CN103951565B - The synthesis of three core quaternary ammonium salt. template agent and the preparation and application of molecular sieve solid acid - Google Patents
The synthesis of three core quaternary ammonium salt. template agent and the preparation and application of molecular sieve solid acid Download PDFInfo
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Abstract
The present invention relates to the synthesis of Novel trinuclear aromatic ring quaternary ammonium salt. template agent SDA III, the preparation of novel HZSM 5 molecular sieve and this molecular sieve are through the modified catalytic performance research in ethylene glycol with Ketohexamethylene condensation reaction of chlorosulfonic acid.Being mainly characterized by of this novel molecular sieve be catalyzed activity height, good stability, reuse often, catalyst convenient separation, post processing simply, pollute little, it is a kind of efficient environment protection solid acid, is expected to exploitation for green catalyst general in laboratory and commercial production.
Description
Technical field
The present invention relates to the preparation and modified through chlorosulfonic acid of new green environment protection catalyst HZSM-5 molecular sieve solid acid, the catalytic performance research in ethylene glycol with Ketohexamethylene condensation reaction.
Background technology
ZSM-5 series high silica alumina ratio zeolite molecular sieve has special pore passage structure and catalytic performance, excellent heat stability and acid resistance, fabulous hydrophobicity and steam stability, thus is paid much attention to by domestic and international petrochemical industry circle.ZSM-5 molecular sieve can be applicable to alkane aromatization, alkylating aromatic hydrocarbon, the very important chemical process such as toluene disproportionation, ZSM-5 molecular sieve prepared by the Novel trinuclear aromatic ring quarternary ammonium salt compound template of our synthesis is respond well in the ortho position of selective catalysis toluene or para-position methylation reaction.In order to expand the range of application of such catalyst, this catalyst has been also employed in acetal (ketone) synthetic reaction by we, uses inorganic acid catalyst (such as H to overcome in tradition acetal (ketone) synthetic reaction2SO4、HCl、H3PO4Deng) side reaction that shows is many, corrosivity is strong, post-reaction treatment is complicated, pollute the shortcomings such as environment.
In commercial production, the catalysis activity height of catalyst is necessary, if but catalyst can repeatedly use, that will be a significantly thing, it is possible not only to be greatly saved production cost, and environmental protection, the repeat performance investigating this molecular sieve the most further is very important.
Summary of the invention
It is an object of the invention to provide the preparation method of a kind of novel HZSM-5 molecular sieve solid acid, the catalysis activity of this solid acid is high, good stability, reuse often, convenient separation, post processing is simple, pollutes little, it is the environment protection solid acid of a kind of efficient green, it is possible to efficient catalytic ethylene glycol and Ketohexamethylene generation condensation reaction.
The present invention is accomplished in that
The synthesis of a.SDA III template
With xylol and N-bromo-succinimide as raw material; chloride is solvent; benzoyl peroxide is to be heated to reflux under initiator, inert gas shielding, and question response is complete; remove unreacted N-bromo-succinimide; decompression distilled removes reaction dissolvent, remains weak yellow liquid, freezing light yellow solid; use alcohols solvent recrystallization, obtain compound 1.
Compound 1 and diethylamine are dissolved in cyclic ether solvents, add catalytic amount K2CO3With 18 hats six, room temperature reaction 48 hours, sucking filtration, mother liquid obtained concentration, obtain compound 2.
Compound 2 and cylite are dissolved in dehydrated alcohol, add catalytic amount K2CO3With 18 hats six, 70 DEG C are refluxed 48 hours, and TLC monitoring reaction is complete, sucking filtration after cooling, by mother liquid obtained concentration, are subsequently adding little polar solvent, separate out white solid, and sucking filtration obtains template SDA III.
The preparation of b.HZSM-5 molecular sieve
SDA III is dissolved in distilled water, after stirring, is added slowly to dense H2SO4And Al2(SO4)3·18H2In the distilled water solution of O, stir and make A liquid.Modulus is in the waterglass addition distilled water of 3.2, stirs and makes B liquid.Under stirring condition, A liquid is added slowly in B liquid, adds continuation stirring 5min and be at room temperature aged 10min.Gained latex material liquid is put in stainless steel autoclave, airtight is warming up to 175 DEG C, and constant temperature stands crystallization 5 days.Crystallization is complete, takes out crystallization thing, and reduce pressure sucking filtration, uses distilled water wash filter cake.Filter cake high temperature is dried 2 hours, obtains Na type ZSM-5 zeolite molecular sieve.Na type ZSM-5 zeolite molecular sieve is placed in round-bottomed flask, adds NH4Cl aqueous solution, 90 DEG C of stirred in water bath 1 hour, reduce pressure sucking filtration, collects filter cake, repeats aforesaid operations 1 time.Exchanging complete, reduce pressure sucking filtration, and is washed till in filtrate without till Cl-with distilled water, and filter cake 110 DEG C dryings both had obtained HZSM-5 molecular sieve.
C. chlorosulfonic acid modified HZSM-5 molecular sieve
HZSM-5 molecular sieve is put in three-necked bottle, slowly drips chlorosulfonic acid, stirred for several hour, sucking filtration, and is washed with distilled water to PH=7, high temperature drying 2 hours.
D. the HZSM-5 molecular sieve catalytic condensation that chlorosulfonic acid is modified
In three-necked bottle, add the HZSM-5 molecular sieve that Ketohexamethylene, ethylene glycol, hexamethylene and chlorosulfonic acid are modified, return stirring 2 hours, terminate reaction, topple over gained reactant liquor and be purified process.In the reaction bulb of original catalyst, continuously add the same amount of reactant of above-mentioned reaction, repeat above-mentioned ketal reaction, investigate the repeat performance of this molecular sieve.
Preferably, the mol ratio of described step a xylol and N-bromo-succinimide is 1:1, and the chlorinated solvent of use is dichloromethane, chloroform, carbon tetrachloride, or the mixture of their different proportion.
Preferably, being heated to reflux under described step a inert gas shielding, the noble gas of use is nitrogen, argon, and the temperature being heated to reflux is 40～80 DEG C, and the time reacting complete is 4～5 hours.
Preferably, the alcohols solvent that described step a recrystallization uses is absolute methanol, dehydrated alcohol, or the mixture of their different proportion.
Preferably, the mol ratio of described step a compound 1 and diethylamine is 1:2.2 to 1:2.5.
Preferably, described step a cyclic ether solvents is oxolane, dioxane, the catalytic amount K of use2CO3, 18 hats six be the 1～5% of compound 1 mole, compound 2 is 1:2.2 to 1:2.5 with the mol ratio of cylite.
Preferably, it is ether, petroleum ether, expoxy propane, three fourth MEEs, diisopropyl ether, glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethyl acetate, butyl acetate, amyl acetate, dimethyl carbonate, or the mixture of their different proportion that described step a adds little polar solvent.
Preferably, described step b filter cake high temperature is dried and within 2 hours, is 110～120 DEG C, adds NH4Cl aqueous solution molar concentration is 1.0～2.0mol/L.
Preferably, described step c stirred for several hour is 4～6 hours, and high temperature drying 2 hours is 110～130 DEG C.
Preferably, described step d adds Ketohexamethylene in three-necked bottle, the mol ratio of ethylene glycol is 1:1.2, continues to repeat above-mentioned ketal reaction, and the repeat performance investigating this molecular sieve is to reuse 18 times, and catalysis activity only declines about 1%.
The present invention has the advantage that compared with other solid acid catalysis activity is high；Good stability；Reuse often；Convenient separation；Post processing is simple；Pollute little；It is the environment protection solid acid of a kind of efficient green, it is possible to efficient catalytic ethylene glycol and Ketohexamethylene generation condensation reaction.
Detailed description of the invention
In order to make the object, technical solutions and advantages of the present invention clearer, below the preferred embodiment of the present invention is described in detail.
Embodiment 1: the synthesis of Novel trinuclear quaternary ammonium salt. template agent and the preparation and application of molecular sieve solid acid
The synthesis of a.SDA III template
With 0.1mol (12.2mL) xylol and 0.1mol (17.6g) N-bromo-succinimide as raw material; 36mL chloride is solvent; 2.4g benzoyl peroxide is initiator; it is heated to reflux under inert gas shielding; react 4～5 hours; the N-bromo-succinimide that unreacted is complete is removed through sucking filtration; decompression distilled removes solvent; residue weak yellow liquid is freezing; obtain light yellow solid; use alcohols solvent recrystallization, obtain compound as white solid 1 (12.4g), yield 47%.
With 0.01mol (3g) compound 1 and appropriate diethylamine as raw material, the mol ratio of compound 1 and diethylamine is 1:2.2 to 1:2.5, is dissolved in cyclic ether solvents, adds catalytic amount (being equivalent to the amount 1～5%mol of compound 1 material) K2CO3With 18 hats six, room temperature reaction 48 hours, sucking filtration, mother liquid obtained concentrating under reduced pressure, obtain compound 2 (1.6g), yield 70%.
By 0.01mol (2.48g) compound 2 and appropriate cylite, being dissolved in 25mL anhydrous ethanol solvent, compound 2 is 1:2.2 to 1:2.5 with the mol ratio of cylite, adds catalytic amount (being equivalent to the amount 1～5%mol of compound 2 material) K2CO3, 18 hats six, 70 DEG C are heated to reflux 48 hours, and TLC monitoring reaction is completely, after cooling, sucking filtration removes potassium carbonate, by mother liquid obtained concentrating under reduced pressure, adds little polar solvent 30mL, separating out white solid, sucking filtration is removed solvent and is obtained template SDA III (3.4g), yield 67%.
The preparation of b.HZSM-5 molecular sieve
7.04mmol (1.15g) SDA III is dissolved in 5mL distilled water, stirs, be then added slowly to the dense H of 0.13mL2SO4Al with 0.08g2(SO4)3·18H2In O distilled water 5mL solution, stir and make A liquid.Modulus is the waterglass 5g of 3.2, adds in 30mL distilled water, stirs and make B liquid.In the case of stirring rapidly, the A liquid of 10mL is added slowly in the B liquid of 15mL, finishes continuation stirring 5min and be at room temperature aged 10min, latex material liquid is put in stainless steel autoclave, enclosed high pressure still, it is warming up to 175 DEG C, constant temperature stands crystallization 5 days.After crystallization, taking out crystallization thing, reduce pressure sucking filtration, uses distilled water wash filter cake.Filter cake high temperature (110～120 DEG C) is dried 2 hours, obtains Na type ZSM-5 zeolite molecular sieve 3.3g, productivity 86.6%.
Claim Na type ZSM-5 zeolite molecular sieve 2g to be placed in 100mL round-bottomed flask, add the NH of 40mL4Cl aqueous solution (1.0～2.0mol/L), 90 DEG C of stirred in water bath 1 hour, reduce pressure sucking filtration, collects filter cake, repeats aforesaid operations 1 time.After exchange, reduce pressure sucking filtration, and is washed till in filtrate without till Cl-with distilled water, and filter cake 110 DEG C dryings both had obtained HZSM-5 molecular sieve.
C. chlorosulfonic acid modified HZSM-5 molecular sieve
1g tri-core aromatic ring is called the HZSM-5 molecular sieve of template synthesis, put in 50mL three-necked bottle, slowly dropping 5mL chlorosulfonic acid, stirred for several hour (4～6h), sucking filtration is also washed with distilled water to PH=7, and high temperature (110～130 DEG C) is dried 2 hours.
D. the HZSM-5 molecular sieve catalytic condensation that chlorosulfonic acid is modified
In the 100mL three-necked bottle having stirring, condensing tube, water knockout drum, add the HZSM-5 molecular sieve 0.2g that 0.1mol Ketohexamethylene, 0.12mol ethylene glycol, 5mL hexamethylene and chlorosulfonic acid are modified, it is heated to reflux stirring reaction 2 hours, stopped reaction, topple over gained reactant liquor, organic facies extracts three times with a small amount of saturated aqueous common salt, then uses anhydrous Mg2SO4It is dried 0.5 hour, filters, by filtrate air-distillation, collect 168～174 DEG C of fractions, obtain 3.6g compound 3, productivity 73.6%.
In the reaction bulb of original catalyst, continuously add same amount of reactant during above-mentioned reaction, repeat above-mentioned ketal reaction, investigate the repeat performance of this molecular sieve.Experiment shows, with the HZSM-5 molecular sieve catalytic ketal reaction that the modified three core aromatic rings of chlorosulfonic acid are template synthesis, reusing 18 times, productivity stills remain in about 73% (column chromatography purification), catalysis activity is reduced only by about 1%, almost in experiment and yield error.
Finally illustrate is; above example is only in order to illustrate technical scheme and unrestricted; although by referring to the preferred embodiment of the present invention, invention has been described; but those skilled in the art is to be understood that; in form and details it can be made suitable modification; without departing from the spirit of the present invention that claims are limited, these retouchings also should be regarded as protection scope of the present invention.
Claims (12)
1. the synthetic method of a core quaternary ammonium salt. template agent, it is characterised in that concretely comprise the following steps:
With xylol and N-bromo-succinimide as raw material; chloride is solvent, and benzoyl peroxide is initiator, is heated to reflux; inert gas shielding; reacting complete, filter and remove unreacted N-bromo-succinimide, decompression is distilled off reaction dissolvent; residue weak yellow liquid is freezing; obtain light yellow solid, use alcohols solvent recrystallization, obtain compound 1;
By compound1It is dissolved in cyclic ether solvents with diethylamine, adds catalytic amount K2CO3, 18 hat six, room temperature reaction 48 hours, sucking filtration remove solid, by mother liquid obtained concentrating under reduced pressure, obtain compound
2;
By compound2It is dissolved in anhydrous ethanol solvent with cylite, adds catalytic amount K2CO3, 18 hat six, 70 DEG C
Being heated to reflux 48 hours, completely, after cooling, sucking filtration removes potassium carbonate in TLC monitoring reaction, by mother liquid obtained concentrating under reduced pressure, adds little polar solvent, separates out white solid, and sucking filtration is removed little polar solvent and obtained template SDA III.
2. the preparation method of a molecular sieve solid acid, it is characterised in that concretely comprise the following steps:
Template SDA III described in claim 1 is dissolved in distilled water, stirs, be then added slowly to dense H2SO4
With in the distilled water solution of aluminum sulfate octadecahydrate, stirring and make A liquid, modulus is
The waterglass of 3.2 adds in distilled water, stir and make B liquid, in the case of stirring rapidly, A liquid is added slowly in B liquid, finish continuation stirring 5 min and be at room temperature aged 10 min, the latex material liquid obtained is put in stainless steel autoclave, airtight it is warming up to 175 DEG C, constant temperature stands crystallization 5 days, after crystallization, take out crystallization thing, decompression sucking filtration, discard mother solution, use distilled water wash filter cake, filter cake high temperature is dried 2 hours, obtain Na type ZSM-5 zeolite molecular sieve, Na type ZSM-5 zeolite molecular sieve is placed in round-bottomed flask, add NH4Cl aqueous solution, 90 DEG C of stirred in water bath 1 hour, reduce pressure sucking filtration, discards mother solution, collects filter cake, repeats aforesaid operations 1 time, and after exchange, reduce pressure sucking filtration, and is washed till in filtrate without Cl with distilled water - Till, filter cake 110 DEG C drying, it is then placed in three-necked bottle, slowly drips chlorosulfonic acid, stirred for several hour, sucking filtration, and be washed with distilled water to
PH=7, high temperature drying 2 hours, obtain the HZSM-5 molecular sieve that chlorosulfonic acid is modified.
3. the application process of a molecular sieve solid acid, it is characterised in that concretely comprise the following steps:
The HZSM-5 molecular sieve that the chlorosulfonic acid described in Ketohexamethylene, ethylene glycol, hexamethylene and claim 2 is modified is added in three-necked bottle, it is heated to reflux stirring, react 2 hours, terminate reaction, topple over gained reactant liquor and be purified process, in the reaction bulb of original catalyst, continuously add same amount of reactant during above-mentioned reaction, repeat above-mentioned ketal reaction, investigate the repeat performance of this molecular sieve.
A kind of synthetic method of three core quaternary ammonium salt. template agent, the mol ratio that it is characterized in that xylol and N-bromo-succinimide is 1:1, the chlorinated solvent used is dichloromethane, chloroform, carbon tetrachloride, or the mixture of their different proportion.
The synthetic method of a kind of three core quaternary ammonium salt. template agent, it is characterised in that the temperature of heating reflux reaction is 40～80 DEG C, and the inert gas shielding of use is nitrogen, argon, and the time reacting complete is 4～5 hours.
The synthetic method of a kind of three core quaternary ammonium salt. template agent, it is characterised in that the alcohols solvent that recrystallization uses is absolute methanol, dehydrated alcohol, or the mixture of their different proportion.
The synthetic method of a kind of three core quaternary ammonium salt. template agent, it is characterised in that the mol ratio of compound 1 and diethylamine is 1:2.2 to 1:2.5.
The synthetic method of a kind of three core quaternary ammonium salt. template agent, it is characterised in that cyclic ether solvents is oxolane, dioxane, the catalytic amount K of use2CO3, 18 hats six be the 1～5% of compound 1 mole, compound 2 is 1:2.2 to 1:2.5 with the mol ratio of cylite.
A kind of synthetic method of three core quaternary ammonium salt. template agent, it is characterized in that adding little polar solvent is ether, petroleum ether, expoxy propane, three fourth MEEs, diisopropyl ether, glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethyl acetate, butyl acetate, amyl acetate, dimethyl carbonate, or the mixture of their different proportion.
The preparation method of a kind of molecular sieve solid the most as claimed in claim 2 acid, it is characterised in that filter cake high temperature is dried and 2 hours is 110～120 DEG C, adds NH4Cl aqueous solution, molar concentration is 1.0～2.0 mol/L.
The preparation method of 11. a kind of molecular sieve solid as claimed in claim 2 acid, it is characterised in that stirred for several hour is 4～6
Hour, high temperature drying 2 hours is 110～130 DEG C.
The application process of 12. a kind of molecular sieve solid as claimed in claim 3 acid, it is characterized in that adding Ketohexamethylene in three-necked bottle, the mol ratio of ethylene glycol is 1:1.2, continue to repeat above-mentioned ketal reaction, the repeat performance investigating this molecular sieve is to reuse 18 times, and catalysis activity only declines about 1%.
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