CN101829559A - Preparation method and application of WO3/ZrO2 solid super acidic catalyst - Google Patents
Preparation method and application of WO3/ZrO2 solid super acidic catalyst Download PDFInfo
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- CN101829559A CN101829559A CN200910047612A CN200910047612A CN101829559A CN 101829559 A CN101829559 A CN 101829559A CN 200910047612 A CN200910047612 A CN 200910047612A CN 200910047612 A CN200910047612 A CN 200910047612A CN 101829559 A CN101829559 A CN 101829559A
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Abstract
The invention belongs to the technical field of catalysts, and particularly relates to a preparation method and application of a WO3/ZrO2 solid super acidic catalyst. The preparation method comprises the following steps of: preparing a zirconium hydroxide precursor by adopting a precipitation method, carrying out hydro-thermal treatment on the precursor, soaking the precursor in ammonium meta-tungstate and roasting at high temperature to obtain the solid super acidic catalyst with larger specific surface. When applying the catalyst to Alpha-pinene isomerization reaction, a favorable effect can be obtained, Alpha-pinene conversion ratio and selectivity to target products of camphene and limonene are high and the catalyst still keeps high activity and high selectivity after multiple regeneration and repeated use.
Description
Technical field
The invention belongs to catalyst technical field, be specifically related to a kind of WO
3/ ZrO
2The preparation method of solid super acid catalyst and application.
Background technology
It is the very important reaction of a class that prior art discloses acid catalysis.In recent years, along with the raising of environmental requirement, for realizing greenization production, people urgently wish to substitute the unfriendly catalyst of the more industrial employed environment of important reactions, as: HF, H
2SO
4, H
3PO
4And AlCl
3Deng.WO
3/ ZrO
2Solid super acid catalyst has recyclability and the high activity of liquid superacid and the advantage of high selectivity of heterogeneous catalyst concurrently, and it is environmentally friendly, very likely replace liquid acid, become the catalyst of new generation under the current Sustainable Development Background, found the cleaning procedure of a collection of non-environmental-pollution.How to improve the specific surface and the reactivity of this class binary composite metal oxide super acidic catalyst, caused relevant researcher's concern.
Studies show that australene is terebinthine main component, can generate a series of isomers under the catalysis of acid material, wherein amphene, citrene etc. all are the important intermediate of preparation spices, medicine.Industrial common employing metatitanic acid is as catalyst, but catalytic activity is lower.In the research in the past, pickling lamellar clay, zeolite molecular sieve, bedded zirconium phosphate and SO
4 2-/ ZrO
2Materials such as solid super-strong acid were all attempted being used for the isomerization reaction of catalysis australene, but these catalyst exist following defective and deficiency: active low, target product selectivity is low, and the reaction temperature height is difficult to recycling etc.
Summary of the invention
The objective of the invention is to overcome the defective and the deficiency of prior art, a kind of high-ratio surface and high activity W O are provided
3/ ZrO
2The preparation method of solid super acid catalyst.
Another object of the present invention provides this WO
3/ ZrO
2The application of solid super acid catalyst.Particularly, the present invention is with WO
3/ ZrO
2Solid super acid catalyst is applied in the australene isomerization reaction.
WO proposed by the invention
3/ ZrO
2The preparation method of solid super acid catalyst, its concrete steps are:
(1) zirconates of solubility is soluble in water, make that the concentration of metal ions of zirconium Zr is 0.1-0.5mol/L, stirring condition drips down concentrated ammonia liquor until pH=9-10, under the room temperature still aging 12-36 hour;
(2) sample after the ageing was at 80-110 ℃ of following hydrothermal treatment consists 12-36 hour;
(3) sediment after filtration and the washing, in filtrate, do not contain Cl
-Ion, with the filter cake of gained in 80-110 ℃ dry 12-36 hour down, be the ammonium metatungstate ((NH of 0.01-0.04mol/L then with concentration
4)
6W
12O
39) aqueous solution soaking ground 0.5-2 hour, liquid-solid ratio is 3-20mL/g, the heating evaporating water, 90-120 ℃ dry 6-24 hour down, in the air atmosphere 700-850 ℃ roasting 3-6 hour, promptly make WO
3/ ZrO
2Solid super acid catalyst, wherein WO
3Content is 12-24wt%.
Among the present invention, the solubility zirconates is ZrO (NO
3)
22H
2O or ZrOCl
28H
2O or ZrCl
4
Among the present invention, the hydrothermal treatment consists optimum condition is 100 ℃ of following hydrothermal treatment consists 24 hours.
Among the present invention, WO
3Preferred content is 18wt%.
Among the present invention, preferred sintering temperature is 800 ℃.
The invention allows for described WO
3/ ZrO
2The application of solid super acid catalyst promptly is applied in the australene isomerization reaction, and concrete reaction condition is as follows:
The reaction procatalyst at first activates 2 hours in 350-450 ℃ of air atmosphere, then in batch reactor, the isomerization reaction of catalysis australene under the condition of normal pressure, the temperature of catalytic reaction is 80-110 ℃, the time of catalytic reaction is 1-5 hour, and catalyst consumption is the 1-3% of australene.
Hydro-thermal assistant soakage provided by the invention prepares WO
3/ ZrO
2The method of solid super-strong acid is compared WO of the present invention with commonsense method (promptly without the hydro-thermal aid in treatment)
3/ ZrO
2Solid super acid catalyst has advantages such as crystal grain is little, and specific surface is big, and acidic site is many.Such catalyst is applied to the australene isomerization reaction, and respond well, the selectivity height of target product amphene and citrene is compared with the catalyst that is prepared by commonsense method, and the australene conversion ratio has improved 140%.And through repeatedly regeneration test, catalyst still keeps advantages of high catalytic activity and selectivity.
For the ease of understanding, below will describe in detail of the present invention by specific embodiment.It needs to be noted, instantiation only is in order to illustrate, obviously those of ordinary skill in the art can illustrate according to this paper, within the scope of the invention the present invention is made various corrections and change, and these corrections and change are also included in the scope of the present invention.
The specific embodiment
Embodiment 1
With 17.105 gram ZrO (NO
3)
22H
2O is dissolved in the 320mL water, and stirring condition drips down slowly concentrated ammonia liquor until pH=9-10, and ageing is 24 hours under the room temperature, and the sample after the ageing is 100 ℃ of hydrothermal treatment consists 24 hours, and sediment after filtration and washing does not contain Cl in filtrate
-Ion, the Zr of gained (OH)
4Filter cake is in 100 ℃ of dryings 24 hours, soaks with the ammonium metatungstate aqueous solution of 0.02mol/L then and grinds 1 hour, and liquid-solid ratio is 3.05mL/g, the heating evaporating water, 100 ℃ dry 12 hours down, 800 ℃ of roastings are 3 hours in the air atmosphere, obtain catalyst-1, wherein WO
3Content is 18wt%, and its specific surface is 70m
2/ g.
Embodiment 2
With 41.248 gram ZrOCl
28H
2O is dissolved in the 320mL water, and stirring condition drips down slowly concentrated ammonia liquor until pH=9-10, and ageing is 36 hours under the room temperature, and the sample after the ageing is 100 ℃ of hydrothermal treatment consists 12 hours, and sediment after filtration and washing does not contain Cl in filtrate
-Ion, the Zr of gained (OH)
4Filter cake is in 110 ℃ of dryings 12 hours, soaks with the ammonium metatungstate aqueous solution of 0.01mol/L then and grinds 2 hours, and liquid-solid ratio is 4.91mL/g, the heating evaporating water, 90 ℃ dry 24 hours down, 800 ℃ of roastings are 3 hours in the air atmosphere, obtain catalyst-2, wherein WO
3Content is 15wt%, and its specific surface is 63m
2/ g.
Embodiment 3
With 22.371 gram ZrCl
4Be dissolved in the 320mL water, stirring condition drips down slowly concentrated ammonia liquor until pH=9-10, and ageing is 12 hours under the room temperature, and the sample after the ageing is 100 ℃ of hydrothermal treatment consists 36 hours, and sediment after filtration and washing does not contain Cl in filtrate
-Ion, the Zr of gained (OH)
4Filter cake is in 90 ℃ of dryings 36 hours, soaks with the ammonium metatungstate aqueous solution of 0.03mol/L then and grinds 0.6 hour, and liquid-solid ratio is 2.47mL/g, the heating evaporating water, 120 ℃ dry 6 hours down, 800 ℃ of roastings are 3 hours in the air atmosphere, obtain catalyst-3, wherein WO
3Content is 21wt%, and its specific surface is 67m
2/ g.
Embodiment 4
Catalyst-1 is used for the australene isomerization reaction.Catalytic reaction is equipped with in the 25mL round-bottomed flask of reflux condensate device and drying device one carries out, 0.16 the gram catalyst is after 400 ℃ of air atmospheres activate 2 hours, it is dropped in the reaction vessel that is added with 8 gram australenes in advance electromagnetic agitation reaction under 90 ℃ of conditions.React that the conversion ratio of australene is 76.2% after 5 hours, the amphene selectivity is 68.8%, and the citrene selectivity is 16.5%.
Embodiment 5
Utilize the activity of the method mensuration catalyst-2 pair australene isomerization reaction of example 4, the conversion ratios of 90 ℃ of reactions australene after 5 hours are 72.3%, and the amphene selectivity is 68.1%, and the citrene selectivity is 16.9%.
Embodiment 6
Utilize the activity of the method mensuration catalyst-3 pair australene isomerization reaction of example 4, the conversion ratios of 90 ℃ of reactions australene after 5 hours are 64.7%, and the amphene selectivity is 68.9%, and the citrene selectivity is 16.4%.
Embodiment 7
Utilize the activity of the method mensuration catalyst-1 pair australene isomerization reaction of example 4, the conversion ratios of 100 ℃ of reactions australene after 5 hours are 89.3%, and the amphene selectivity is 65.5%, and the citrene selectivity is 17.5%.
Embodiment 8
Utilize the activity of the method mensuration catalyst-1 pair australene isomerization reaction of example 4, the conversion ratios of 110 ℃ of reactions australene after 1.5 hours are 97.7%, and the amphene selectivity is 61.2%, and the citrene selectivity is 13.5%.
Embodiment 9
90 ℃ of reaction catalyst-1 centrifugations from reaction system after 5 hours are come out, drying is 12 hours under 100 ℃, 550 ℃ of blowing air roastings 3 hours, utilize the reactivity after the method for example 4 is measured catalyst-1 regeneration, the conversion ratio of 90 ℃ of reactions australene after 5 hours is 69.2%, the amphene selectivity is 68.4%, the citrene selectivity is 16.7%, after third-order reaction regeneration, the conversion ratio of 90 ℃ of reactions australene after 5 hours is 65.5%, the amphene selectivity is 68.7%, and the citrene selectivity is 16.5%.
Comparative Examples 1: with 17.105 gram ZrO (NO
3)
22H
2O is dissolved in the 320mL water, and stirring condition drips down slowly concentrated ammonia liquor until pH=9-10, and ageing is 24 hours under the room temperature, and sediment after filtration and washing does not contain Cl in filtrate
-Ion, the Zr of gained (OH)
4Filter cake is in 100 ℃ of dryings 24 hours, soaks with the ammonium metatungstate aqueous solution of 0.02mol/L then and grinds 1 hour, and liquid-solid ratio is 3.05mL/g, the heating evaporating water, 100 ℃ dry 12 hours down, 800 ℃ of roastings are 3 hours in the air atmosphere, obtain comparative catalyst-1, wherein WO
3Content is 18wt%, and its specific surface is 42m
2/ g.Utilize the activity of the method mensuration comparative catalyst-1 pair australene isomerization reaction of example 4, the conversion ratios of 90 ℃ of reactions australene after 5 hours are 31.8%, and the amphene selectivity is 67.8%, and the citrene selectivity is 16.4%.
Claims (6)
1. WO
3/ ZrO
2The preparation method of solid super acid catalyst is characterized in that comprising the steps:
(1) zirconates of solubility is soluble in water, make that the concentration of metal ions of zirconium Zr is 0.1-0.5mol/L, stirring condition drips down concentrated ammonia liquor to pH=9-10, under the room temperature still aging 12-36 hour;
(2) sample after the ageing was at 80-110 ℃ of following hydrothermal treatment consists 12-36 hour;
(3) sediment after filtration and the washing, to filtrate, do not contain Cl
-Ion, with the filter cake of gained in 80-110 ℃ dry 12-36 hour down, be the ammonium metatungstate ((NH of 0.01-0.04mol/L then with concentration
4)
6W
12O
39) aqueous solution soaking ground 0.5-2 hour, liquid-solid ratio is 3-20mL/g, the heating evaporating water, 90-120 ℃ dry 6-24 hour down, in the air atmosphere 700-850 ℃ roasting 3-6 hour, promptly make WO
3/ ZrO
2Solid super acid catalyst, wherein WO
3Content is 12-24wt%.
2. the preparation method of solid super acid catalyst according to claim 1 is characterized in that the solubility zirconates is ZrO (NO
3)
22H
2O or ZrOCl
28H
2O or ZrCl
4
3. the preparation method of solid super acid catalyst according to claim 1 is characterized in that described step 2) ageing after sample 100 ℃ of following hydrothermal treatment consists 24 hours.
4. the preparation method of solid super acid catalyst according to claim 1 is characterized in that the sintering temperature described in the described step 3) is 800 ℃.
5. the preparation method of solid super acid catalyst according to claim 1 is characterized in that the WO described in the described step 3)
3Content is 18wt%.
6. the application of solid super acid catalyst as claimed in claim 1 in the australene isomerization reaction, it is characterized in that concrete reaction condition is as follows: the reaction procatalyst at first activates 2 hours in 350-450 ℃ of air atmosphere, then in batch reactor, the isomerization reaction of catalysis australene under the condition of normal pressure, the temperature of catalytic reaction is 80-110 ℃, the time of catalytic reaction is 1-5 hour, and catalyst consumption is the 1-3% of australene.
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|---|---|---|---|
| CN2009100476125A CN101829559B (en) | 2009-03-13 | 2009-03-13 | Preparation method and application of WO3/ZrO2 solid super acidic catalyst |
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| CN101829559A true CN101829559A (en) | 2010-09-15 |
| CN101829559B CN101829559B (en) | 2012-06-06 |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103041800A (en) * | 2013-01-03 | 2013-04-17 | 东北石油大学 | Preparation method of WO3/ZrO2 solid super acidic catalyst |
| CN103316696A (en) * | 2013-07-03 | 2013-09-25 | 宁波永顺精细化工有限公司 | Preparation method of acetyl tri-n-butyl citrate and catalyst used in preparation method |
| CN103819300A (en) * | 2014-02-26 | 2014-05-28 | 山东广恒化工有限公司 | Method for preparing camphene from alpha-pinene |
| CN108358872A (en) * | 2018-03-21 | 2018-08-03 | 天津市职业大学 | A method of utilize ammonium tungstate to synthesize lemon olefinic oxide at room temperature |
| CN110152688A (en) * | 2019-04-29 | 2019-08-23 | 南京师范大学 | A kind of composite solid super acidic catalyst, preparation method and N, the method for N- diethylaniline are catalyzed and synthesized with it |
| CN113634247A (en) * | 2021-08-31 | 2021-11-12 | 福州大学 | Deoxygenation and isomerization catalyst, and preparation method and application thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101347740B (en) * | 2008-08-28 | 2011-06-29 | 复旦大学 | Method for preparing SO4<2->/ZrO2-MxOy solid superacid catalyst and use |
-
2009
- 2009-03-13 CN CN2009100476125A patent/CN101829559B/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103041800A (en) * | 2013-01-03 | 2013-04-17 | 东北石油大学 | Preparation method of WO3/ZrO2 solid super acidic catalyst |
| CN103316696A (en) * | 2013-07-03 | 2013-09-25 | 宁波永顺精细化工有限公司 | Preparation method of acetyl tri-n-butyl citrate and catalyst used in preparation method |
| CN103316696B (en) * | 2013-07-03 | 2015-02-25 | 宁波永顺精细化工有限公司 | Preparation method of acetyl tri-n-butyl citrate and catalyst used in preparation method |
| CN103819300A (en) * | 2014-02-26 | 2014-05-28 | 山东广恒化工有限公司 | Method for preparing camphene from alpha-pinene |
| CN103819300B (en) * | 2014-02-26 | 2015-06-17 | 山东广恒化工有限公司 | Method for preparing camphene from alpha-pinene |
| CN108358872A (en) * | 2018-03-21 | 2018-08-03 | 天津市职业大学 | A method of utilize ammonium tungstate to synthesize lemon olefinic oxide at room temperature |
| CN110152688A (en) * | 2019-04-29 | 2019-08-23 | 南京师范大学 | A kind of composite solid super acidic catalyst, preparation method and N, the method for N- diethylaniline are catalyzed and synthesized with it |
| CN113634247A (en) * | 2021-08-31 | 2021-11-12 | 福州大学 | Deoxygenation and isomerization catalyst, and preparation method and application thereof |
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|---|---|
| CN101829559B (en) | 2012-06-06 |
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