CN100336592C - Microcellular structured heteropoly acid/ silicon dioxide catalyst - Google Patents
Microcellular structured heteropoly acid/ silicon dioxide catalyst Download PDFInfo
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- CN100336592C CN100336592C CNB2004100678482A CN200410067848A CN100336592C CN 100336592 C CN100336592 C CN 100336592C CN B2004100678482 A CNB2004100678482 A CN B2004100678482A CN 200410067848 A CN200410067848 A CN 200410067848A CN 100336592 C CN100336592 C CN 100336592C
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- heteropoly acid
- silicon dioxide
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Abstract
The present invention relates to a heteropoly acid/ silicon dioxide catalyst with a microcellular structure, which mainly solves the problems of no microcellular structure, surface load of heteropoly acid and easy running-off of catalysts in traditional techniques. The present invention solves the problem via adopting the technical scheme that the catalyst has an average pore size of 10 to 20 angstroms and a specific surface area of 400 to 650 m<2>/g, the weight of heteropoly acid and the weight of silicon dioxide are respectively 1 to 70% and 30 to 99% of the total weight of the catalyst, and the silicon dioxide is composed of microcellular non-crystal silicon dioxide. The catalyst of the present invention can be used in the industrial production of dioctyl phthalate.
Description
Technical field
The present invention relates to a kind of heteropoly acid/silicon dioxide catalyst of microcellular structure.
Background technology
Heteropoly acid is a kind of important catalysis material, can be widely used in the reactions such as acid catalysis and redox catalysis.In order to make catalyst be easy to separate with product, it is a main path that heteropoly acid is prepared into a kind of support type heterogeneous catalyst.The existing employed method of patent report be by heteropoly acid solution impregnation method with loaded by heteropoly acid on the solid silica carrier surface, wherein Chinese patent CN1265940A has introduced various loaded by heteropoly acid at silica gel, aerosil, on HZSM-5 molecular sieve, activated carbon, atlapulgite, diatomite and the titanium dioxide surface, be used for the esterification of etherification reaction and the ethylene glycol and the acetate of oxirane and methyl alcohol as catalyst.CN1184797A has introduced phosphorus heteropoly tungstic acid and has been carried on the solid silica, is used for the catalytic reaction that alkane is converted into alkene; CN1185992A has introduced and has been carried on solid silica surface phosphotungstic acid and is used for the catalytic reaction that ether is converted into isobutene; US5856575A5 has introduced the catalytic reaction that the phosphotungstic acid that is carried on the solid silica surface is used for phenol and acid amides; EP955284A1 has introduced heteropolyacid salt and has been carried on the solid silica surface and is used for the alkene hydrolysis catalysis reaction.WO2000074842, WO2002020157, WO200200589 and JP2000342980 have introduced heteropoly acid respectively or heteropolyacid salt loads on the esterification that silica surface is used for the acid of low-carbon ester fat.
Heteropoly acid/silicon dioxide catalyst in the above-mentioned patent report since adopt solid silica do carrier with loaded by heteropoly acid in the surface, the heteropoly acid/silicon dioxide catalyst that obtains does not thus have the feature of microcellular structure.
Summary of the invention
Technical problem to be solved by this invention is that catalyst does not have the structure of micropore in the solution conventional art, and loaded by heteropoly acid is in the surface, heteropoly acid easily runs off and causes the problem of stability in use, and a kind of heteropoly acid/silicon dioxide catalyst of new microcellular structure is provided.This catalyst has heteropoly acid and is difficult for running off the characteristics that reactivity is high.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of heteropoly acid/silicon dioxide catalyst of microcellular structure, average pore size are 10～20 , and specific area is 400～650 meters
2/ gram comprises following component by weight percentage:
A) 1～70% heteropoly acid, wherein heteropoly acid is selected from phosphorus heteropoly tungstic acid or phosphato-molybdic heteropolyacid;
B) 30～99% silica, wherein silica is the noncrystal silica of porous.
In the technique scheme, the consumption preferable range of heteropoly acid is 5～50% by weight percentage.The average pore size preferable range is 12～15 ; The specific area preferable range is 500～600 meters
2/ gram.
The microcellular structure heteropoly acid/silicon dioxide catalyst is to be feedstock production with organosilicon acid esters and heteropoly acid, in water one alcohol/acetone system solution, be equipped with by hydrolysis gel legal system, wherein alcohol can be low-carbon alcohols such as ethanol or isopropyl alcohol, and wherein the organosilicon acid esters can be esters of silicon acis such as tetraethyl orthosilicate or quanmethyl silicate.
Above-mentioned catalyst is used for the dioctyl phthalate reaction, and 110 ℃ of reaction temperatures, phthalic anhydride/octanol mol ratio is 1/2, WHSV 2.0 hours
-1Under the reaction velocity, phthalic anhydride conversion ratio＞95%, selectivity of product＞98%, catalyst life＞300 hour.
This catalyst has that general heteropoly acid/silicon dioxide lacks select the shape selecting catalytic performance can and good stability in use, have significant application value.
The concrete preparation process of the heteropoly acid/silicon dioxide catalyst of microcellular structure of the present invention is as follows:
(1) is made into the aqueous solution of alcohol or acetone by a certain percentage, and is metered into the heteropoly acid dissolving by required.Be dissolved in the isopropyl alcohol esters of silicon acis standby by required metering simultaneously.
(2) in flask, add above-mentioned heteropoly acid solution, under agitation add the alcoholic solution of esters of silicon acis, heat up and add water, formed white jelly in 1～2 hour 80 ℃ of left and right sides hydrolysis.
(3) the hydrolysis evaporation that finishes removes and to desolvate, and dry below 120 ℃, obtains white solid, 180～200 ℃ of following preliminary treatment 2 hours, can be used for catalytic reaction again.
Be raw material with the organosilicon acid esters among the present invention, adopt the hydrolysis gel method, heteropoly acid and silica bound are formed together the heteropoly acid/silicon dioxide material of microcellular structure, has different structures with the heteropolyacid catalyst contrast of general silica surface load, and have catalysis and select shape selectivity and better catalytic stability, obtained better technical effect.
The invention will be further elaborated below by embodiment.
The specific embodiment
[embodiment 1]
20 weight % phosphorus heteropoly tungstic acid/concrete preparation processes of SiO 2 catalyst A of micro-structural are as follows:
(1) is made into 30 liters of the aqueous solution of ethanol in 50 weight % ratios, and adds 2.0 gram phosphorus heteropoly tungstic acids dissolvings.Be dissolved in 20 milliliters of isopropyl alcohols tetraethyl orthosilicate standby by the required metering of preparation 20 weight % phosphorus heteropoly tungstic acid/silica simultaneously.
(2) in flask, add above-mentioned heteropoly acid solution, under agitation add the alcoholic solution of esters of silicon acis, heat up and add 10 milliliters in water, formed white jelly in 1～2 hour 80 ℃ of left and right sides hydrolysis.
(3) alcoholic solvent is removed in the hydrolysis evaporation that finishes, and, obtain white solid, again 180～200 ℃ of following preliminary treatment 2 hours dry below 120 ℃, 20 weight % phosphorus heteropoly tungstic acid/SiO 2 catalysts are the microcellular structures with average pore size 14.2 , and its surface area is about 526 meters
2/ gram.
[embodiment 2]
The concrete preparation process of 60 weight % phosphorus heteropoly tungstic acid/SiO 2 catalyst B of microcellular structure is as follows:
(1) is made into 40 milliliters of the aqueous solution of ethanol in 50 weight % ratios, and adds 5.0 gram phosphorus heteropoly tungstic acids dissolvings.Be dissolved in 20 milliliters of isopropyl alcohols quanmethyl silicate standby by the required metering of preparation 60 weight % phosphorus heteropoly tungstic acid/silica simultaneously.
(2) in flask, add above-mentioned heteropoly acid solution, under agitation add the alcoholic solution of esters of silicon acis, heat up and add 20 milliliters in water, formed white jelly in 1～2 hour 80 ℃ of left and right sides hydrolysis.
(3) alcoholic solvent is removed in the hydrolysis evaporation that finishes, and, obtain white solid, again 180～200 ℃ of following preliminary treatment 2 hours dry below 120 ℃, the 60 weight % phosphorus heteropoly tungstic acid/SiO 2 catalysts that obtain are the microcellular structures with average pore size 10.4 , and its surface area is about 453 meters
2/ gram.
[embodiment 3]
The concrete preparation process of 30 weight % phosphato-molybdic heteropolyacid/SiO 2 catalyst C of microcellular structure is as follows:
(1) is made into 30 milliliters of the aqueous solution of acetone in 50 weight % ratios, and adds 1.0 gram phosphato-molybdic heteropolyacids dissolvings.Be dissolved in 20 milliliters of isopropyl alcohols tetraethyl orthosilicate standby by the required metering of preparation 30 weight % phosphato-molybdic heteropolyacid/silica simultaneously.
(2) in flask, add above-mentioned heteropoly acid solution, under agitation add the alcoholic solution of esters of silicon acis, heat up and add 10 milliliters in water, formed white jelly in 1～2 hour 80 ℃ of left and right sides hydrolysis.
(3) alcohol/acetone solvent is removed in the hydrolysis evaporation that finishes, and, obtain white solid, again 180～200 ℃ of following preliminary treatment 2 hours dry below 120 ℃, the 30 weight % phosphato-molybdic heteropolyacid/SiO 2 catalysts that obtain are the microcellular structures with average pore size 12.5 , and its surface area is about 588 meters
2/ gram.
[embodiment 4]
The concrete preparation process of 50 weight % phosphato-molybdic heteropolyacid/SiO 2 catalyst D of microcellular structure is as follows:
(1) is made into 30 milliliters of the aqueous solution of acetone in 50 weight % ratios, and adds 1.0 gram phosphato-molybdic heteropolyacids dissolvings.Be dissolved in 20 milliliters of isopropyl alcohols tetraethyl orthosilicate standby by the required metering of preparation 5 weight % phosphato-molybdic heteropolyacid/silica simultaneously.
(2) in flask, add above-mentioned heteropoly acid solution, under agitation add the alcoholic solution of esters of silicon acis, heat up and add 10 milliliters in water, formed white jelly in 1～2 hour 80 ℃ of left and right sides hydrolysis.
(3) alcohol/acetone solvent is removed in the hydrolysis evaporation that finishes, and, obtain white solid, again 180～200 ℃ of following preliminary treatment 2 hours dry below 120 ℃, the 5 weight % phosphato-molybdic heteropolyacid/SiO 2 catalysts that obtain are the microcellular structures with average pore size 17.8 , and its surface area is about 610 meters
2/ gram.
[embodiment 5]
Micropore phosphato-molybdic heteropolyacid/SiO 2 catalyst A～D that embodiment 1～4 is made, be used for the dioctyl phthalate reaction, on the fixed bed reaction evaluating apparatus, react investigation, loaded catalyst is 5.0 gram catalyst, 110 ℃ of reaction temperatures, phthalic anhydride/octanol mol ratio is 1/2, reaction velocity WHSV 2.0 hours
-1, reaction result is: catalyst A: phthalic anhydride conversion ratio 97.5%, selectivity of product 98.7%, catalyst B: phthalic anhydride conversion ratio 98.4%, selectivity of product 98.2%, catalyst C: phthalic anhydride conversion ratio 95.6%, selectivity of product 99.3%; Catalyst D: phthalic anhydride conversion ratio 94.1%, selectivity of product 99.5%; Catalytic stability: catalyst A reaction 300 hours, phthalic anhydride conversion ratio 98.1%, selectivity of product 98.4%.
Claims (4)
1, a kind of heteropoly acid/silicon dioxide catalyst of microcellular structure, average pore size are 10～20 , and specific area is 400～650 meters
2/ gram comprises following component by weight percentage:
A) 1～70% heteropoly acid, wherein heteropoly acid is selected from phosphorus heteropoly tungstic acid or phosphato-molybdic heteropolyacid;
B) 30～99% silica, wherein silica is the noncrystal silica of porous.
2,, it is characterized in that the consumption of heteropoly acid is 5～50% by weight percentage according to the heteropoly acid/silicon dioxide catalyst of the described microcellular structure of claim 1.
3,, it is characterized in that average pore size is 12～15 according to the heteropoly acid/silicon dioxide catalyst of the described microcellular structure of claim 1.
4,, it is characterized in that specific area is 500～600 meters according to the heteropoly acid/silicon dioxide catalyst of the described microcellular structure of claim 1
2/ gram.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2004100678482A CN100336592C (en) | 2004-11-05 | 2004-11-05 | Microcellular structured heteropoly acid/ silicon dioxide catalyst |
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| CNB2004100678482A CN100336592C (en) | 2004-11-05 | 2004-11-05 | Microcellular structured heteropoly acid/ silicon dioxide catalyst |
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| CN100336592C true CN100336592C (en) | 2007-09-12 |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100450609C (en) * | 2006-11-01 | 2009-01-14 | 南京师范大学 | Hybridization materials of polymetallic salts of oxygen and acid / mesoporous molecular sieve, and preparation method |
| CN102658191B (en) * | 2012-05-16 | 2014-03-19 | 河北工业大学 | Catalyst for preparing caprolactam from cyclohexanone-oxime by liquid-phase Beckmann rearrangement |
| CN104307568A (en) * | 2014-09-10 | 2015-01-28 | 东北电力大学 | Preparation method of hydroxypropyl-beta-cyclodextrin/ aluminium phosphotungstate catalyst used for preparation of dioctyl phthalate |
| CN108080012A (en) * | 2017-11-20 | 2018-05-29 | 武梦如 | A kind of preparation method for the solid acid catalyst for being used to prepare mixed dioctyl phthalate |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1235951A (en) * | 1998-04-29 | 1999-11-24 | 英国石油化学品有限公司 | Olefin hydration process |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1235951A (en) * | 1998-04-29 | 1999-11-24 | 英国石油化学品有限公司 | Olefin hydration process |
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