded down with trivial details, load is unstable, the rate of recovery and the defect such as recycling rate of waterused is low.
Summary of the invention
The object of the invention is to there is catalyst when solution polyacid uses as catalyst be difficult to reclaim, cost is high, but also the problem to environment.Solve the solid catalyst that polyacid formed to there is preparation method loaded down with trivial details simultaneously, and load is unstable, the rate of recovery and the low problem of recycling rate of waterused.
The present invention is based on large ring cage compound-hexa-atomic melon ring Q [6], the polyacid compounds such as phosphomolybdic acid, phosphotungstic acid, silico-tungstic acid are object, utilize the hydrogen bond action between host and guest compound, dipole effect etc., self assembly forms the stable immobilized polyacid catalyst of melon ring of structure and properties, and be successfully applied in esterification, obtain good catalytic effect.
A kind of immobilized polyacid catalyst of the present invention, it is Q [the 6]-POMs self-assembly formed with phosphomolybdic acid, phosphotungstic acid or silico-tungstic acid polyacid class Substance P OMs self assembly effect by hexa-atomic melon ring (Q [6]), Q [6] and POMs mol ratio are 1.8 ~ 2.5:1, Q [6]-POMs self-assembly is a kind of novel solid polyacid catalyst, be insoluble in water, acid, aqueous alkali and organic solvent, in Synthesis Diethyl ether, have catalytic action.
1. above-mentioned indication polyacid is Keggin-type phosphomolybdic acid H 3pM o12o 40, be abbreviated as PM o12; Phosphotungstic acid H 3pW 12o 40, be abbreviated as PW 12; Silico-tungstic acid H 4siW 12o 40, be abbreviated as SiW 12, the immobilized polyacid catalyst of generation is respectively Q [6]-PW 12, Q [6]-PMo, Q [6]-SiW 12.
The preparation method of a kind of immobilized polyacid catalyst of the present invention, follows these steps to preparation:
(1) Q [6] is dissolved in 1MHCl solution, obtains Q [6] hydrochloric acid solution;
(2) by water-soluble to phosphomolybdic acid, phosphotungstic acid or silico-tungstic acid class Substance P OMs, the POMs aqueous solution is obtained;
(3) under stirring or ultrasonic oscillation condition, the POMs aqueous solution is slowly added drop-wise in Q [6] hydrochloric acid solution, makes Q [6] be 1.8 ~ 2.5:1 with the mol ratio of POMs, after two kinds of solution mixing, produce a large amount of precipitation;
(4) filter after precipitation being left standstill 24 hours;
(5) wash with water and be precipitated to neutrality;
(6) Q [6]-POMs self-assembly is obtained after precipitation being dried at 50 ~ 100 DEG C.
When above-mentioned steps (3) Q [6] and POMs mol ratio are 2:1, the output of Q [6]-POMs is the highest.
The application of a kind of immobilized polyacid catalyst of the present invention is in Synthesis Diethyl ether reaction, Q [6]-PW 12, Q [6]-PMo, Q [6]-SiW 12as catalyst.
4., in Synthesis Diethyl ether reaction, when glacial acetic acid and absolute ethyl alcohol mol ratio are 1:2, join Q [6]-PW by every 100mL absolute ethyl alcohol 12catalyst 2.61g, the reaction time is that the 1 little ethyl acetate of gained constantly productive rate is the highest; When glacial acetic acid and absolute ethyl alcohol mol ratio are 1:2, join Q [6]-PMo catalyst 4.35g by every 100mL absolute ethyl alcohol, the reaction time is that the 2 little productive rates of products therefrom are constantly the highest; When glacial acetic acid and absolute ethyl alcohol mol ratio are 1:2, join Q [6]-SiW by every 100mL absolute ethyl alcohol 12catalyst 2.61g, the reaction time is that the 2.5 little productive rates of products therefrom are constantly the highest.
invention effect: the present invention utilizes the hydrogen bond action between Q [6] and POMs, dipole effect, form the immobilized polyacid catalyst of melon ring that structure and properties is stable, not only solve polyacid to be difficult to reclaim as the catalyst that catalyst is used alone existence, cost is high, but also the problem to environment, and solve that polyacid is combined with other carriers that the preparation method that the solid catalyst that formed exists is loaded down with trivial details, load is unstable, the rate of recovery and the low problem of recycling rate of waterused.Generate in the process of ethyl acetate at catalysis ethanol and acetic acidreaction and obtain good application, be embodied in catalyst and repeatedly recycle, the productive rate of ethyl acetate is high, reduces production of ethyl cost.
The present invention's immobilized polyacid catalyst of hexa-atomic melon ring, preparation is simple, stable in properties, easy to use, be easy to reclaim, the features such as profit can be repeated, be a kind of environmental friendliness, economical and practical novel polyacid catalyst, there is potential application prospect and economic benefit.
Accompanying drawing explanation
Fig. 1-Fig. 3 is respectively Q [6]-PMo 12, Q [6]-PW 12, Q [6]-SiW 12the infrared spectrogram of self-assembly system.Wherein a be polyacid, the infrared spectrogram of b to be Q [6], c be Q [6]-POM self-assembly.
From Fig. 1-3, the characteristic peak of melon ring and polyacid all appears in the spectrogram of self-assembly, but has all occurred displacement, and illustrate that melon ring and polyacid there occurs interaction, in self-assembly, both structures do not change.
Detailed description of the invention
Embodiment 1: immobilized phosphomolybdic acid catalyst preparing
(1) 1.18gQ [6] is dissolved in 20mL1MHCl solution, obtains Q [6] hydrochloric acid solution;
(2) by 0.92g phosphomolybdic acid PMo 12be dissolved in 15mL water, obtain the phosphomolybdic acid aqueous solution;
(3) under stirring or ultrasonic oscillation condition, the phosphomolybdic acid aqueous solution is slowly added drop-wise in Q [6] hydrochloric acid solution, after two kinds of solution mixing, produces a large amount of precipitation;
(4) filter after precipitation being left standstill 24 hours;
(5) wash with water and be precipitated to neutrality;
(6) 2.19gQ [6]-PMo is obtained after precipitation being dried at 80 DEG C 12self-assembly.
Embodiment 2: prepared by Catalyzed By Immobilized Phosphotungstic agent
(1) 1.18gQ [6] is dissolved in 20mL1MHCl solution, obtains Q [6] hydrochloric acid solution;
(2) by 1.44g phosphotungstic acid PW 12be dissolved in 15mL water, obtain phosphotungstic acid aqueous solution;
(3) under stirring or ultrasonic oscillation condition, phosphotungstic acid aqueous solution is slowly added drop-wise in Q [6] hydrochloric acid solution, after two kinds of solution mixing, produces a large amount of precipitation;
(4) filter after precipitation being left standstill 24 hours;
(5) wash with water and be precipitated to neutrality;
(6) 2.32gQ [6]-PW is obtained after precipitation being dried at 80 DEG C 12self-assembly
Embodiment 3: immobilized silicotungstic acid catalyst preparation
(1) 1.18gQ [6] is dissolved in 20mL1MHCl solution, obtains Q [6] hydrochloric acid solution;
(2) by 1.43g silico-tungstic acid SiW 12be dissolved in 15mL water, obtain silicon tungsten acid solution;
(3) under stirring or ultrasonic oscillation condition, silicon tungsten acid solution is slowly added drop-wise in Q [6] hydrochloric acid solution, after two kinds of solution mixing, produces a large amount of precipitation;
(4) filter after precipitation being left standstill 24 hours;
(5) wash with water and be precipitated to neutrality;
(6) 2.37gQ [6]-PW is obtained after precipitation being dried at 80 DEG C 12self-assembly
Embodiment 4: the synthesis of ethyl acetate be separated
Q [the 6]-PMo of 7.2mL glacial acetic acid, 11.5mL absolute ethyl alcohol and 0.3g is added in 100mL round-bottomed flask 12(or Q [6]-PW 12) catalyst, after stirring and refluxing a period of time, stop heating, after being cooled to room temperature, change distilling apparatus into, heating water bath distills, and obtains ethyl acetate crude product.
In crude product, saturated sodium carbonate solution is added, until no longer including carbon dioxide effusion, till organic phase pH is neutrality under stirring.Proceeded to by liquid in 60mL separatory funnel, leave standstill after shake, divide phase of anhydrating, the saturated calcium chloride solution of organic phase 15mL washes twice.Discard subnatant, ester layer proceeds in dry conical flask and uses anhydrous magnesium sulfate drying.Dried thick ethyl acetate is filtered in 25mL cucurbit, water-bath is distilled, collect 73 ~ 78 DEG C of cuts, calculate output, and differentiate product purity with abbe's refractometer.
Q [6]-POMs self-assembly makes catalyst, carries out orthogonal test to the reaction of synthesizing ethyl acetate.Experimental result shows, is 1:2 at glacial acetic acid and absolute ethyl alcohol mol ratio, when calculating by every 100mL absolute ethyl alcohol, as Q [6]-PW 12catalyst amount is 2.61g, and the reaction time is 1 constantly little, and the productive rate of products therefrom is the highest, is 75.5%, index of refraction n d 20be 1.3727; Q [6]-PMo 12the consumption of catalyst is 4.35g, and the reaction time is 2 constantly little, and the productive rate of products therefrom is the highest, is 89.1%, index of refraction n d 20be 1.3713.Q [6]-SiW 12the consumption of catalyst is 2.61g, and the reaction time is 2.5 constantly little, and the productive rate of products therefrom is the highest, is 88.3%, index of refraction n d 20be 1.3720.
Embodiment 5: the recovery of catalyst and recycling
By reacting liquid filtering, filter cake distilled water washs, and weighs after vacuum drying, desorption, calculates catalyst recovery yield.Catalyst will be reclaimed and repeat embodiment 1 by above optimum synthesis condition.Detecting catalyst reuses the result of 5 times.
Experimental result shows, Q [6]-PW 12catalyst reuses the rate of recovery of 5 times all more than 96%, and productive rate is all more than 66%, and maximum output is 68.1%; Q [6]-PM o12catalyst reuses the rate of recovery of 5 times all more than 94%, and productive rate is all more than 86%, and maximum output is 88.1%.Q [6]-SiW 12catalyst reuses the rate of recovery of 5 times all more than 94%, and productive rate is all more than 85%, and maximum output is 87.5%.

Claims (6)

1. an immobilized polyacid catalyst, it is characterized in that Q [the 6]-POMs self-assembly formed with phosphomolybdic acid, phosphotungstic acid or silico-tungstic acid polyacid class Substance P OMs self assembly effect by hexa-atomic melon ring Q [6], Q [6] and POMs mol ratio are 1.8 ~ 2.5:1, Q [6]-POMs self-assembly is a kind of novel solid polyacid catalyst, be insoluble in water, acid, aqueous alkali and organic solvent, in Synthesis Diethyl ether, have catalytic action.
2. immobilized polyacid catalyst according to claim 1, is characterized in that indication polyacid is Keggin-type phosphomolybdic acid H 3pM o12o 40, be abbreviated as PM o12, phosphotungstic acid H 3pW 12o 40, be abbreviated as PW 12, silico-tungstic acid H 4siW 12o 40, be abbreviated as SiW 12, the immobilized polyacid catalyst of generation is respectively Q [6]-PW 12, Q [6]-PMo, Q [6]-SiW 12.
3., according to the preparation method of a kind of immobilized polyacid catalyst according to claim 1, it is characterized in that following these steps to preparation:
(1) Q [6] is dissolved in 1MHCl solution, obtains Q [6] hydrochloric acid solution;
(2) by water-soluble to phosphomolybdic acid, phosphotungstic acid or silico-tungstic acid class Substance P OMs, the POMs aqueous solution is obtained;
(3) under stirring or ultrasonic oscillation condition, the POMs aqueous solution is slowly added drop-wise in Q [6] hydrochloric acid solution, makes Q [6] be 1.8 ~ 2.5:1 with the mol ratio of POMs, after two kinds of solution mixing, produce a large amount of precipitation;
(4) filter after precipitation being left standstill 24 hours;
(5) wash with water and be precipitated to neutrality;
(6) Q [6]-POMs self-assembly is obtained after precipitation being dried at 50 ~ 100 DEG C.
4. the preparation method of a kind of immobilized polyacid catalyst according to claim 3, when it is characterized in that step (3) Q [6] and POMs mol ratio are 2:1, the output of Q [6]-POMs is the highest.
5. the application of a kind of immobilized polyacid catalyst as claimed in claim 1, is characterized in that in Synthesis Diethyl ether reaction, Q [6]-PW 12, Q [6]-PMo, Q [6]-SiW 12as catalyst.
6. the application of a kind of immobilized polyacid catalyst according to claim 5, is characterized in that, in Synthesis Diethyl ether reaction, when glacial acetic acid and absolute ethyl alcohol mol ratio are 1:2, joining Q [6]-PW by every 100mL absolute ethyl alcohol 12catalyst 2.61g, the reaction time is that the 1 little ethyl acetate of gained constantly productive rate is the highest; When glacial acetic acid and absolute ethyl alcohol mol ratio are 1:2, join Q [6]-PMo catalyst 4.35g by every 100mL absolute ethyl alcohol, the reaction time is that the 2 little productive rates of products therefrom are constantly the highest; When glacial acetic acid and absolute ethyl alcohol mol ratio are 1:2, join Q [6]-SiW by every 100mL absolute ethyl alcohol 12catalyst 2.61g, the reaction time is that the 2.5 little productive rates of products therefrom are constantly the highest.
CN201510880671.6A 2015-12-04 2015-12-04 Immobilized polyacid catalyst as well as preparation method and application thereof Pending CN105289731A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111841644A (en) * 2020-08-27 2020-10-30 郑州大学 Metal-organic complex immobilized phosphotungstic acid catalyst for synthesizing epoxy cyclohexane

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101033394A (en) * 2007-04-17 2007-09-12 厦门大学 Photochromism material and synthetic method thereof
CN101157053A (en) * 2007-10-17 2008-04-09 贵州大学 Catalyst and use thereof new type solid catalyst as well as its preparing method and usage
CN103386326A (en) * 2013-08-05 2013-11-13 贵州大学 Phosphomolybdic acid-hydroxyl cucurbit[5]uril based porous heterocomplex and synthetic method thereof
CN103467531A (en) * 2013-10-10 2013-12-25 贵州大学 H3PMo12O40-(HO)10Q[5]-light rare earth metal heterocomplex and synthesis and application

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101033394A (en) * 2007-04-17 2007-09-12 厦门大学 Photochromism material and synthetic method thereof
CN101157053A (en) * 2007-10-17 2008-04-09 贵州大学 Catalyst and use thereof new type solid catalyst as well as its preparing method and usage
CN103386326A (en) * 2013-08-05 2013-11-13 贵州大学 Phosphomolybdic acid-hydroxyl cucurbit[5]uril based porous heterocomplex and synthetic method thereof
CN103467531A (en) * 2013-10-10 2013-12-25 贵州大学 H3PMo12O40-(HO)10Q[5]-light rare earth metal heterocomplex and synthesis and application

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111841644A (en) * 2020-08-27 2020-10-30 郑州大学 Metal-organic complex immobilized phosphotungstic acid catalyst for synthesizing epoxy cyclohexane
CN111841644B (en) * 2020-08-27 2022-10-28 郑州大学 Metal-organic complex immobilized phosphotungstic acid catalyst for synthesizing epoxy cyclohexane

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