CN103316697B - 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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CN103316697B
CN103316697B CN201310301255.7A CN201310301255A CN103316697B CN 103316697 B CN103316697 B CN 103316697B CN 201310301255 A CN201310301255 A CN 201310301255A CN 103316697 B CN103316697 B CN 103316697B
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acid catalyst
deionized water
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solid acid
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CN103316697A (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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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 reverse microemulsion process is prepared the technique of 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 group, esterification, isomerization, polymerization, oligomerisation and oxidation reaction etc. in organic synthesis; and because the advantage such as its pollution to the corrosion little ﹑ environment of equipment is little; in Green Chemistry, environmental friendly catalysis, prospect has a very wide range of applications.Traditional TiO 2-Al 2o 3/ SO 4 2-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 easily there is particle diameter distribution Bu Jun ﹑ granularity greatly and agglomeration Yan Chong ﹑ specific area shortcoming on the low side in the solid acid catalyst of preparing through the method.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 technique is simple, can regulate pattern, particle size, distribution of preparing nano-powder etc. by changing the parameter of technique.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 water in the concentration of 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 poor ﹑ size of the poly-﹑ particle decentralization of easy group that the synthetic solid super-strong acid of traditional handicraft exists.One pack system solid super acid catalyst, the sulfate radical that plays an important role more easily runs off in reaction, easy inactivation under high-temperature condition, so one pack system solid catalyst has good catalytic activity at the beginning, but service life is shorter.By to mixing the modification of metal oxide to 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 reverse microemulsion process to prepare the technique of solid acid catalyst, synthesized TiO 2-Al 2o 3/ SO 4 2+solid super-strong acid, synthetic solid super-strong acid has the advantages such as the Hao ﹑ specific area of particle decentralization great ﹑ particle size is controlled.
The technical scheme that the present invention takes is:
Reverse microemulsion process is prepared a technique for solid acid catalyst, comprises that step is as follows:
(1) by Ti (SO 4) 29H 2o ﹑ Al (NO 3) 39H 2o mixes and is made into inorganic salt solution with deionized water, Ti (SO 4) 29H 2o and Al (NO 3) 39H 2o amount of substance is than being 1:0.5-2, and 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 stirring, four volume ratio is 1-6:1-4:5-20:1, mixes, and continues to stir 30-40min, the reverse micro emulsion that obtains clear, makes solution A;
(3) ammonium carbonate is dissolved in deionized water, stirs, be configured to ammonium carbonate solution, concentration 3-8molL -1;
(4) ammonium carbonate solution of separately getting in Biao Mian Huo Ji ﹑ Zhu Biao Mian Huo Ji ﹑ oil phase and stirring mixes, four volume ratio is 1-6:1-4:5-20:1, continues to stir 30-40min, mixes, the reverse micro emulsion that obtains clear, makes 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, until filtrate is not containing Cl -till, filter cake is dried, standby;
(6) configuration (NH 4) 2sO 4solution, by above-mentioned filter cake incipient impregnation 10-30min, temperature-controlled drying, standby;
(7) in filter cake powder dislocation Muffle furnace step (6) being obtained, temperature control calcining, 600-650 ℃ of calcining 3-5h, obtains TiO 2-Al 2o 3/ SO 4 2-solid super-strong acid.
In above-mentioned preparation method, the described surfactant in step (2) and (4) is Span-80, and described cosurfactant is a kind of of n-butanol, n-amyl alcohol, n-heptanol, and oil phase is cyclohexane.
(the NH that step (6) is described 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 operation of (1) synthesized solid acid catalyst of the present invention step is simple and easy; (2) the synthetic nano particle size such as general coprecipitation is difficult to control, distribute also wider, in the reverse micro emulsion forming at non-ionic surface active/water in the present invention, volume ratio by control surface activating agent and water, water inorganic salt concentration etc. reaction condition, the nanoparticulate dispersed degree of synthesized is better, particle diameter is less and controlled, has larger 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
Below in conjunction with embodiment, further illustrate.
Embodiment 1
(1) by the Ti (SO of 0.8g 4) 29H 2o ﹑ 0.8gAl (NO 3) 39H 2o joins in 5mL deionized water, stirs, standby;
(2) get 11mL Span-80,11mL n-butanol, 25mL cyclohexane and mix with the solution 5mL of step (1), stir 30min, obtain the reverse micro emulsion of clear, standby;
(3) ammonium carbonate of 1.5g is joined in 5mL deionized water, stir, obtain sal volatile;
(4) get 11mLSpan-80,11mL n-butanol, 25mL cyclohexane and mix with the solution 5mL of above-mentioned steps (3), stir 30-40min, obtain the reverse micro emulsion of clear, standby;
(5) solution of configuration in above-mentioned steps (2) and step (4) is mixed, stirring reaction 1.5h, staticly settles 20h, filters, and with deionized water ﹑ ethanol cyclic washing, uses AgNO 3solution detects, until filtrate does not contain Cl-, filter cake is dried, standby;
(6) use 0.25molL -1(NH 4) 2sO 4solution, by the filter cake incipient impregnation 30min in above-mentioned steps (5), filters, 110 ℃ of temperature controls, and dry 12h, standby;
(7) by the nano-powder dislocation Muffle furnace in 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) by the Ti (SO of 0.8g 4) 29H 2o ﹑ 0.8gAl (NO 3) 39H 2o joins in 6mL deionized water, stirs, standby;
(2) get 11mlSpan-80,6mL n-butanol, 25mL cyclohexane and mix with the solution 6mL of above-mentioned steps (1), stir 30-40min, obtain the reverse micro emulsion of clear, standby;
(3) ammonium carbonate of 1.5g is joined in 6mL deionized water, stir, standby;
(4) get 11mlSpan-80,6mL n-butanol, 25mL cyclohexane and mix with the 6mL solution of above-mentioned steps 3, stir 30-40min, obtain the reverse micro emulsion of clear, standby;
(5) solution of configuration in above-mentioned steps (2) and step (4) is mixed, stirring reaction 1.5h, staticly settles 20h, filters, and with deionized water ﹑ ethanol cyclic washing, uses AgNO 3solution detects, until filtrate is not containing Cl -till, filter cake is dried, standby;
(6) use 0.25molL -1(NH 4) 2sO 4solution, by the filter cake incipient impregnation 30min in above-mentioned steps (5), filters, 110 ℃ of temperature controls, and dry 12h, standby;
(7) by the nano-powder dislocation Muffle furnace in 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) by the Ti (SO of 0.8g 4) 29H 2o ﹑ 0.8gAl (NO 3) 39H 2o joins in 5mL deionized water, stirs, standby;
(2) get 11mlSpan-80,6mL n-butanol, 25mL cyclohexane and mix with the solution 5mL of above-mentioned steps (1), stir 30-40min, obtain the reverse micro emulsion of clear, standby;
(3) ammonium carbonate of 1.5g is joined in 5mL deionized water, stir, standby;
(4) get 11mlSpan-80,6mL n-butanol, 25mL cyclohexane and mix with the solution 5mL of above-mentioned steps (3), stir 30-40min, obtain the reverse micro emulsion of clear, standby;
(5) solution of configuration in above-mentioned steps (2) and step (4) is mixed, stirring reaction 1.5h, staticly settles 20h, filters, and with deionized water ﹑ ethanol cyclic washing, uses AgNO 3solution detects, until filtrate does not contain Cl-, filter cake is dried, standby;
(6) use 0.25molL -1(NH 4) 2sO 4solution, by the filter cake incipient impregnation 30min in above-mentioned steps (5), filters, 110 ℃ of temperature controls, and dry 12h, standby;
(7) by the nano-powder dislocation Muffle furnace in 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) by the Ti (SO of 0.8g 4) 29H 2o ﹑ 0.8gAl (NO 3) 39H 2o joins in 5mL deionized water, stirs, standby;
(2) get 11mlSpan-80,20mL n-butanol, 25mL cyclohexane and mix with the solution 5mL of above-mentioned steps (1), stir 30-40min, obtain the reverse micro emulsion of clear, standby;
(3) ammonium carbonate of 2g is joined in 5mL deionized water, stir, standby;
(4) get 11mlSpan-80,20mL n-butanol, 25mL cyclohexane and mix with the solution 5mL of above-mentioned steps (3), stir 30-40min, obtain the reverse micro emulsion of clear, standby;
(5) solution of configuration in above-mentioned steps (2) and step (4) is mixed, stirring reaction 1.5h, staticly settles 20h, filters, and with deionized water ﹑ ethanol cyclic washing, uses AgNO 3solution detects, until filtrate does not contain Cl-, filter cake is dried, standby;
(6) use 0.25molL -1(NH 4) 2sO 4solution, by the filter cake incipient impregnation 30min in above-mentioned steps (5), filters, 110 ℃ of temperature controls, and dry 12h, standby;
(7) by the nano-powder dislocation Muffle furnace in 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. reverse microemulsion process is prepared a technique for solid acid catalyst, it is characterized in that, comprises that step is as follows:
(1) by Ti (SO 4) 29H 2o ﹑ Al (NO 3) 39H 2o mixes and is made into inorganic salt solution with deionized water, Ti (SO 4) 29H 2o and Al (NO 3) 39H 2o amount of substance is than being 1:0.5-2, and 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 stirring, four volume ratio is 1-6:1-4:5-20:1, mixes, and continues to stir 10-40min, the reverse micro emulsion that obtains clear, makes solution A;
(3) ammonium carbonate is dissolved in deionized water, stirs, be configured to ammonium carbonate solution, concentration 3-8molL -1;
(4) ammonium carbonate solution of separately getting in Biao Mian Huo Ji ﹑ Zhu Biao Mian Huo Ji ﹑ oil phase and stirring mixes, four volume ratio is 1-6:1-4:5-20:1, continues to stir 10-40min, mixes, the reverse micro emulsion that obtains clear, makes 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, until filtrate does not contain Cl-, filter cake is dried, standby;
(6) configuration (NH 4) 2sO 4solution, by above-mentioned filter cake incipient impregnation 30min, temperature-controlled drying, standby;
(7) in filter cake powder dislocation Muffle furnace step (6) being obtained, temperature control calcining, 600-650 ℃ of calcining 3-5h, obtains TiO 2-Al 2o 3/ SO 4 2-solid super-strong acid.
2. a kind of reverse microemulsion process according to claim 1 is prepared the technique of solid acid catalyst, it is characterized in that, the described surfactant in step (2) and (4) is Span-80, described cosurfactant is a kind of of n-butanol, n-amyl alcohol, n-heptanol, and oil phase is cyclohexane.
3. a kind of reverse microemulsion process according to claim 1 is prepared the technique of solid acid catalyst, it is characterized in that (the NH that step (6) is described 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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