CN101618349A - Preparation method of heteropoly acid catalysts by taking organic modified concave-convex soil as carrier - Google Patents
Preparation method of heteropoly acid catalysts by taking organic modified concave-convex soil as carrier Download PDFInfo
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- CN101618349A CN101618349A CN200910031954A CN200910031954A CN101618349A CN 101618349 A CN101618349 A CN 101618349A CN 200910031954 A CN200910031954 A CN 200910031954A CN 200910031954 A CN200910031954 A CN 200910031954A CN 101618349 A CN101618349 A CN 101618349A
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Abstract
The invention relates to a preparation method of heteropoly acid loaded on organic modified concave-convex soil, belonging to the technical field of the concave-convex soil utilization and heteropoly acid fixation. The method takes the organic modified concave-convex soil as a carrier, and loading is carried out to the heteropoly acid, so as to obtain loaded heteropoly acid catalysts. On one hand, the method can improve the performance of the heteropoly acid, realizes repeated utilization of the heteropoly acid, and improves the utilization rate of the heteropoly acid and the application range, thereby laying the foundation for the fixation of the heteropoly acid; on the other hand, the application range of the concave-convex soil is expanded, the added value of the concave-convex soil is increased, and the method has good guiding function to the application that the concave-convex soil is used as the catalyst carrier.
Description
Technical field
The preparation method of the organically-modified attapulgite carried heteropoly acid of a kind of silane coupler belongs to the utilization and the heteropoly acid immobilization technology field of attapulgite.
Background technology
Heteropoly acid and its esters are a kind of catalyst that development potentiality is arranged very much, have superpower acidity and oxidation-reduction quality, and under the condition that does not change the heteropolyanion structure, by selecting component (coordination atom, central atom and gegenion etc.), catalytic performance can systematically be regulated and control, and development is very fast aspect application study and exploitation in recent years.Heteropoly acid can dissolve in the reaction system that water and other polar organic matter exist, to react catalysis in a homogeneous system, and the reaction condition gentleness, toxicity and volatility are little, and catalytic efficiency is high, still owing to the very little (＜10m of heteropoly acid specific area
2/ g), especially in homogeneous catalysis, be soluble in polar solvent and cause the recovery difficulty.Therefore heteropoly acid is immobilized on high specific surface carrier, not only can solve the separation problem of catalyst in the homogeneous catalytic reaction, and can improve the catalytic efficiency of catalyst in the heterogeneous catalytic reaction.
The application of carried heteropoly acid catalyst has obtained comparatively extensive studies.Used carrier has Al
2O
3, MgO, silica gel, active carbon, TiO
2, ion exchange resin, molecular sieve, diatomite and other natural silicate material etc.Attapulgite be a kind of layer of chain structure contain Shuifu County's zeopan clay mineral, the aboundresources in China mainly is distributed in ground such as Su Wan.Attapulgite clay mineral has the attribute of nano material, it is natural nano structure mineral material with nanochannel structure, because they have very large specific area, voidage and certain ion exchangeable, can effectively improve the effective active acid position of acid catalyst in the catalytic reaction, simultaneously because the good adsorption performance of attapulgite clay own, can in catalytic reaction, contact with reaction substrate better, make it become a kind of well behaved catalyst carrier.It for example is the preparation (CN 1844382A) of carrier fixed fat enzyme with the attapulgite, preparation and application (CN 101406842A) with Al-pillared paligorskite modified solid acid catalyst, with the palygorskite is hydroxyl nickel powder, the carbonyl iron dust Preparation of catalysts (CN 1857775A) of carrier, is the preparation method (CN 1698958A) of the nickel base hydrogenation reaction catalyst of carrier with the palygorskite.
Summary of the invention
The purpose of this invention is to provide a kind of is the heteropolyacid catalyst of carrier with the attapulgite; Attapulgite has bigger specific area as a kind of fibrous silicate than phyllosilicate, so, utilizing the attapulgite resource of China's abundant, research and development solid-carrying heteropolyacid attapulgite is to improve the value and the utilization rate of existing resource.
Technical scheme: being to be raw material with attapulgite and heteropoly acid, is the carrier of heteropoly acid with organically-modified attapulgite, adopts the excessive infusion process of vacuum that heteropoly acid is carried out immobilization, obtains heterogeneous catalyst, and heteropoly acid has kept its intrinsic structure.
The content of heteropoly acid in catalyst is 5%～40% by weight percentage.
Heteropoly acid is as follows in attapulgite modified load step:
Attapulgite carrier crushing screening final vacuum after organically-modified is heated 30～150min down, add heteropoly acid solution by liquid-solid ratio 10: 1～2: 1 (v/g) then, stir 3～24h, suction filtration, washing thoroughly removes residual solvent under the vacuum, crosses 100 orders～200 mesh sieves, obtain the heteropolyacid catalyst of attapulgite modified load, specific area is 60m
2/ g～250m
2/ g.
The present invention is carrier loaded heteropolyacid catalyst (the effect schematic diagram is seen accompanying drawing 1) with the attapulgite of aminosilane coupling agent modifying, be with the heteropoly acid high degree of dispersion on the attapulgite of the bigger amino coupling agent modification of specific area, the heteropoly acid heat endurance is improved, improve the decentralization of heteropoly acid, make the heteropoly acid chemistry, uniformly, in the space of unbodied surface that is dispersed in carrier or carrier, improved the activity of heteropoly acid, vacuum impregnation has improved the touch opportunity of carrier and heteropoly acid, because the amino of the carrier outer end after amino modified and the chemical action of heteropolyacid anions, in conjunction with stable, the reuse of the catalyst of preparation is greatly improved, and this Preparation of Catalyst production technology is simple, reliably, raw material is inexpensive.
The catalyst of the present invention's preparation is the amino effect with heteropolyanion and modified support surface, formed heterogeneous catalysis, overcome and be soluble in polar solvent in the homogeneous catalyst and cause the problem that reclaims difficulty, can be repeatedly used and activity is still stable, little to equipment corrosion.
Because the present invention does not limit the reaction system of application, all is widely used in polar reaction system such as esterification or ester exchange reaction system or gas-solid reaction.In heterogeneous catalytic reaction, adopt the catalyst of the inventive method preparation, because heteropoly acid is scattered on carrier, the catalytic efficiency height is reused effective.
The present invention adopts the amino coupling agent modification that attapulgite is carried out the fixing of heteropoly acid, can improve performance, utilization rate and the range of application of heteropoly acid, and the efficient increment deep process technology to the exploitation attapulgite has important and practical meanings, for the scope of utilizing that enlarges attapulgite is laid a good foundation.
Description of drawings
The effect schematic diagram of the attapulgite modified and carried heteropoly acid of Fig. 1 KH550.
The X-ray energy spectrum (XPS) of the attapulgite modified carried heteropoly acid of Fig. 2 SG-Si900.A represents the XPS figure of the attapulgite of SG-Si900 modification, and b represents the XPS figure of load phosphotungstic acid catalyst.
The binding energy of N element 399.73eV and 401.83eV from (a) are reduced to 399.27eV and 401.25eV in (b) behind the load phosphotungstic acid as seen from Figure 2, and the 35.63eV place has the peak of W element to occur in (b), the appearance at the skew of N element binding energy and W element peak behind the load phosphotungstic acid, illustrate between amino modified attapulgite and the phosphotungstic anion it is chemical b `, in conjunction with more stable.
The specific embodiment
Embodiment 1
Attapulgite with silane coupler KH550 modification is the preparation of the phosphotungstic acid catalyst of carrier: the attapulgite 2g of KH550 modification, heating vacuumizes handles 90min, add the phosphotungstic acid alcohol-water (1: 1 contain phosphotungstic acid 0.6g under the vacuum, v: v) solution, stirring is spent the night, and filters the ethanol-water mixture washing, remove residual solvent under the vacuum, obtain the phosphotungstic acid catalyst of load.
After measured, the load capacity of phosphotungstic acid is 20%, and specific area is 160.3m
2/ g, pore volume are 0.255cm
3/ g.
Embodiment 2
Attapulgite with silane coupler KH550 modification is the phosphomolybdic acid Preparation of catalysts of carrier: the attapulgite 2g of KH550 modification, heating vacuumizes handles 150min, add and contain phosphomolybdic acid ethanol solution 50mL, stirring is spent the night, filter, residual solvent is removed in the ethanol washing under the vacuum, obtain the phosphomolybdic acid catalyst of load.
After measured, the load capacity of phosphomolybdic acid is 25%, and specific area is 146.7m
2/ g, pore volume are 0.238cm
3/ g.
Attapulgite with silane coupler SG-Si900 modification is the preparation of the phosphotungstic acid catalyst of carrier: the attapulgite 2g of SG-Si900 modification, heating vacuumizes handles 90min, add and contain phosphotungstic acid second cyanogen solution 50mL, stirring is spent the night, filter, residual solvent is removed in washing under the vacuum, obtain the phosphotungstic acid catalyst of load.
After measured, the relative amount of some elements sees Table 1 in the product.
X-ray energy spectrum (XPS) relative amount of table 1 sample
By the XPS relative amount of sample in the table 1 as can be seen after the modification relative amount of 0 element be increased to 51.16%, the relative amount of W, P element is respectively 3.43% and 0.55%.
Claims (6)
1, a kind of is the heteropolyacid catalyst of carrier with organically-modified attapulgite, it is characterized in that with attapulgite and heteropoly acid be raw material, is the carrier of heteropoly acid with the attapulgite, carries out organically-modified to attapulgite, carry out the immobilized of heteropoly acid then, obtain heterogeneous catalyst.
2, be the heteropolyacid catalyst of carrier with the attapulgite according to claim 1, it is characterized in that described attapulgite is acid activation and organically-modified attapulgite, granule size＞100 orders.
3, can contain amino silane coupler for gamma-aminopropyl-triethoxy-silane (KH-550), γ-An Bingjisanjiayangjiguiwan (KH-540), γ-aminopropyl methyldiethoxysilane (SG-Si902), N-β-aminoethyl-γ-An Bingjisanjiayangjiguiwan (SG-Si900), N-(β-aminoethyl)-γ-aminopropyl methyl dimethoxysilane ends such as (SG-Si602) as the used organic modifiers of organically-modified attapulgite as described in the claim 2.
4, the content of the attapulgite modified middle nitrogen element of amino coupling agent as claimed in claim 3 is 0.1%～5%.
5, the heteropolyacid catalyst that is carrier with claim 1,2 described organically-modified attapulgites, it is characterized in that: described heteropoly acid is phosphotungstic acid, phosphomolybdic acid, silico-tungstic acid etc.
6, the preparation method of the organically-modified attapulgite as claimed in claim 4 heteropolyacid catalyst that is carrier is as follows: to the heating of the attapulgite carrier crushing screening final vacuum after organically-modified 30～150min, add heteropoly acid solution by liquid-solid ratio 10: 1～2: 1 (v/g) then, stir 3～36h, suction filtration, washing thoroughly removes residual solvent under the vacuum, crosses 80 orders～200 mesh sieves, obtain the heteropoly acid or the heteropolyacid salt catalyst of attapulgite modified load, the product specific area is 60m
2/ g～250m
2/ g.
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| CN101862678A (en) * | 2010-06-28 | 2010-10-20 | 浙江树人大学 | Method for preparing tungstosilicic acid-supported catalyst for use in preparation of menthyl lactate |
| CN101869849A (en) * | 2010-06-28 | 2010-10-27 | 浙江树人大学 | Phosphomolybdic and tungstogermanate heteropoly acid supported catalyst for preparing menthyl lactate |
| CN101890357A (en) * | 2010-06-28 | 2010-11-24 | 浙江树人大学 | Preparation method and application of phosphotungstic acid-supported catalyst to preparation of menthyl lactate |
| CN102382811A (en) * | 2011-11-08 | 2012-03-21 | 中国农业科学院油料作物研究所 | Preparation method of attapulgite immobilized enzyme for ester exchange reaction |
| CN102962099A (en) * | 2012-11-01 | 2013-03-13 | 淮阴师范学院 | Preparation method of attapulgite immobilized salicylidene schiff base Co<2+> and Mn<2+> complex oxidation catalyst |
| CN103418440A (en) * | 2012-05-16 | 2013-12-04 | 中国石油化工股份有限公司 | Catalyst for ethylene glycol preparation through ethylene carbonate hydrolysis |
| CN103420794A (en) * | 2012-05-16 | 2013-12-04 | 中国石油化工股份有限公司 | Method for preparing ethylene glycol through ethylene carbonate hydrolysis |
| CN103657696B (en) * | 2013-12-12 | 2015-12-02 | 中科院广州能源所盱眙凹土研发中心 | For the preparation method of the epoxidised attapulgite based solid acid catalyst of vegetable fat |
| CN105363491A (en) * | 2015-10-21 | 2016-03-02 | 中国科学院过程工程研究所 | Loaded heteropolyacid catalyst for preparing methacrylic acid through oxidization of methacrolein |
| CN106423235A (en) * | 2016-09-23 | 2017-02-22 | 淮阴工学院 | Method for preparing silicon-dioxide-and-attapulgite-compounded-loaded heteropolyacid catalyst |
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| CN108623836A (en) * | 2018-05-15 | 2018-10-09 | 东华大学 | A kind of heteropolyacid salt carrying fiber element porous material and preparation method thereof |
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| CN1843911A (en) * | 2006-04-17 | 2006-10-11 | 江南大学 | Method for preparing silane coupler modified attapulgite |
| CN100549108C (en) * | 2007-12-28 | 2009-10-14 | 江苏南大紫金科技集团有限公司 | Organic surface modifying method of attapulgite |
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2009
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| CN101869849A (en) * | 2010-06-28 | 2010-10-27 | 浙江树人大学 | Phosphomolybdic and tungstogermanate heteropoly acid supported catalyst for preparing menthyl lactate |
| CN101890357A (en) * | 2010-06-28 | 2010-11-24 | 浙江树人大学 | Preparation method and application of phosphotungstic acid-supported catalyst to preparation of menthyl lactate |
| CN101862678A (en) * | 2010-06-28 | 2010-10-20 | 浙江树人大学 | Method for preparing tungstosilicic acid-supported catalyst for use in preparation of menthyl lactate |
| CN102382811A (en) * | 2011-11-08 | 2012-03-21 | 中国农业科学院油料作物研究所 | Preparation method of attapulgite immobilized enzyme for ester exchange reaction |
| CN102382811B (en) * | 2011-11-08 | 2013-06-05 | 中国农业科学院油料作物研究所 | Preparation method of attapulgite immobilized enzyme for ester exchange reaction |
| CN103418440B (en) * | 2012-05-16 | 2015-08-12 | 中国石油化工股份有限公司 | The catalyst of preparing ethyl glycol by hydrolysis of ethylene carbonate |
| CN103418440A (en) * | 2012-05-16 | 2013-12-04 | 中国石油化工股份有限公司 | Catalyst for ethylene glycol preparation through ethylene carbonate hydrolysis |
| CN103420794A (en) * | 2012-05-16 | 2013-12-04 | 中国石油化工股份有限公司 | Method for preparing ethylene glycol through ethylene carbonate hydrolysis |
| CN103420794B (en) * | 2012-05-16 | 2015-06-10 | 中国石油化工股份有限公司 | Method for preparing ethylene glycol through ethylene carbonate hydrolysis |
| CN102962099A (en) * | 2012-11-01 | 2013-03-13 | 淮阴师范学院 | Preparation method of attapulgite immobilized salicylidene schiff base Co<2+> and Mn<2+> complex oxidation catalyst |
| CN103657696B (en) * | 2013-12-12 | 2015-12-02 | 中科院广州能源所盱眙凹土研发中心 | For the preparation method of the epoxidised attapulgite based solid acid catalyst of vegetable fat |
| CN105363491A (en) * | 2015-10-21 | 2016-03-02 | 中国科学院过程工程研究所 | Loaded heteropolyacid catalyst for preparing methacrylic acid through oxidization of methacrolein |
| CN105363491B (en) * | 2015-10-21 | 2018-09-04 | 中国科学院过程工程研究所 | A kind of carried heteropoly acid catalyst for methacrolein oxidation preparing isobutene acid |
| CN106423235A (en) * | 2016-09-23 | 2017-02-22 | 淮阴工学院 | Method for preparing silicon-dioxide-and-attapulgite-compounded-loaded heteropolyacid catalyst |
| CN106466615A (en) * | 2016-09-23 | 2017-03-01 | 淮阴工学院 | The preparation method of glycerol method synthesizing dichloropropanol catalyst |
| CN106466615B (en) * | 2016-09-23 | 2018-12-25 | 淮阴工学院 | The preparation method of glycerol method synthesizing dichloropropanol catalyst |
| CN106423235B (en) * | 2016-09-23 | 2019-02-01 | 淮阴工学院 | The preparation method of silica and the heteropolyacid catalyst of attapulgite clay compounded load |
| CN108623836A (en) * | 2018-05-15 | 2018-10-09 | 东华大学 | A kind of heteropolyacid salt carrying fiber element porous material and preparation method thereof |
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