CN106588705B - A kind of technique by nano solid base catalyst synthesizing glycol DAADBSA ester - Google Patents
A kind of technique by nano solid base catalyst synthesizing glycol DAADBSA ester Download PDFInfo
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- CN106588705B CN106588705B CN201611134991.8A CN201611134991A CN106588705B CN 106588705 B CN106588705 B CN 106588705B CN 201611134991 A CN201611134991 A CN 201611134991A CN 106588705 B CN106588705 B CN 106588705B
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Abstract
The invention discloses a kind of technique by nano solid base catalyst synthesizing glycol DAADBSA ester, with glycol, pyridine, benzene sulfonyl chloride, the raw materials such as the nanoscale Ti/Al complex solid base catalysts that homemade caesium is modified pass through ice-water bath, it is evaporated under reduced pressure, the operational means such as magnetic agitation prepares Glycol dibenzenesulfonate.
Description
Technical field
The present invention relates to a kind of technique by nano solid base catalyst synthesizing glycol DAADBSA ester, belong to organic
Synthesis field.
Background technology
Since Pedersen in 1967 has found first crown compound, the research and development to cyclic polyether
Fast development.Further investigation of the people to its specific structure and complex performance, not only organic chemistry started " Crownether Chemistry ",
" host-guest chemistry ", " supramolecular chemistry " frontier, and the crown ether of a large amount of Various Functions and its functional derivative are synthesized out
Come.One of the most frequently used intermediate of crown ether is multiethylene-glycol DAADBSA ester.The process route of synthesis glycol DAADBSA ester at present
More complicated, yield is also bad.I have invented a kind of nanoscale Ti/Al complex solids base catalyst being modified with homemade caesium to close
Into the technique of Glycol dibenzenesulfonate, the technological operation is simple, and raw material sources are convenient, and product purity yield is good.
The content of the invention
In view of the above-mentioned problems of the prior art, the present invention provides one kind synthesizes second two by nano solid base catalyst
The technique of alcohol DAADBSA ester.
To achieve these goals, the technical solution adopted by the present invention is：A kind of nanoscale Ti/ being modified with homemade caesium
The technique of Al complex solid base catalyst synthesizing glycol DAADBSA esters.Comprise the following steps：
Step 1, glycol and pyridine be mixed evenly in a reservoir, be cooled to 2 DEG C with ice-water bath under magnetic agitation；
Step 2, the nanoscale Ti/Al complex solid base catalysts for being modified homemade caesium, are added in container, then
Benzene sulfonyl chloride is added in beaker with chloroform, and then magnetic agitation 2h is well mixed, and is then added drop-wise in container with per minute 90
Drip speed to be added dropwise, the magnetic agitation when being added dropwise, control temperature continues magnetic agitation 5h after 3-5 DEG C, completion of dropwise addition；
Step 3 and then mixture is poured into 500mL frozen water, abundant magnetic agitation, separates organic layer, recovery is homemade
The nanoscale Ti/Al complex solid base catalysts that caesium is modified, it is 7.0 that number to pH value, which is washed with deionized,；
Step 4 and then it is being evaporated under reduced pressure, by moisture, solvent evaporates, and obtains crude product；
Step 5 and then crude product is recrystallized with absolute ethyl alcohol, finally give Glycol dibenzenesulfonate.
The nanoscale Ti/Al complex solid base catalysts that caesium is modified, preparation technology are as follows：
Step 1, by aluminum oxide, titanium dioxide first handles 2h under ultrasonic wave；
Step 2 and then progress calcination processing：First in air, 500 DEG C, 4h is calcined under 0.2kpa, then in nitrogen, 600
DEG C, calcine 3h under 0.4kpa；
Step 3, calcining carry out helium-atmosphere after terminating and enclose lower purging 3h；
Step 4 and then use infusion process introduce cesium element：By 10g aluminum oxide, 5g titanium dioxide in mass ratio 2:1 is mixed
Close, be then immersed in 12h in 0.5mol/L Cs2CO3 solution；
Step 5 and then using hot alkali treatment, 2h is handled under 180 DEG C of hot-airs, is then immersed in 5% sodium hydroxide
5h is handled in solution, is then transferred into beaker；
Step 6, carry out coupling processing：0.05mol coupling agents kh500 is added drop-wise in the mixture after hot alkali treatment, side
Side magnetic agitation is added dropwise；
Step 7,0.05mol surfactant diglycollic amides are added drop-wise in the mixture after coupling processing, side is added dropwise
Side magnetic agitation, then carrying out microwave treatment；
After step 8, microwave treatment terminate, first in 110 DEG C of dry 12h of thermostatic drying chamber, then calcined in tube furnace
Processing：First in nitrogen and ammonia 1:3,650 DEG C, 4h is calcined under 0.3kpa, then in nitrogen, 700 DEG C, is calcined under 0.6kpa
5h, finally give the nanoscale Ti/Al complex solid base catalysts of caesium modification.
Beneficial effect:A kind of nanoscale Ti/Al complex solids base catalyst being modified with homemade caesium of the present invention synthesizes second
The technique of glycol DAADBSA ester, the technological operation is simple, and raw material relatively easily obtains, by adding receiving for homemade caesium modification
Meter level Ti/Al complex solid base catalysts, effectively raise reaction rate, reduce the generation of side reaction, in building-up process
In handled by magnetic agitation etc., activation can be played to reactant enables reaction to be more smoothed out, and makes reaction towards pre-
The direction of phase is carried out, and is improved the yield of target product.By ice-water bath, vacuum distillation can obtain purer ethylene glycol
DAADBSA ester.Wherein embodiment 1 produces glycol, benzene sulfonyl chloride, and the nanoscale Ti/Al complex solid alkali that homemade caesium is modified is urged
Agent mass ratio 18:105:0.6 sample.Glycol 18g, benzene sulfonyl chloride 105g, the nanoscale Ti/Al composite solids that homemade caesium is modified
Body base catalyst 0.6g.Pyridine 1.2mol, chloroform 150ml.And embodiment 2 produces glycol, benzene sulfonyl chloride, homemade caesium is modified
Nanoscale Ti/Al complex solid base catalysts mass ratio 26:100:0.5 sample.Glycol 26g, benzene sulfonyl chloride 100g, it is homemade
The nanoscale Ti/Al complex solid base catalysts 0.5g that caesium is modified.Pyridine 1.1mol, chloroform 160ml.Obtained ethylene glycol hexichol
Sulphonic acid ester purity and yield is best.
Embodiment
Embodiment 1
The nanoscale Ti/Al complex solid base catalysts that caesium is modified, preparation technology are as follows：
Step 1, by aluminum oxide, titanium dioxide first handles 2h under ultrasonic wave；
Step 2 and then progress calcination processing：First in air, 500 DEG C, 4h is calcined under 0.2kpa, then in nitrogen, 600
DEG C, calcine 3h under 0.4kpa；
Step 3, calcining carry out helium-atmosphere after terminating and enclose lower purging 3h；
Step 4 and then use infusion process introduce cesium element：By 10g aluminum oxide, 5g titanium dioxide in mass ratio 2:1 is mixed
Close, be then immersed in 12h in 0.5mol/L Cs2CO3 solution；
Step 5 and then using hot alkali treatment, 2h is handled under 180 DEG C of hot-airs, is then immersed in 5% sodium hydroxide
5h is handled in solution, is then transferred into beaker；
Step 6, carry out coupling processing：0.05mol coupling agents kh500 is added drop-wise in the mixture after hot alkali treatment, side
Side magnetic agitation is added dropwise；
Step 7,0.05mol surfactant diglycollic amides are added drop-wise in the mixture after coupling processing, side is added dropwise
Side magnetic agitation, then carrying out microwave treatment；
After step 8, microwave treatment terminate, first in 110 DEG C of dry 12h of thermostatic drying chamber, then calcined in tube furnace
Processing：It is 1 first in nitrogen and ammonia volume ratio:3 mixing, 650 DEG C, 4h is calcined under 0.3kpa, then in nitrogen, 700 DEG C,
5h is calcined under 0.6kpa, finally gives the nanoscale Ti/Al complex solid base catalysts of caesium modification.
The preparation of Glycol dibenzenesulfonate：
Produce glycol, benzene sulfonyl chloride, the nanoscale Ti/Al complex solid base catalysts mass ratio 18 that homemade caesium is modified:
105:0.6 sample.Glycol 18g, benzene sulfonyl chloride 105g, the nanoscale Ti/Al complex solid base catalysts that homemade caesium is modified
0.6g.Pyridine 1.2mol, chloroform 150ml.
Step 1,18g glycol and 1.2mol pyridines be mixed evenly in a reservoir, be cooled to 2 with ice-water bath under magnetic agitation
℃；
Step 2, the nanoscale Ti/Al complex solid base catalysts for being modified the homemade caesiums of 0.6g, are added in container, so
105g benzene sulfonyl chlorides and 150ml chloroforms are added in beaker afterwards, then magnetic agitation 2h is well mixed, and is then added drop-wise to container
In be added dropwise with per minute 90 drop speed, the magnetic agitation when being added dropwise, control temperature continues magnetic force after 3-5 DEG C, completion of dropwise addition and stirred
Mix 5h；
Step 3 and then mixture is poured into 500mL frozen water, abundant magnetic agitation, separates organic layer, recovery is homemade
The nanoscale Ti/Al complex solid base catalysts that caesium is modified, it is 7.0 that number to pH value, which is washed with deionized,；
Step 4 and then it is being evaporated under reduced pressure, by moisture, solvent evaporates, and obtains crude product；
Step 5 and then crude product is recrystallized with absolute ethyl alcohol, finally give Glycol dibenzenesulfonate.
Embodiment 2 produces glycol, benzene sulfonyl chloride, the nanoscale Ti/Al complex solid base catalyst matter that homemade caesium is modified
Measure ratio 26:100:0.5 sample.Glycol 26g, benzene sulfonyl chloride 100g, the nanoscale Ti/Al complex solid alkali that homemade caesium is modified are urged
Agent 0.5g.Pyridine 1.1mol, chloroform 160ml.Operating procedure is as embodiment 1.
Embodiment 3 produces glycol, benzene sulfonyl chloride, the nanoscale Ti/Al complex solid base catalyst matter that homemade caesium is modified
Measure ratio 18:105:0.5 sample.Glycol 18g, benzene sulfonyl chloride 105g, the nanoscale Ti/Al complex solid alkali that homemade caesium is modified are urged
Agent 0.5g.Other raw materials, operating procedure is as embodiment 1.
Embodiment 4 produces glycol, benzene sulfonyl chloride, the nanoscale Ti/Al complex solid base catalyst matter that homemade caesium is modified
Measure ratio 18:105:0.4 sample.Glycol 18g, benzene sulfonyl chloride 105g, the nanoscale Ti/Al complex solid alkali that homemade caesium is modified are urged
Agent 0.4g.Other raw materials, operating procedure is as embodiment 1.
Embodiment 5 produces glycol, benzene sulfonyl chloride, the nanoscale Ti/Al complex solid base catalyst matter that homemade caesium is modified
Measure ratio 18:105:0.3 sample.Glycol 18g, benzene sulfonyl chloride 105g, the nanoscale Ti/Al complex solid alkali that homemade caesium is modified are urged
Agent 0.3g.Other raw materials, operating procedure is as embodiment 1.
Embodiment 6 produces glycol, benzene sulfonyl chloride, the nanoscale Ti/Al complex solid base catalyst matter that homemade caesium is modified
Measure ratio 18:105:0.2 sample.Glycol 18g, benzene sulfonyl chloride 105g, the nanoscale Ti/Al complex solid alkali that homemade caesium is modified are urged
Agent 0.2g.Other raw materials, operating procedure is as embodiment 1.
Embodiment 7 produces glycol, benzene sulfonyl chloride, the nanoscale Ti/Al complex solid base catalyst matter that homemade caesium is modified
Measure ratio 18:105:0.1 sample.Glycol 18g, benzene sulfonyl chloride 105g, the nanoscale Ti/Al complex solid alkali that homemade caesium is modified are urged
Agent 0.1g.Other raw materials, operating procedure is as embodiment 1.
Embodiment 8 produces glycol, benzene sulfonyl chloride, the nanoscale Ti/Al complex solid base catalyst matter that homemade caesium is modified
Measure ratio 18:105:0.7 sample.Glycol 18g, benzene sulfonyl chloride 105g, the nanoscale Ti/Al complex solid alkali that homemade caesium is modified are urged
Agent 0.7g.Other raw materials, operating procedure is as embodiment 1.
Embodiment 9 produces glycol, benzene sulfonyl chloride, the nanoscale Ti/Al complex solid base catalyst matter that homemade caesium is modified
Measure ratio 18:105:0.8 sample.Glycol 18g, benzene sulfonyl chloride 105g, the nanoscale Ti/Al complex solid alkali that homemade caesium is modified are urged
Agent 0.8g.Other raw materials, operating procedure is as embodiment 1.
Embodiment 10 produces glycol, benzene sulfonyl chloride, the nanoscale Ti/Al complex solid base catalyst matter that homemade caesium is modified
Measure ratio 18:105:0.9 sample.Glycol 18g, benzene sulfonyl chloride 105g, the nanoscale Ti/Al complex solid alkali that homemade caesium is modified are urged
Agent 0.9g.Other raw materials, operating procedure is as embodiment 1.
Embodiment 11 produces glycol, benzene sulfonyl chloride, the nanoscale Ti/Al complex solid base catalyst matter that homemade caesium is modified
Measure ratio 18:105:1 sample.Glycol 18g, benzene sulfonyl chloride 105g, the nanoscale Ti/Al complex solid base catalysis that homemade caesium is modified
Agent 1g.Other raw materials, operating procedure is as embodiment 1.
Embodiment 12 produces glycol, benzene sulfonyl chloride, the nanoscale Ti/Al complex solid base catalyst matter that homemade caesium is modified
Measure ratio 18:105:1.1 sample.Glycol 18g, benzene sulfonyl chloride 105g, the nanoscale Ti/Al complex solid alkali that homemade caesium is modified are urged
Agent 1.1g.Other raw materials, operating procedure is as embodiment 1.
Embodiment 13 produces glycol, benzene sulfonyl chloride, the nanoscale Ti/Al complex solid base catalyst matter that homemade caesium is modified
Measure ratio 18:105:1.2 sample.Glycol 18g, benzene sulfonyl chloride 105g, the nanoscale Ti/Al complex solid alkali that homemade caesium is modified are urged
Agent 1.2g.Other raw materials, operating procedure is as embodiment 1.
Embodiment 14 produces glycol, benzene sulfonyl chloride, the nanoscale Ti/Al complex solid base catalyst matter that homemade caesium is modified
Measure ratio 18:105:1.3 sample.Glycol 18g, benzene sulfonyl chloride 105g, the nanoscale Ti/Al complex solid alkali that homemade caesium is modified are urged
Agent 1.3g.Other raw materials, operating procedure is as embodiment 1.
Embodiment 15 produces glycol, benzene sulfonyl chloride, the nanoscale Ti/Al complex solid base catalyst matter that homemade caesium is modified
Measure ratio 18:105:1.4 sample.Glycol 18g, benzene sulfonyl chloride 105g, the nanoscale Ti/Al complex solid alkali that homemade caesium is modified are urged
Agent 1.4g.Other raw materials, operating procedure is as embodiment 1.
Reference examples 1 produce glycol, benzene sulfonyl chloride, the nanoscale Ti/Al complex solid base catalyst matter that homemade caesium is modified
Measure ratio 18:105:0.6 sample.Glycol 18g, benzene sulfonyl chloride 105g, the nanoscale Ti/Al complex solid alkali that homemade caesium is modified are urged
Agent 0.6g.Without magnetic agitation, but mechanical agitation, other raw materials, operating procedure is as embodiment 1.
Reference examples 2 produce glycol, benzene sulfonyl chloride, the nanoscale Ti/Al complex solid base catalyst matter that homemade caesium is modified
Measure ratio 18:105:0.6 sample.Glycol 18g, benzene sulfonyl chloride 105g, the nanoscale Ti/Al complex solid alkali that homemade caesium is modified are urged
Agent 0.6g.Without ice-water bath controlling reaction temperature, but carry out at room temperature, other raw materials, operating procedure is with embodiment 1 one
Sample.
Reference examples 3 produce glycol, benzene sulfonyl chloride, the nanoscale Ti/Al complex solid base catalyst matter that homemade caesium is modified
Measure ratio 18:105:06 sample.Glycol 18g, benzene sulfonyl chloride 105g, the nanoscale Ti/Al complex solid alkali that homemade caesium is modified are urged
Agent 0.6g.Deionized water washing terminate after not into neutrality, other raw materials, operating procedure is as embodiment 1.
Reference examples 4 produce glycol, benzene sulfonyl chloride, the nanoscale Ti/Al complex solid base catalyst matter that homemade caesium is modified
Measure ratio 18:105:0.6 sample.Glycol 18g, benzene sulfonyl chloride 105g, the nanoscale Ti/Al complex solid alkali that homemade caesium is modified are urged
Agent 0.5g.Handled without recrystallization, other raw materials, operating procedure is as embodiment 1.
Reference examples 5 are added without the nanoscale Ti/Al complex solid base catalysts that homemade caesium is modified, other raw material dosages,
Operating procedure is as embodiment 1.
Reference examples 6 add neopelex catalyst 0.5g, and other raw materials, operating procedure is as embodiment 1.
Reference examples 7, technique, raw material proportioning and embodiment 1 are completely the same, and difference is, the nanoscale that homemade caesium is modified
The preparation of Ti/Al complex solid base catalysts, main difference are, after step 8, microwave treatment terminate, first in thermostatic drying chamber 110
DEG C dry 12h, then tube furnace carry out calcination processing：First in nitrogen and ammonia 1:1,650 DEG C, 4h is calcined under 0.3kpa,
Then in nitrogen, 5h is calcined under 0.6kpa, finally gives the nanoscale Ti/Al complex solid base catalysts of caesium modification by 700 DEG C.
Reference examples 8, technique, raw material, proportioning and embodiment 1 are completely the same, and difference is, the nanoscale that homemade caesium is modified
The preparation of Ti/Al complex solid base catalysts, main difference are, after step 8, microwave treatment terminate, first in thermostatic drying chamber 110
DEG C dry 12h, then tube furnace carry out calcination processing：First in nitrogen and ammonia 3:1,650 DEG C, 4h is calcined under 0.3kpa,
Then in nitrogen, 5h is calcined under 0.6kpa, finally gives the nanoscale Ti/Al complex solid base catalysts of caesium modification by 700 DEG C.
Reference examples 9, technique, raw material, proportioning and embodiment 1 are completely the same, and difference is, the nanoscale that homemade caesium is modified
The preparation of Ti/Al complex solid base catalysts, main difference are, after step 8, microwave treatment terminate, first in thermostatic drying chamber 110
DEG C dry 12h, then tube furnace carry out calcination processing：In nitrogen, 5h is calcined under 0.6kpa, finally gives caesium modification by 700 DEG C
Nanoscale Ti/Al complex solid base catalysts.
Reference examples 10, technique, raw material, proportioning and embodiment 1 are completely the same, and difference is, the nanometer that homemade caesium is modified
The preparation of level Ti/Al complex solid base catalysts, main difference is, after step 8, microwave treatment terminate, first in thermostatic drying chamber
110 DEG C of dry 12h, then carry out calcination processing in tube furnace：First under ammonia atmosphere, 650 DEG C, 4h is calcined under 0.3kpa,
Finally give the nanoscale Ti/Al complex solid base catalysts of caesium modification.
Reference examples 11, technique, raw material, proportioning and embodiment 1 are completely the same, and difference is, self-control nanoscale Ti/Al is compound
The preparation of solid base catalyst does not contain cesium element, and preparation technology is as follows：
Step 1, by aluminum oxide, titanium dioxide first handles 2h under ultrasonic wave；
Step 2 and then progress calcination processing：First in air, 500 DEG C, 4h is calcined under 0.2kpa, then in nitrogen, 600
DEG C, calcine 3h under 0.4kpa；
Step 3, calcining carry out helium-atmosphere after terminating and enclose lower purging 3h；
Step 4, by 10g aluminum oxide, 5g titanium dioxide in mass ratio 2:1 mixing；
Step 5 and then using hot alkali treatment, 2h is handled under 180 DEG C of hot-airs, is then immersed in 5% sodium hydroxide
5h is handled in solution, is then transferred into beaker；
Step 6, carry out coupling processing：0.05mol coupling agents kh500 is added drop-wise in the mixture after hot alkali treatment, side
Side magnetic agitation is added dropwise；
Step 7,0.05mol surfactant diglycollic amides are added drop-wise in the mixture after coupling processing, side is added dropwise
Side magnetic agitation, then carrying out microwave treatment；
After step 8, microwave treatment terminate, first in 110 DEG C of dry 12h of thermostatic drying chamber, then calcined in tube furnace
Processing：It is 1 first in nitrogen and ammonia volume ratio:3 mixing, 650 DEG C, 4h is calcined under 0.3kpa, then in nitrogen, 700 DEG C,
5h is calcined under 0.6kpa, finally gives nanoscale Ti/Al complex solid base catalysts.
The yield purity of experiment test product：
Liquid chromatogram：Agilent1200 high performance liquid chromatographs, chromatographic column:EclipseXDB-C18 chromatographic columns (250mm
× 4.6mm, 5 μm)；Mobile phase is A:5mmol/L ammonium acetate solutions, B:Acetonitrile；Linear gradient elution program:0min (20%A+
80%B), 5min (5%A+95%B), 10min (100%), 20min (5%A+95%B), 22min (20%A+80%B)；Stream
Speed:0.5mL/min；Column temperature:30℃；Excitation wavelength:350nm；Launch wavelength:430nm..Detection product component, calculated purity,
Yield.
The purity of the Glycol dibenzenesulfonate of one each product of table, yield result
Test result indicates that：It can be found that the Glycol dibenzenesulfonate product purity that the technique of embodiment 1,2 obtains, yield
Preferably, proportioning of both techniques in raw material is illustrated, the production of the operation of technique most beneficial for target product.Made under other techniques
The product obtained is not especially desirable in purity, yield.Comparative example 1, comparative example 1,2,3,4,5,6 are can be found that.No
Carry out magnetic agitation, without ice-water bath controlling reaction temperature, but carry out at room temperature, deionized water washing terminate after not in
Property, handled without recrystallization, be added without the nanoscale Ti/Al complex solid base catalysts that homemade caesium is modified, using 12
The purity of Glycol dibenzenesulfonate made from alkyl benzene sulphonate sodium catalyst, yield be not high.
Control group 7-10, it can be seen that the condition of calcining and environment are for the complex solid base catalyst for preparing
Apply in synthesis technique, for product purity, yield has tremendous influence.
Claims (1)
1. a kind of technique by nano solid base catalyst synthesizing glycol DAADBSA ester, it is characterised in that including as follows
Step：
Step 1,18g glycol and 1.2mol pyridines be mixed evenly in a reservoir, be cooled to 2 DEG C with ice-water bath under magnetic agitation；
Step 2, the nanoscale Ti/Al complex solid base catalysts for being modified the homemade caesiums of 0.6g, are added in container, then
105g benzene sulfonyl chlorides and 150ml chloroforms are added in beaker, and then magnetic agitation 2h is well mixed, be then added drop-wise in container with
90 drop speed per minute is added dropwise, and the magnetic agitation when being added dropwise, control temperature continues magnetic agitation 5h after 3-5 DEG C, completion of dropwise addition；
Step 3 and then mixture is poured into 500mL frozen water, abundant magnetic agitation, separates organic layer, reclaim homemade caesium and change
Property nanoscale Ti/Al complex solid base catalysts, be washed with deionized number to pH value be 7.0；
Step 4 and then it is evaporated under reduced pressure again, by moisture, solvent evaporates, and obtains crude product；
Step 5 and then crude product is recrystallized with absolute ethyl alcohol, finally give Glycol dibenzenesulfonate；
The nanoscale Ti/Al complex solid base catalysts that described caesium is modified, preparation technology are as follows：
Step 1, by aluminum oxide, titanium dioxide first handles 2h under ultrasonic wave；
Step 2 and then progress calcination processing：First in air, 500 DEG C, 4h is calcined under 0.2kpa, then in nitrogen, 600 DEG C,
3h is calcined under 0.4kpa；
Step 3, calcining carry out helium-atmosphere after terminating and enclose lower purging 3h；
Step 4 and then use infusion process introduce cesium element：By 10g aluminum oxide, 5g titanium dioxide in mass ratio 2:1 mixing, so
12h in 0.5mol/L Cs2CO3 solution is immersed in afterwards；
Step 5 and then using hot alkali treatment, 2h is handled under 180 DEG C of hot-airs, is then immersed in 5% sodium hydroxide solution
In handle 5h, be then transferred into beaker；
Step 6, carry out coupling processing：0.05mol coupling agents kh500 is added drop-wise in the mixture after hot alkali treatment, side is added dropwise
Side magnetic agitation；
Step 7,0.05mol surfactant diglycollic amides are added drop-wise in the mixture after coupling processing, the magnetic when being added dropwise
Power stirs, and is then carrying out microwave treatment；
After step 8, microwave treatment terminate, first in 110 DEG C of dry 12h of thermostatic drying chamber, then calcination processing is carried out in tube furnace：
It is 1 first in nitrogen and ammonia volume ratio:3 mixing, 650 DEG C, 4h is calcined under 0.3kpa, then in nitrogen, 700 DEG C, 0.6kpa
Lower calcining 5h, finally give the nanoscale Ti/Al complex solid base catalysts of caesium modification.
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