CN101347740B - Method for preparing SO4<2->/ZrO2-MxOy solid superacid catalyst and use - Google Patents
Method for preparing SO4<2->/ZrO2-MxOy solid superacid catalyst and use Download PDFInfo
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- CN101347740B CN101347740B CN2008100421753A CN200810042175A CN101347740B CN 101347740 B CN101347740 B CN 101347740B CN 2008100421753 A CN2008100421753 A CN 2008100421753A CN 200810042175 A CN200810042175 A CN 200810042175A CN 101347740 B CN101347740 B CN 101347740B
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Abstract
The invention relates to a prepration method of a SO4<2->/ZrO2-MxOy solid superacid catalyst and the application thereof. The preparation method adopts the coprecipitation method for the preparation, thereby obtaining a precursor of a binary mixed hydroxide containing Zr and M (M is equal to Al or Fe), the precursor is hydrothermally treatmented, dilute sulfuric acid is used for soaking, and the solid superacid catalyst with the larger specific surface area is obtained after the high-temperature calcination. The catalyst can obtain good effect, high conversion rate of Alpha-pineneand high selectivity of target products of camphene and limonene by being applied in the Alpha-pinene isomerization reaction.
Description
Technical field
The invention belongs to catalyst technical field, be specifically related to a kind of SO
4 2-/ ZrO
2-M
xO
yThe preparation method of solid super acid catalyst and application.
Background technology
Acid catalysis is the very important reaction of a class.In recent years, along with the raising of environmental requirement, 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, realize greenization production.SO
4 2-Accelerating oxidation thing type solid super-strong acid can activate C-C and c h bond at a lower temperature, and have recyclability and the high activity of liquid superacid and the advantage of high selectivity of heterogeneous catalyst concurrently, very likely become the substitute of the unfriendly catalyst of these environment, found the cleaning procedure of a collection of non-environmental-pollution.In this system again with SO
4 2-/ ZrO
2Acidity the strongest, also maximum to its research.Bibliographical information SO is arranged
4 2-/ ZrO
2The a small amount of Al of middle interpolation
2O
3Or Fe
2O
3Can improve the acid catalysis activity of catalyst, but the specific surface and the reactivity that how further to improve these binary composite metal oxide super acidic catalysts are worth further investigation.
Australene is terebinthine main component, can generate a series of isomers under the catalysis of acid material, and wherein amphene, citrene etc. all are the important intermediate of preparation spices, medicine.Industrial employing metatitanic acid is as catalyst, but catalytic activity is lower.In the research in the past, materials such as pickling lamellar clay, zeolite molecular sieve and bedded zirconium phosphate were all attempted being used for the isomerization reaction of catalysis australene, but there be active hanging down and shortcomings such as target product selectivity is low in these catalyst.With SO
4 2-/ ZrO
2-M
xO
y(M=Al or Fe) solid super acid catalyst is applied to have not yet to see bibliographical information in the australene isomerization reaction.
Summary of the invention
The purpose of this invention is to provide a kind of high-ratio surface and high activity SO
4 2-/ ZrO
2-M
xO
yThe preparation method of solid super acid catalyst.
Another object of the present invention provides this SO
4 2-/ ZrO
2-M
xO
yThe application of solid super acid catalyst.
The SO that the present invention proposes
4 2-/ ZrO
2-M
xO
yThe preparation method of solid super acid catalyst adopts coprecipitation again through the preparation of hydro-thermal aid in treatment earlier, and its concrete steps are as follows:
(1) zirconates of solubility and aluminum soluble salt or soluble ferric iron salt is soluble in water, make that the metal ion total concentration of zirconium Zr and aluminium Al or iron Fe is 0.2-1.0mol/L, under the stirring condition dropping ammonia until pH=9-10, under the room temperature ageing 12-36 hour; Wherein the mass ratio of aluminium or iron and zirconium is 0.005-0.05;
(2) sample after the ageing was at 80-100 ℃ of following hydrothermal treatment consists 12-48 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, the sulfuric acid with 0.2-2.0mol/L soaked 0.5-2 hour then, refilter, filter cake after 80-110 ℃ of dry 12-36 hour in air atmosphere 550-700 ℃ roasting 2-4 hour, promptly make SO
4 2-/ ZrO
2-M
xO
ySolid super acid catalyst, M are Al or Fe.
The solubility zirconates is ZrOCl among the present invention
28H
2O or ZrO (NO
3)
22H
2O or ZrCl
4, aluminum soluble salt is Al (NO
3)
39H
2O, soluble ferric iron salt is Fe (NO
3)
39H
2O or Fe
2(SO
4)
39H
2O.
The optimum quality ratio of aluminium or iron and zirconium is Al/Zr=0.018 among the present invention, Fe/Zr=0.028.
The hydrothermal treatment consists optimum condition is 90 ℃ of following hydrothermal treatment consists 24 hours among the present invention.
Employed sulfuric acid optium concentration is 0.5-1.0mol/L among the present invention.
Optimum calcination temperature is 650 ℃ among the present invention.
The invention allows for described SO
4 2-/ ZrO
2-M
xO
yThe 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 300-500 ℃ of air atmosphere, best activation temperature is 400 ℃; Then in batch reactor, the isomerization reaction of catalysis australene under the condition of normal pressure, the temperature of catalytic reaction is 100-120 ℃; The time of catalytic reaction is 1-8 hour; Catalyst amount is the 1-3wt% of australene.
Hydro-thermal Assisted Preparation SO provided by the invention
4 2-/ ZrO
2-M
xO
yThe method of solid super acid catalyst is compared SO of the present invention with commonsense method (promptly without the hydro-thermal aid in treatment)
4 2-/ ZrO
2-M
xO
ySolid super acid catalyst has that crystal grain is little, and specific surface is big, surperficial SO
4 2-The content height, heat endurance height, advantage such as 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 50-60%.
The specific embodiment
Example 1: with 26.223 gram ZrOCl
28H
2O and 1.856 gram Al (NO
3)
39H
2O is dissolved in the 190mL water, and stirring condition drips down concentrated ammonia liquor until pH=9-10, and ageing is 24 hours under the room temperature, and the sample after the ageing is 90 ℃ of hydrothermal treatment consists 24 hours, and sediment after filtration and washing does not contain Cl until filtrate
-Ion, the filter cake of gained were in 100 ℃ of dryings 24 hours, and the dilute sulfuric acid with 0.5mol/L soaked 1 hour then, filtered, and 100 ℃ of dryings in 650 ℃ of roastings of air atmosphere 3 hours, obtained catalyst-1 after 24 hours, and its specific surface is 133m
2/ g.
Example 2: with 18.977 gram ZrCl
4Reach 1.856 gram Al (NO
3)
39H
2O is dissolved in the 190mL water, and stirring condition drips down concentrated ammonia liquor until pH=9-10, and ageing is 12 hours under the room temperature, and the sample after the ageing is 90 ℃ of hydrothermal treatment consists 12 hours, and sediment after filtration and washing does not contain Cl until filtrate
-Ion, the filter cake of gained were in 110 ℃ of dryings 12 hours, and the dilute sulfuric acid with 0.5mol/L soaked 0.5 hour then, filtered, and 110 ℃ of dryings in 650 ℃ of roastings of air atmosphere 3 hours, obtained catalyst-2 after 12 hours, and its specific surface is 128m
2/ g.
Example 3: with 21.746 gram ZrO (NO
3)
22H
2O and 1.856 gram Al (NO
3)
39H
2O is dissolved in the 190mL water, and stirring condition drips down concentrated ammonia liquor until pH=9-10, and ageing is 36 hours under the room temperature, and the sample after the ageing is 90 ℃ of hydrothermal treatment consists 36 hours, and sediment after filtration and washing does not contain Cl until filtrate
-Ion, the filter cake of gained were in 80 ℃ of dryings 36 hours, and the dilute sulfuric acid with 1mol/L soaked 0.5 hour then, filtered, and 80 ℃ of dryings in 650 ℃ of roastings of air atmosphere 3 hours, obtained catalyst-3 after 36 hours, and its specific surface is 135m
2/ g.
Example 4: with 26.223 gram ZrOCl
28H
2O and 1.504 gram Fe (NO
3)
39H
2O is dissolved in the 190mL water, utilizes the method for example 1 to make catalyst-4, and its specific surface is 144m
2/ g.
Example 5: with 18.977 gram ZrCl
4Reach 0.736 gram Fe (NO
3)
39H
2O is dissolved in the 190mL water, and stirring condition drips down concentrated ammonia liquor until pH=9-10, and ageing is 30 hours under the room temperature, and the sample after the ageing is 90 ℃ of hydrothermal treatment consists 24 hours, and sediment after filtration and washing does not contain Cl until filtrate
-Ion, the filter cake of gained were in 100 ℃ of dryings 30 hours, and the dilute sulfuric acid with 0.8mol/L soaked 1 hour then, filtered, and 100 ℃ of dryings in 650 ℃ of roastings of air atmosphere 3 hours, obtained catalyst-5 after 30 hours, and its specific surface is 133m
2/ g.
Example 6: with 21.746 gram ZrO (NO
3)
22H
2O and 2.617 gram Fe
2(SO
4)
39H
2O is dissolved in the 190mL water, and stirring condition drips down concentrated ammonia liquor until pH=9-10, and ageing is 32 hours under the room temperature, and the sample after the ageing is 90 ℃ of hydrothermal treatment consists 24 hours, and sediment after filtration and washing does not contain Cl until filtrate
-Ion, the filter cake of gained were in 85 ℃ of dryings 33 hours, and the dilute sulfuric acid with 1.2mol/L soaked 0.7 hour then, filtered, and 85 ℃ of dryings in 650 ℃ of roastings of air atmosphere 3 hours, obtained catalyst-6 after 33 hours, and its specific surface is 135m
2/ g.
Example 7: 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 110 ℃ of conditions.React that the conversion ratio of australene is 80.8% after 8 hours, the amphene selectivity is 53.7%, and the citrene selectivity is 14.9%.
Example 8: utilize the activity of the method mensuration catalyst-2 pair australene isomerization reaction of example 7, the conversion ratios of 110 ℃ of reactions australene after 8 hours are 58.7%, and the amphene selectivity is 53.7%, and the citrene selectivity is 17.5%.
Example 9: utilize the activity of the method mensuration catalyst-3 pair australene isomerization reaction of example 7, the conversion ratios of 110 ℃ of reactions australene after 8 hours are 69.2%, and the amphene selectivity is 54.4%, and the citrene selectivity is 16.8%.
Example 10: utilize the activity of the method mensuration catalyst-4 pair australene isomerization reaction of example 7, the conversion ratios of 110 ℃ of reactions australene after 8 hours are 71.3%, and the amphene selectivity is 54.2%, and the citrene selectivity is 15.3%.
Example 11: utilize the activity of the method mensuration catalyst-5 pair australene isomerization reaction of example 7, the conversion ratios of 110 ℃ of reactions australene after 8 hours are 59.3%, and the amphene selectivity is 53.4%, and the citrene selectivity is 17.9%.
Example 12: utilize the activity of the method mensuration catalyst-6 pair australene isomerization reaction of example 7, the conversion ratios of 110 ℃ of reactions australene after 8 hours are 60.3%, and the amphene selectivity is 56.2%, and the citrene selectivity is 17.2%.
Comparative Examples 1: with 26.223 gram ZrOCl
28H
2O and 1.856 gram Al (NO
3)
39H
2O is dissolved in the 190mL water, and stirring condition drips down 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 until filtrate
-Ion, the filter cake of gained were in 100 ℃ of dryings 24 hours, and the dilute sulfuric acid with 0.5mol/L soaked 1 hour then, filtered, and 100 ℃ of dryings in 650 ℃ of roastings of air atmosphere 3 hours, obtained comparative catalyst-1 after 24 hours, and its specific surface is 115m
2/ g.Utilize the activity of the method mensuration comparative catalyst-1 pair australene isomerization reaction of example 7, the conversion ratios of 110 ℃ of reactions australene after 8 hours are 52.3%, and the amphene selectivity is 54.1%, and the citrene selectivity is 16.7%.
Comparative Examples 2: with 26.223 gram ZrOCl
28H
2O and 1.504 gram Fe (NO
3)
39H
2O is dissolved in the 190mL water, utilizes the method for preparing catalyst of Comparative Examples 1 to make comparative catalyst-2, and its specific surface is 110m
2/ g.Utilize the activity of the method mensuration comparative catalyst-2 pair australene isomerization reaction of example 7, the conversion ratios of 110 ℃ of reactions australene after 8 hours are 45.8%, and the amphene selectivity is 53.9%, and the citrene selectivity is 16.7%.
Claims (3)
1. SO
4 2-/ ZrO
2-M
xO
yThe preparation method of solid super acid catalyst is characterized in that its concrete steps are as follows:
(1) zirconates of solubility and aluminum soluble salt or soluble ferric iron salt is soluble in water, make that the metal ion total concentration of zirconium Zr and aluminium Al or iron Fe is 0.2-1.0mol/L, under the stirring condition dropping ammonia until pH=9-10, under the room temperature ageing 12-36 hour; Wherein the mass ratio of aluminium or iron and zirconium is 0.005-0.05;
(2) sample after the ageing was at 80-100 ℃ of following hydrothermal treatment consists 12-48 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, the sulfuric acid with 0.2-2.0mol/L soaked 0.5-2 hour then, refilter, filter cake after 80-110 ℃ of dry 12-36 hour in air atmosphere 550-700 ℃ roasting 2-4 hour, promptly make SO
4 2-/ ZrO
2-M
xO
ySolid super acid catalyst, M are Al or Fe.
2. the preparation method of solid super acid catalyst according to claim 1 is characterized in that the solubility zirconates is ZrOCl
28H
2O or ZrO (NO
3)
22H
2O or ZrCl
4, aluminum soluble salt is Al (NO
3)
39H
2O, soluble ferric iron salt is Fe (NO
3)
39H
2O or Fe
2(SO
4)
39H
2O.
3. 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 300-500 ℃ of air atmosphere, then in batch reactor, the isomerization reaction of catalysis australene under the condition of normal pressure, the temperature of catalytic reaction are 100-120 ℃; The time of catalytic reaction is 1-8 hour; Catalyst amount is the 1-3wt% of australene.
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|---|---|---|---|
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|---|---|---|---|
| CN2008100421753A CN101347740B (en) | 2008-08-28 | 2008-08-28 | Method for preparing SO4<2->/ZrO2-MxOy solid superacid catalyst and use |
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Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101829559B (en) * | 2009-03-13 | 2012-06-06 | 复旦大学 | Preparation method and application of WO3/ZrO2 solid super acidic catalyst |
| CN101530788B (en) * | 2009-04-03 | 2011-06-01 | 中国科学院上海硅酸盐研究所 | Multilevel porous structure solid super acidic catalyst and preparation method thereof |
| CN102126904B (en) * | 2011-01-20 | 2013-07-17 | 大连理工大学 | Method for isomerizing alpha-pinene |
| CN102658174B (en) * | 2012-05-04 | 2014-04-16 | 四川大学 | Mesoporous fibrous SO4<2->/MxOy type solid acid catalyst and preparation method thereof |
| 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 |
| CN104324734B (en) * | 2014-09-26 | 2016-08-17 | 沈阳化工大学 | A kind of 1-butylene oligomerisation reaction that is suitable for synthesizes C8and C12method for preparing catalyst |
| CN106140197B (en) * | 2015-03-24 | 2019-03-12 | 中国石油天然气股份有限公司 | Solid super acidic catalyst, preparation method thereof and isomerization method of light normal paraffin |
| CN105396602B (en) * | 2015-11-06 | 2018-01-16 | 济南同誉新材料科技有限公司 | A kind of composite solid-acid catalyst and its preparation and renovation process |
| CN106311286A (en) * | 2016-08-24 | 2017-01-11 | 安徽金邦医药化工有限公司 | Solid acid catalyst and preparing method of diethyl ether by using the same |
| CN111097453A (en) * | 2018-10-25 | 2020-05-05 | 中国石油化工股份有限公司 | Preparation method of zirconium oxide sulfate |
| CN109721451A (en) * | 2018-12-21 | 2019-05-07 | 怀集县长林化工有限责任公司 | A kind of australene bisabolene isomer prepares the preparation method of limonene |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101108355A (en) * | 2007-07-17 | 2008-01-23 | 华东理工大学 | Method of manufacturing high isomerization active solid super acidic catalyst |
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|---|---|---|---|---|
| CN101108355A (en) * | 2007-07-17 | 2008-01-23 | 华东理工大学 | Method of manufacturing high isomerization active solid super acidic catalyst |
Non-Patent Citations (1)
| Title |
|---|
| Yinyong Sun et al..Investigation of factors influencing catalytic activity for n-butane isomerization in the presence of hydrogen on Al-promoted sulfated zirconia.《Applied Catalysis A: General》.2005,第292卷200-207. * |
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