CN103316697A - Technology for preparing solid acid catalyst by reversed-phase microemulsion method - Google Patents

Technology for preparing solid acid catalyst by reversed-phase microemulsion method Download PDF

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CN103316697A
CN103316697A CN2013103012557A CN201310301255A CN103316697A CN 103316697 A CN103316697 A CN 103316697A CN 2013103012557 A CN2013103012557 A CN 2013103012557A CN 201310301255 A CN201310301255 A CN 201310301255A CN 103316697 A CN103316697 A CN 103316697A
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acid catalyst
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CN103316697B (en
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张志德
王重斌
陈玉琴
满城娜
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Shandong Normal University
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Shandong Normal University
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Abstract

The invention relates to a technology for preparing a solid acid catalyst by a reversed-phase microemulsion method. the technology comprises the following steps: mixing Ti(SO4)2.9H2O, Al(NO3)3.9H2O and deionized water to prepare an inorganic salt solution, adding a surfactant, a cosurfactant and an oil phase into the stirred inorganic salt solution and mixing to obtain a microemulsion A, mixing the surfactant, the cosurfactant, the oil phase and a stirred ammonium carbonate aqueous solution to obtain a microemulsion B, mixing A and B, filtering, dipping by the use of a (NH4)2SO4 solution, and calcining to obtain solid superacid. The catalyst provided by the invention has advantages of good dispersity of synthesized particles, small and controllable particle size and large specific surface area. In comparison with catalysts prepared by existing methods, the catalyst provided by the invention has better catalytic activity and its catalytic efficiency is raised by 5%-10%.

Description

A kind of technology of prepared by reverse microemulsion method solid acid catalyst
Technical field
The invention belongs to the preparation that relates to a kind of solid acid catalyst, particularly TiO 2-Al 2O 3/ SO 4 2+Solid super-strong acid nano powder preparation technology belongs to catalyst preparation technical field.
Background technology
Solid super acid catalyst can be widely used in cracking, alkylation, acyl groupization, esterification, isomerization, polymerization, oligomerisation and oxidation reaction etc. in organic synthesis; and because advantage such as its pollution to the corrosion Xiao ﹑ environment of equipment is little; in Green Chemistry, environmental friendliness catalysis, prospect has a very wide range of applications.Traditional TiO 2-Al 2O 3/ SO 4 2+The solid super-strong acid preparation method mainly comprises precipitation-infusion process, hydro-thermal method, coprecipitation, sol-gal process, self-assembly method etc., but these method complex operations, and there is the big and agglomeration Yan Chong ﹑ specific area shortcoming on the low side of particle diameter distribution Bu Jun ﹑ granularity easily through the solid acid catalyst of the method preparation.Thereby invent a kind of granule-morphology is even, tiny, specific area is high solid acid for TiO 2-Al 2O 3/ SO 4 2+The commercial Application of solid acid has very important significance.
It is even that microemulsion method reaction system Wen is Dinged ﹑, and technology is simple, can regulate pattern, particle size, distribution of preparation nano-powder etc. by the parameter that changes technology.In reverse micro emulsion, water is as a microreactor, and nano particle is Cheng He ﹑ growth in water.The amount of substance that can control water and surfactant than and the concentration of aqueous phase inorganic salts change the size of nano particle.The design of this synthesis methods for nanoparticles is expected to overcome the uneven first-class shortcoming of the poly-﹑ particle decentralization difference ﹑ size of easy group that the synthetic solid super-strong acid of traditional handicraft exists.The one pack system solid super acid catalyst, the sulfate radical that plays an important role more easily runs off in reaction, inactivation easily under the high-temperature condition, so the one pack system solid catalyst has catalytic activity preferably at the beginning, but service life is shorter.By to mixing metal oxide to the modification of carrier, make catalyst suitable specific area can be provided, strengthen acid site density, increase the service life, increase poison resistance etc.
Summary of the invention
The object of the present invention is to provide a kind of technology of prepared by reverse microemulsion method solid acid catalyst, synthesized TiO 2-Al 2O 3/ SO 4 2+Solid super-strong acid, synthetic solid super-strong acid have advantages such as the Hao ﹑ specific area of particle decentralization Da ﹑ particle size is controlled.
The technical scheme that the present invention takes is:
A kind of technology of prepared by reverse microemulsion method solid acid catalyst comprises that step is as follows:
(1) with Ti(SO 4) 29H 2O ﹑ Al(NO 3) 39H 2O mixes with deionized water and is made into inorganic salt solution, Ti(SO 4) 29H 2O and Al(NO 3) 39H 2The O amount of substance is than being 1:0.5-2, and the inorganic salt solution total concentration of solutes is 0.5-1.2molL -1
(2) Biao Mian Huo Ji ﹑ Zhu Biao Mian Huo Ji ﹑ oil phase is joined in the inorganic salt solution in the stirring, four volume ratio is 1-6:1-4:5-20:1, mixes, and continues to stir 30-40min, obtain the reverse micro emulsion of clear, make solution A;
(3) ammonium carbonate is dissolved in the deionized water, stirs, it is water-soluble to be configured to ammonium carbonate, concentration 3-8molL -1
(4) ammonium carbonate solution of getting in addition in Biao Mian Huo Ji ﹑ Zhu Biao Mian Huo Ji ﹑ oil phase and the stirring mixes, four volume ratio is 1-6:1-4:5-20:1, continues to stir 30-40min, mixes, obtain the reverse micro emulsion of clear, make solution B;
(5) solution A and solution B are mixed according to volume ratio 1:1-6, stirring reaction 1.5h staticly settles 20h, filters, and with deionized water ﹑ ethanol cyclic washing, uses AgNO 3Solution detects, and does not contain Cl up to filtrate -Till, the filter cake oven dry, standby;
(6) configuration (NH 4) 2SO 4Solution, with above-mentioned filter cake incipient impregnation 10-30min, temperature-controlled drying, standby;
(7) in the filter cake powder dislocation Muffle furnace that step (6) is obtained, the temperature control calcining, 600-650 ℃ of calcining 3-5h obtains TiO 2-Al 2O 3/ SO 4 2+Solid super-strong acid.
Among the above-mentioned preparation method, step (2) and (4) described surfactant are Span-80, and described cosurfactant is a kind of of n-butanol, n-amyl alcohol, n-heptanol, and oil phase is cyclohexane.
Described (the NH of step (6) 4) 2SO 4The concentration of solution is 0.25-1molL -1, temperature control is 90-110 ℃, be 12-24h drying time.
The present invention compared with prior art has remarkable advantage: the synthesis of solid acid catalyst step operation of (1) institute of the present invention is simple and easy; (2) general synthetic nano particle sizes such as coprecipitation are difficult to control, it is also wideer to distribute, among the present invention in the reverse micro emulsion that non-ionic surface active/water is formed, volume ratio by control surface activating agent and water, water inorganic salt concentration etc. reaction condition, the nanoparticulate dispersed degree that is synthesized is better, particle diameter is less and controlled, has bigger reference area; (3) composite catalyst of the present invention has better catalytic activity with such catalyst ratio that existing method makes, and catalytic efficiency improves 5%-10%.
The specific embodiment
Further specify below in conjunction with embodiment.
Embodiment 1
(1) with the Ti(SO of 0.8g 4) 29H 2O ﹑ 0.8gAl(NO 3) 39H 2O joins in the 5mL deionized water, stirs, and is standby;
(2) the solution 5mL that gets 11mL Span-80,11mL n-butanol, 25mL cyclohexane and step (1) mixes, and stirs 30min, obtains the reverse micro emulsion of clear, and is standby;
(3) ammonium carbonate with 1.5g joins in the 5mL deionized water, stirs, and gets sal volatile;
(4) the solution 5mL that gets 11mLSpan-80,11mL n-butanol, 25mL cyclohexane and above-mentioned steps (3) mixes, and stirs 30-40min, obtains the reverse micro emulsion of clear, and is standby;
(5) solution with configuration in above-mentioned steps (2) and the step (4) mixes, and stirring reaction 1.5h staticly settles 20h, filters, and with deionized water ﹑ ethanol cyclic washing, uses AgNO 3Solution detects, and does not contain Cl up to filtrate -Till, the filter cake oven dry, standby;
(6) use 0.25molL -1(NH 4) 2SO 4Solution with the filter cake incipient impregnation 30min in the above-mentioned steps (5), filters, 110 ℃ of temperature controls, and dry 12h, standby;
(7) with in the nano-powder dislocation Muffle furnace in the step (6), 600 ℃ of temperature controls, calcining 3.5h obtains TiO 2-Al 2O 3/ SO 4 2+Solid super-strong acid.Record specific area 400m 2/ g, corresponding average particle size 15nm.
Embodiment 2
(1) with the Ti(SO of 0.8g 4) 29H 2O ﹑ 0.8gAl(NO 3) 39H 2O joins in the 6mL deionized water, stirs, and is standby;
(2) the solution 6mL that gets 11mlSpan-80,6mL n-butanol, 25mL cyclohexane and above-mentioned steps (1) mixes, and stirs 30-40min, obtains the reverse micro emulsion of clear, and is standby;
(3) ammonium carbonate with 1.5g joins in the 6mL deionized water, stirs, and is standby;
(4) the 6mL solution of getting 11mlSpan-80,6mL n-butanol, 25mL cyclohexane and above-mentioned steps 3 mixes, and stirs 30-40min, obtains the reverse micro emulsion of clear, and is standby;
(5) solution with configuration in above-mentioned steps (2) and the step (4) mixes, and stirring reaction 1.5h staticly settles 20h, filters, and with deionized water ﹑ ethanol cyclic washing, uses AgNO 3Solution detects, and does not contain Cl up to filtrate -Till, the filter cake oven dry, standby;
(6) use 0.25molL -1(NH 4) 2SO 4Solution with the filter cake incipient impregnation 30min in the above-mentioned steps (5), filters, 110 ℃ of temperature controls, and dry 12h, standby;
(7) with in the nano-powder dislocation Muffle furnace in the step (6), 600 ℃ of temperature controls, calcining 3.5h obtains TiO 2-Al 2O 3/ SO 4 2+Solid super-strong acid.Record specific area 380m 2/ g, corresponding average particle size 20nm.
Embodiment 3
(1) with the Ti(SO of 0.8g 4) 29H 2O ﹑ 0.8gAl(NO 3) 39H 2O joins in the 5mL deionized water, stirs, and is standby;
(2) the solution 5mL that gets 11mlSpan-80,6mL n-butanol, 25mL cyclohexane and above-mentioned steps (1) mixes, and stirs 30-40min, obtains the reverse micro emulsion of clear, and is standby;
(3) ammonium carbonate with 1.5g joins in the 5mL deionized water, stirs, and is standby;
(4) the solution 5mL that gets 11mlSpan-80,6mL n-butanol, 25mL cyclohexane and above-mentioned steps (3) mixes, and stirs 30-40min, obtains the reverse micro emulsion of clear, and is standby;
(5) solution with configuration in above-mentioned steps (2) and the step (4) mixes, and stirring reaction 1.5h staticly settles 20h, filters, and with deionized water ﹑ ethanol cyclic washing, uses AgNO 3Solution detects, and does not contain Cl up to filtrate -Till, the filter cake oven dry, standby;
(6) use 0.25molL -1(NH 4) 2SO 4Solution with the filter cake incipient impregnation 30min in the above-mentioned steps (5), filters, 110 ℃ of temperature controls, and dry 12h, standby;
(7) with in the nano-powder dislocation Muffle furnace in the step (6), 600 ℃ of temperature controls, calcining 3.5h obtains TiO 2-Al 2O 3/ SO 4 2+Solid super-strong acid.Record specific area 390m 2/ g, corresponding average particle size 16nm.
Embodiment 4
(1) with the Ti(SO of 0.8g 4) 29H 2O ﹑ 0.8gAl(NO 3) 39H 2O joins in the 5mL deionized water, stirs, and is standby;
(2) the solution 5mL that gets 11mlSpan-80,20mL n-butanol, 25mL cyclohexane and above-mentioned steps (1) mixes, and stirs 30-40min, obtains the reverse micro emulsion of clear, and is standby;
(3) ammonium carbonate with 2g joins in the 5mL deionized water, stirs, and is standby;
(4) the solution 5mL that gets 11mlSpan-80,20mL n-butanol, 25mL cyclohexane and above-mentioned steps (3) mixes, and stirs 30-40min, obtains the reverse micro emulsion of clear, and is standby;
(5) solution with configuration in above-mentioned steps (2) and the step (4) mixes, and stirring reaction 1.5h staticly settles 20h, filters, and with deionized water ﹑ ethanol cyclic washing, uses AgNO 3Solution detects, and does not contain Cl up to filtrate -Till, the filter cake oven dry, standby;
(6) use 0.25molL -1(NH 4) 2SO 4Solution with the filter cake incipient impregnation 30min in the above-mentioned steps (5), filters, 110 ℃ of temperature controls, and dry 12h, standby;
(7) with in the nano-powder dislocation Muffle furnace in the step (6), 600 ℃ of temperature controls, calcining 3.5h obtains TiO 2-Al 2O 3/ SO 4 2+Solid super-strong acid.Record specific area 420m 2/ g, corresponding average particle size 12nm.

Claims (3)

1. the technology of a prepared by reverse microemulsion method solid acid catalyst is characterized in that, comprises that step is as follows:
(1) with Ti(SO 4) 29H 2O ﹑ Al(NO 3) 39H 2O mixes with deionized water and is made into inorganic salt solution, Ti(SO 4) 29H 2O and Al(NO 3) 39H 2The O amount of substance is than being 1:0.5-2, and the inorganic salt solution total concentration of solutes is 0.5-1.2molL -1
(2) Biao Mian Huo Ji ﹑ Zhu Biao Mian Huo Ji ﹑ oil phase is joined in the inorganic salt solution in the stirring, four volume ratio is 1-6:1-4:5-20:1, mixes, and continues to stir 10-40min, obtain the reverse micro emulsion of clear, make solution A;
(3) ammonium carbonate is dissolved in the deionized water, stirs, it is water-soluble to be configured to ammonium carbonate, concentration 3-8molL -1
(4) ammonium carbonate solution of getting in addition in Biao Mian Huo Ji ﹑ Zhu Biao Mian Huo Ji ﹑ oil phase and the stirring mixes, four volume ratio is 1-6:1-4:5-20:1, continues to stir 10-40min, mixes, obtain the reverse micro emulsion of clear, make solution B;
(5) solution A and solution B are mixed according to volume ratio 1:1-6, stirring reaction 1.5h staticly settles 20h, filters, and with deionized water ﹑ ethanol cyclic washing, uses AgNO 3Solution detects, and does not contain Cl up to filtrate -Till,
The filter cake oven dry, standby;
(6) configuration (NH 4) 2SO 4Solution, with above-mentioned filter cake incipient impregnation 30min, temperature-controlled drying, standby;
(7) in the filter cake powder dislocation Muffle furnace that step (6) is obtained, the temperature control calcining, 600-650 ℃ of calcining 3-5h obtains TiO 2-Al 2O 3/ SO 4 2+Solid super-strong acid.
2. the technology of a kind of prepared by reverse microemulsion method solid acid catalyst according to claim 1, it is characterized in that, step (2) and (4) described surfactant are Span-80, and described cosurfactant is a kind of of n-butanol, n-amyl alcohol, n-heptanol, and oil phase is cyclohexane.
3. the technology of a kind of prepared by reverse microemulsion method solid acid catalyst according to claim 1 is characterized in that, the described (NH of step (6) 4) 2SO 4The concentration of solution is 0.25-1molL -1, temperature control is 90-110 ℃, be 12-24h drying time.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112006028A (en) * 2020-07-29 2020-12-01 合肥皖科凌霄环境科技合伙企业(有限合伙) Preparation method of titanium-based solid acid-containing air bactericide
CN113527645A (en) * 2021-07-20 2021-10-22 浙江恒澜科技有限公司 Method for preparing titanium dioxide polyester catalyst in reverse microemulsion
CN113527651A (en) * 2021-07-20 2021-10-22 浙江恒澜科技有限公司 Method for preparing titanium dioxide polyester catalyst in alkane solvent

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101020631A (en) * 2007-03-23 2007-08-22 上海工程技术大学 S2O8 2-/TiO2 Al2 O3 super solid acid catalyzed n-butyl acetate synthesizing process
CN101062481A (en) * 2006-04-30 2007-10-31 肇庆学院 Preparation method of solid super-strong acid
CN101172238A (en) * 2006-11-01 2008-05-07 中国石油化工股份有限公司 Nano solid supper corrosive acid and preparation method thereof
CN101249447A (en) * 2008-03-14 2008-08-27 华侨大学 Novel solid acid catalyst preparation method
CN101318139A (en) * 2008-07-22 2008-12-10 上海应用技术学院 Composite solid super acidic catalyst and preparation method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101062481A (en) * 2006-04-30 2007-10-31 肇庆学院 Preparation method of solid super-strong acid
CN101172238A (en) * 2006-11-01 2008-05-07 中国石油化工股份有限公司 Nano solid supper corrosive acid and preparation method thereof
CN101020631A (en) * 2007-03-23 2007-08-22 上海工程技术大学 S2O8 2-/TiO2 Al2 O3 super solid acid catalyzed n-butyl acetate synthesizing process
CN101249447A (en) * 2008-03-14 2008-08-27 华侨大学 Novel solid acid catalyst preparation method
CN101318139A (en) * 2008-07-22 2008-12-10 上海应用技术学院 Composite solid super acidic catalyst and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
陈志胜等: "Ｏ／Ｗ 微乳体系制备固体超强酸SO42-/SnO2-Ta2O5及其表征", 《石油炼制与化工》, vol. 43, no. 10, 31 October 2012 (2012-10-31) *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112006028A (en) * 2020-07-29 2020-12-01 合肥皖科凌霄环境科技合伙企业(有限合伙) Preparation method of titanium-based solid acid-containing air bactericide
CN113527645A (en) * 2021-07-20 2021-10-22 浙江恒澜科技有限公司 Method for preparing titanium dioxide polyester catalyst in reverse microemulsion
CN113527651A (en) * 2021-07-20 2021-10-22 浙江恒澜科技有限公司 Method for preparing titanium dioxide polyester catalyst in alkane solvent
CN113527645B (en) * 2021-07-20 2022-12-16 浙江恒逸石化研究院有限公司 Method for preparing titanium dioxide polyester catalyst in reverse microemulsion

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