CN112209806A - Preparation method of ethyl benzyl chloride - Google Patents
Preparation method of ethyl benzyl chloride Download PDFInfo
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Abstract
The invention discloses a preparation method of ethyl benzyl chloride, which comprises the following steps: (1) adding ethylbenzene, hydrochloric acid, solid formaldehyde and liquid formaldehyde into a reaction kettle, fully stirring and mixing, adding a Lewis acid catalyst, introducing hydrogen chloride gas for reaction, simultaneously adding a small amount of modified molecular sieve water absorbent for multiple times, and preparing a crude product of ethyl benzyl chloride after the reaction is finished; (2) washing the crude product of ethyl benzyl chloride with water and alkali until the pH value is 4-8; (3) carrying out dehydration treatment; (4) adding polymerization inhibitor for rectification; (5) adding propylene oxide and a nitrogen protective agent into the rectification product; the modified molecular sieve water absorbent replaces the traditional strong acid water absorbent, overcomes the defect that the traditional strong acid water absorbent is easy to generate corrosion, does not additionally generate waste liquid, can be easily recycled, reduces the production cost, meets the green production requirement, and has the advantages of environmental protection and economy.
Description
Technical Field
The invention relates to the technical field of preparation of bactericidal corrosion inhibitor intermediates, in particular to a preparation method of ethylbenzyl chloride.
Background
If effective measures such as sterilization, disinfection, algae removal and the like are not adopted in industrial circulating water which is used in a large amount in industry, エ industrial pollution is easily caused, and a large amount of sterilization corrosion inhibitors are needed in the treatment of waste water of steel mills, the treatment of oilfield flooding water and the treatment of boilers, pipelines and cooling water. The bactericidal corrosion inhibitor produced by the intermediate ethyl benzyl chloride can be widely applied to the protection of pipelines in petroleum exploration and chemical raw material transportation, prevents the pipelines from being rusted and blocked by algae, ensures the smoothness of the pipelines, has low and unstable bactericidal efficiency and is not beneficial to long-term storage.
Patent number ZL011080965 discloses a production process of ethyl benzyl chloride, which is synthesized by ethylbenzene, formaldehyde and hydrogen chloride in the presence of a zinc chloride catalyst and a water absorbent, wherein the water absorbent is concentrated sulfuric acid, phosphorus trichloride or hydrogen chloride gas, and has strong acid corrosivity, which puts higher requirements on production equipment and safety production, and the water absorbent is difficult to recycle.
Disclosure of Invention
Aiming at the problems, the invention provides a preparation method of ethylbenzyl chloride.
The purpose of the invention is realized by adopting the following technical scheme:
a preparation method of ethylbenzyl chloride specifically comprises the following steps:
(1) adding ethylbenzene, hydrochloric acid, solid formaldehyde and liquid formaldehyde into a reaction kettle, fully stirring and mixing, adding a Lewis acid catalyst, heating to 55-95 ℃, gradually introducing hydrogen chloride gas under 0-0.4MPa for reaction, simultaneously adding a small amount of modified molecular sieve water absorbent for multiple times, reacting for 4-14h, and keeping the temperature and pressure for 4-14h after the reaction is finished to prepare a crude product of the ethyl benzyl chloride;
(2) washing the prepared crude product of ethyl benzyl chloride with water and alkali until the pH value is 4-8;
(3) dehydrating the washed crude product of the ethyl benzyl chloride;
(4) adding a polymerization inhibitor into the dehydrated ethyl benzyl chloride for rectification;
(5) adding propylene oxide and a nitrogen protective agent into the rectification product.
Preferably, the mass ratio of the ethylbenzene, the hydrochloric acid, the solid formaldehyde, the liquid formaldehyde, the Lewis acid catalyst, the hydrogen chloride gas and the modified molecular sieve water absorbent is 5 (5-7): 2-5): 1-12): 6-8): 5-12.
Preferably, the preparation method of the modified molecular sieve water absorbent comprises the following steps:
s1, weighing 3A type zeolite molecular sieve particles with the particle size within the range of 200-;
s2, heating the sealed yeast at 65-70 ℃ for 20min for inactivation, adding water for dilution, filtering impurities, standing and settling the filtrate, washing with 10-20% sodium chloride solution and deionized water respectively, dispersing in the deionized water according to the liquid-material ratio of 30ml/g, adding 1ml of tetraethoxysilane per g of yeast, adding 2mol/L hydrochloric acid solution with the same volume as the tetraethoxysilane, stirring and reacting for 1-2h under the water bath condition of 30-40 ℃, and filtering out precipitates to obtain a product B;
s3, weighing sodium silicate with the modulus of 2.5, 30% silica sol, sodium metaaluminate and sodium hydroxide, adding the sodium silicate, the silica sol, the sodium metaaluminate and the sodium hydroxide into deionized water, quickly stirring and mixing for 10min, sealing and standing for aging for 24h at room temperature, stirring again, dropwise adding a sulfuric acid solution with the concentration of 1-2mol/L, adjusting the pH value to 10-11, adding bacterial cellulose, a product A and a product B under the condition of quick stirring, stirring for 0.5-1h in a constant-temperature water bath at 60 ℃, transferring the mixed solution into a polytetrafluoroethylene lining high-pressure reaction kettle, preserving the temperature for 48-96h at 150 ℃ under the autogenous pressure, filtering out precipitates after cooling, washing with absolute ethyl alcohol and deionized water, drying for 12-24h in vacuum at 100 ℃, placing in a muffle furnace for roasting for 1-2h at 400 ℃ to obtain a product C;
wherein the mass ratio of the sodium silicate, the silica sol, the sodium metaaluminate, the sodium hydroxide, the deionized water, the bacterial cellulose, the product A and the product B is as follows: 1 (3.80-3.86), (3.90-4.02), (7.60-7.80), (44-45), (3.2-3.3), (19.5-19.8), (6.2-6.4);
s4, adding the product C into 1mol/L ammonium chloride solution, stirring for 10h under the condition of 80 ℃ water bath, filtering out precipitate, washing with deionized water, stirring for 2-3 times by repeating the water bath, and vacuum drying the precipitate for 24-48h at 100 ℃ to obtain the modified molecular sieve water absorbent.
Preferably, the Lewis acid catalyst is zinc chloride.
Preferably, the Lewis acid catalyst is sulfated alumina solid acid doped with zinc ions.
Preferably, the preparation method of the zinc ion doped sulfated titanium aluminum oxide solid acid comprises the following steps:
weighing aluminum nitrate nonahydrate and zinc nitrate hexahydrate, adding the aluminum nitrate nonahydrate and the zinc nitrate hexahydrate into an 80% ethanol water solution for dissolving, adding citric acid, polyethylene glycol-2000 and ammonium sulfate, fully stirring and dissolving to obtain a clear solution, continuously stirring at normal temperature for 10-20min to obtain a precursor solution, heating to 65-70 ℃, stirring and reacting for 3-5h to obtain a foamy gel, drying at 110 ℃ for 12h, grinding, roasting in a muffle furnace at 400 ℃ and 500 ℃ for 4-6h, adding 1mol/L ammonium chloride solution for dispersing, standing for 6-8h, filtering, and drying to obtain the zinc nitrate/aluminum nitrate/zinc sulfate/aluminum nitrate composite material;
wherein the mass ratio of the aluminum nitrate nonahydrate to the zinc nitrate hexahydrate to the ethanol aqueous solution to the citric acid to the polyethylene glycol-2000 to the ammonium sulfate is 1: 2: (200-300): (5-6): (1-2): (1-2).
Preferably, the polymerization inhibitor is hydroquinone.
Preferably, the polymerization inhibitor is a tertiary amine, and the three hydrocarbon groups connected with the tertiary amine are alkyl groups with 1-14 carbon atoms.
The invention has the beneficial effects that:
the modified molecular sieve water absorbent replaces the traditional strong acid water absorbent, overcomes the defect that the traditional strong acid water absorbent is easy to generate corrosion, and has the advantages of no extra generation of waste liquid, easy recovery and reutilization, reduced production cost, environmental protection and economy.
Detailed Description
The invention is further described with reference to the following examples.
The embodiment of the invention relates to a preparation method of ethylbenzyl chloride, which comprises the following steps:
(1) adding ethylbenzene, hydrochloric acid, solid formaldehyde and liquid formaldehyde into a reaction kettle, fully stirring and mixing, adding a Lewis acid catalyst, heating to 55-95 ℃, gradually introducing hydrogen chloride gas under 0-0.4MPa for reaction, simultaneously adding a small amount of modified molecular sieve water absorbent for multiple times, reacting for 4-14h, and keeping the temperature and pressure for 4-14h after the reaction is finished to prepare a crude product of the ethyl benzyl chloride;
(2) washing the prepared crude product of ethyl benzyl chloride with water and alkali until the pH value is 4-8;
(3) dehydrating the washed crude product of the ethyl benzyl chloride;
(4) adding a polymerization inhibitor into the dehydrated ethyl benzyl chloride for rectification;
(5) adding propylene oxide and a nitrogen protective agent into the rectification product.
The modified molecular sieve water absorbent is used for replacing the traditional strong acid water absorbent, the defect that the traditional strong acid water absorbent is easy to generate corrosion is overcome, compared with the defect that the traditional water absorbent is easy to generate a large amount of strong acid waste liquid, the modified molecular sieve water absorbent does not additionally generate waste liquid, can be easily recycled, reduces the production cost, meets the green production requirement, and has the advantages of environmental protection and economy;
the propylene oxide is added into the finished product, so that the protective effect can be achieved, the ethyl benzyl chloride is prevented from being decomposed and polymerized, and a certain amount of nitrogen is filled to isolate air, so that the product can be stored for a long time.
Preferably, the mass ratio of the ethylbenzene, the hydrochloric acid, the solid formaldehyde, the liquid formaldehyde, the Lewis acid catalyst, the hydrogen chloride gas and the modified molecular sieve water absorbent is 5 (5-7): 2-5): 1-12): 6-8): 5-12.
Preferably, the preparation method of the modified molecular sieve water absorbent comprises the following steps:
s1, weighing 3A type zeolite molecular sieve particles with the particle size within the range of 200-;
s2, heating the sealed yeast at 65-70 ℃ for 20min for inactivation, adding water for dilution, filtering impurities, standing and settling the filtrate, washing with 10-20% sodium chloride solution and deionized water respectively, dispersing in the deionized water according to the liquid-material ratio of 30ml/g, adding 1ml of tetraethoxysilane per g of yeast, adding 2mol/L hydrochloric acid solution with the same volume as the tetraethoxysilane, stirring and reacting for 1-2h under the water bath condition of 30-40 ℃, and filtering out precipitates to obtain a product B;
s3, weighing sodium silicate with the modulus of 2.5, 30% silica sol, sodium metaaluminate and sodium hydroxide, adding the sodium silicate, the silica sol, the sodium metaaluminate and the sodium hydroxide into deionized water, quickly stirring and mixing for 10min, sealing and standing for aging for 24h at room temperature, stirring again, dropwise adding a sulfuric acid solution with the concentration of 1-2mol/L, adjusting the pH value to 10-11, adding bacterial cellulose, a product A and a product B under the condition of quick stirring, stirring for 0.5-1h in a constant-temperature water bath at 60 ℃, transferring the mixed solution into a polytetrafluoroethylene lining high-pressure reaction kettle, preserving the temperature for 48-96h at 150 ℃ under the autogenous pressure, filtering out precipitates after cooling, washing with absolute ethyl alcohol and deionized water, drying for 12-24h in vacuum at 100 ℃, placing in a muffle furnace for roasting for 1-2h at 400 ℃ to obtain a product C;
wherein the mass ratio of the sodium silicate, the silica sol, the sodium metaaluminate, the sodium hydroxide, the deionized water, the bacterial cellulose, the product A and the product B is as follows: 1 (3.80-3.86), (3.90-4.02), (7.60-7.80), (44-45), (3.2-3.3), (19.5-19.8), (6.2-6.4);
s4, adding the product C into 1mol/L ammonium chloride solution, stirring for 10h under the condition of 80 ℃ water bath, filtering out precipitate, washing with deionized water, stirring for 2-3 times by repeating the water bath, and vacuum drying the precipitate for 24-48h at 100 ℃ to obtain the modified molecular sieve water absorbent.
The 3A type molecular sieve has proper pore size, only allows water molecules to enter, is usually used as a drying agent in the prior art, but has weaker hydrophilicity and limited water absorption capacity, and takes the 3A type molecular sieve as a core to construct a porous hydrophilic zeolite framework shell layer outside the molecular sieve so as to improve the water absorption capacity of the molecular sieve; silicified saccharomycetes and bacterial cellulose are used as pore forming agents and are removed through high-temperature roasting, hydrophilic continuous microporous channels are provided for the shell layer, the hydrophilicity and the water holding capacity of the surface of the molecular sieve are greatly improved, and the water absorption capacity is improved.
Preferably, the Lewis acid catalyst is zinc chloride.
Preferably, the Lewis acid catalyst is sulfated alumina solid acid doped with zinc ions.
Preferably, the preparation method of the zinc ion doped sulfated titanium aluminum oxide solid acid comprises the following steps:
weighing aluminum nitrate nonahydrate and zinc nitrate hexahydrate, adding the aluminum nitrate nonahydrate and the zinc nitrate hexahydrate into an 80% ethanol water solution for dissolving, adding citric acid, polyethylene glycol-2000 and ammonium sulfate, fully stirring and dissolving to obtain a clear solution, continuously stirring at normal temperature for 10-20min to obtain a precursor solution, heating to 65-70 ℃, stirring and reacting for 3-5h to obtain a foamy gel, drying at 110 ℃ for 12h, grinding, roasting in a muffle furnace at 400 ℃ and 500 ℃ for 4-6h, adding 1mol/L ammonium chloride solution for dispersing, standing for 6-8h, filtering, and drying to obtain the zinc nitrate/aluminum nitrate/zinc sulfate/aluminum nitrate composite material;
wherein the mass ratio of the aluminum nitrate nonahydrate to the zinc nitrate hexahydrate to the ethanol aqueous solution to the citric acid to the polyethylene glycol-2000 to the ammonium sulfate is 1: 2: (200-300): (5-6): (1-2): (1-2).
The invention is characterized in that zinc element is doped on the basis of sulfated titanium aluminum oxide solid acid, on one hand, Lewis acid active sites can be provided for the solid acid, so that the solid acid has Lewis acid and Brewster acid sites at the same time, and the two active sites have synergistic effect to improve the catalytic activity of the solid acid, on the other hand, the zinc doping slows down the loss of active sulfur on the surface of the solid acid, and can improve the repeated use efficiency of the solid acid.
Preferably, the polymerization inhibitor is hydroquinone.
Preferably, the polymerization inhibitor is a tertiary amine, and the three hydrocarbon groups connected with the tertiary amine are alkyl groups with 1-14 carbon atoms.
After hydroquinone or tertiary amine is added, the polymerization reaction of the crude product caused by high temperature in the rectification process can be prevented.
As another embodiment of the invention, the yeast is zinc-rich yeast, and the bacterial cellulose is zinc-loaded bacterial cellulose;
the preparation method of the zinc-loaded bacterial cellulose comprises the following steps:
weighing zinc acetate dihydrate, dissolving the zinc acetate dihydrate in absolute ethyl alcohol to prepare a solution with the concentration of 2g/L, dropwise adding (4mL/min) a sodium hydroxide ethanol solution with the concentration of 1.5g/L under the condition of rapid stirring, wherein the volume ratio of the zinc acetate solution to the sodium hydroxide solution is 8:1, continuously stirring and reacting for 30min after dropwise adding is finished, centrifugally separating and precipitating, washing the absolute ethyl alcohol, redispersing the solution in a 10% gamma-aminopropyltriethoxysilane ethanol solution, adding deionized water with the volume of 3% of the solution, rapidly stirring for 30min, centrifugally separating and precipitating, washing the absolute ethyl alcohol to obtain zinc oxide, and preparing the deionized water into a zinc oxide solution with the mass concentration of 0.1%; and (3) fully absorbing water and swelling the bacterial cellulose, extruding to remove water, soaking into the zinc oxide solution, and carrying out adsorption balance to obtain the zinc oxide.
The zinc-rich yeast is characterized in that zinc element is added in the process of culturing yeast, and the zinc element is absorbed and transformed in the growth process of the yeast, so that the zinc is organically combined with protein and polysaccharide in the yeast body;
based on the technical scheme, the modified molecular sieve water absorbent and the solid acid catalyst can be recycled, but the service lives of the modified molecular sieve water absorbent and the solid acid catalyst are different, and the modified molecular sieve water absorbent and the solid acid catalyst need to be recycled respectively, so that the process requirement is increased.
Example 1
A preparation method of ethylbenzyl chloride comprises the following steps:
(1) adding ethylbenzene, hydrochloric acid, solid formaldehyde and liquid formaldehyde into a reaction kettle, fully stirring and mixing, adding zinc chloride, heating to 55-95 ℃, gradually introducing hydrogen chloride gas under 0-0.4MPa for reaction, simultaneously adding a small amount of modified molecular sieve water absorbent for multiple times, reacting for 4-14h, and preserving heat and pressure for 4-14h after the reaction is finished to obtain a crude product of ethyl benzyl chloride;
(2) washing the prepared crude product of ethyl benzyl chloride with water and alkali until the pH value is 4-8;
(3) dehydrating the washed crude product of the ethyl benzyl chloride;
(4) adding hydroquinone into the dehydrated ethyl benzyl chloride for rectification;
(5) adding propylene oxide and a nitrogen protective agent into the rectification product;
the mass ratio of the ethylbenzene, the hydrochloric acid, the solid formaldehyde, the liquid formaldehyde, the zinc chloride, the hydrogen chloride gas and the modified molecular sieve water absorbent is 5: 6: 3.5: 2: 5: 7: 9;
the preparation method of the modified molecular sieve water absorbent comprises the following steps:
s1, weighing 3A type zeolite molecular sieve particles with the particle size within the range of 200-;
s2, heating the sealed yeast at 65-70 ℃ for 20min for inactivation, adding water for dilution, filtering impurities, standing and settling the filtrate, washing with 10-20% sodium chloride solution and deionized water respectively, dispersing in the deionized water according to the liquid-material ratio of 30ml/g, adding 1ml of tetraethoxysilane per g of yeast, adding 2mol/L hydrochloric acid solution with the same volume as the tetraethoxysilane, stirring and reacting for 1-2h under the water bath condition of 30-40 ℃, and filtering out precipitates to obtain a product B;
s3, weighing sodium silicate with the modulus of 2.5, 30% silica sol, sodium metaaluminate and sodium hydroxide, adding the sodium silicate, the silica sol, the sodium metaaluminate and the sodium hydroxide into deionized water, quickly stirring and mixing for 10min, sealing and standing for aging for 24h at room temperature, stirring again, dropwise adding a sulfuric acid solution with the concentration of 1-2mol/L, adjusting the pH value to 10-11, adding bacterial cellulose, a product A and a product B under the condition of quick stirring, stirring for 0.5-1h in a constant-temperature water bath at 60 ℃, transferring the mixed solution into a polytetrafluoroethylene lining high-pressure reaction kettle, preserving the temperature for 48-96h at 150 ℃ under the autogenous pressure, filtering out precipitates after cooling, washing with absolute ethyl alcohol and deionized water, drying for 12-24h in vacuum at 100 ℃, placing in a muffle furnace for roasting for 1-2h at 400 ℃ to obtain a product C;
wherein the mass ratio of the sodium silicate, the silica sol, the sodium metaaluminate, the sodium hydroxide, the deionized water, the bacterial cellulose, the product A and the product B is 1: 3.82: 3.93: 7.68: 45: 3.2: 19.6: 6.3;
s4, adding the product C into 1mol/L ammonium chloride solution, stirring for 10h under the condition of 80 ℃ water bath, filtering out precipitate, washing with deionized water, stirring for 2-3 times by repeating the water bath, and vacuum drying the precipitate for 48h at 100 ℃ to obtain the modified molecular sieve water absorbent.
Example 2
A preparation method of ethylbenzyl chloride comprises the following steps:
(1) adding ethylbenzene, hydrochloric acid, solid formaldehyde and liquid formaldehyde into a reaction kettle, fully stirring and mixing, adding a Lewis acid catalyst, heating to 55-95 ℃, gradually introducing hydrogen chloride gas under 0-0.4MPa for reaction, simultaneously adding a small amount of modified molecular sieve water absorbent for multiple times, reacting for 4-14h, and keeping the temperature and pressure for 4-14h after the reaction is finished to prepare a crude product of the ethyl benzyl chloride;
(2) washing the prepared crude product of ethyl benzyl chloride with water and alkali until the pH value is 4-8;
(3) dehydrating the washed crude product of the ethyl benzyl chloride;
(4) adding N-235 into the dehydrated ethyl benzyl chloride for rectification;
(5) adding propylene oxide and a nitrogen protective agent into the rectification product;
the mass ratio of the ethylbenzene, the hydrochloric acid, the solid formaldehyde, the liquid formaldehyde, the Lewis acid catalyst, the hydrogen chloride gas and the modified molecular sieve water absorbent is 5: 6: 3.5: 2: 5: 7: 9;
the Lewis acid catalyst is sulfated alumina solid acid doped with zinc ions;
the preparation method of the modified molecular sieve water absorbent comprises the following steps:
s1, weighing 3A type zeolite molecular sieve particles with the particle size within the range of 200-;
s2, heating the sealed yeast at 65-70 ℃ for 20min for inactivation, adding water for dilution, filtering impurities, standing and settling the filtrate, washing with 10-20% sodium chloride solution and deionized water respectively, dispersing in the deionized water according to the liquid-material ratio of 30ml/g, adding 1ml of tetraethoxysilane per g of yeast, adding 2mol/L hydrochloric acid solution with the same volume as the tetraethoxysilane, stirring and reacting for 1-2h under the water bath condition of 30-40 ℃, and filtering out precipitates to obtain a product B;
s3, weighing sodium silicate with the modulus of 2.5, 30% silica sol, sodium metaaluminate and sodium hydroxide, adding the sodium silicate, the silica sol, the sodium metaaluminate and the sodium hydroxide into deionized water, quickly stirring and mixing for 10min, sealing and standing for aging for 24h at room temperature, stirring again, dropwise adding a sulfuric acid solution with the concentration of 1-2mol/L, adjusting the pH value to 10-11, adding bacterial cellulose, a product A and a product B under the condition of quick stirring, stirring for 0.5-1h in a constant-temperature water bath at 60 ℃, transferring the mixed solution into a polytetrafluoroethylene lining high-pressure reaction kettle, preserving the temperature for 48-96h at 150 ℃ under the autogenous pressure, filtering out precipitates after cooling, washing with absolute ethyl alcohol and deionized water, drying for 12-24h in vacuum at 100 ℃, placing in a muffle furnace for roasting for 1-2h at 400 ℃ to obtain a product C;
wherein the mass ratio of the sodium silicate, the silica sol, the sodium metaaluminate, the sodium hydroxide, the deionized water, the bacterial cellulose, the product A and the product B is 1: 3.82: 3.93: 7.68: 45: 3.2: 19.6: 6.3;
s4, adding the product C into 1mol/L ammonium chloride solution, stirring for 10h under the condition of 80 ℃ water bath, filtering out precipitate, washing with deionized water, stirring for 2-3 times by repeating the water bath, and vacuum drying the precipitate for 24-48h at 100 ℃ to obtain the modified molecular sieve water absorbent, wherein the liquid-material ratio is 5 ml/g;
the preparation method of the zinc ion doped sulfated titanium aluminum oxide solid acid comprises the following steps:
weighing aluminum nitrate nonahydrate and zinc nitrate hexahydrate, adding the aluminum nitrate nonahydrate and the zinc nitrate hexahydrate into an 80% ethanol water solution for dissolving, adding citric acid, polyethylene glycol-2000 and ammonium sulfate, fully stirring and dissolving to obtain a clear solution, continuously stirring at normal temperature for 10-20min to obtain a precursor solution, heating to 65-70 ℃, stirring and reacting for 3-5h to obtain a foamy gel, drying at 110 ℃ for 12h, grinding, roasting in a muffle furnace at 400 ℃ and 500 ℃ for 4-6h, adding 1mol/L ammonium chloride solution for dispersing, standing for 6-8h, filtering, and drying to obtain the zinc nitrate/aluminum nitrate/zinc sulfate/aluminum nitrate composite material;
wherein the mass ratio of the aluminum nitrate nonahydrate to the zinc nitrate hexahydrate to the ethanol aqueous solution to the citric acid to the polyethylene glycol-2000 to the ammonium sulfate is 1: 2: 230: 5: 1.2: 1.2.
the zinc ion doped sulfated titanium oxide aluminum solid acid prepared in the embodiment has better reuse efficiency, can be reused for 6-8 times, and can be reused for 2-3 times compared with the undoped sulfated titanium oxide aluminum solid acid.
Example 3
A preparation method of ethylbenzyl chloride comprises the following steps:
(1) adding ethylbenzene, hydrochloric acid, solid formaldehyde and liquid formaldehyde into a reaction kettle, fully stirring and mixing, adding zinc chloride, heating to 55-95 ℃, gradually introducing hydrogen chloride gas under 0-0.4MPa for reaction, simultaneously adding a small amount of modified molecular sieve water absorbent for multiple times, reacting for 4-14h, and preserving heat and pressure for 4-14h after the reaction is finished to obtain a crude product of ethyl benzyl chloride;
(2) washing the prepared crude product of ethyl benzyl chloride with water and alkali until the pH value is 4-8;
(3) dehydrating the washed crude product of the ethyl benzyl chloride;
(4) adding hydroquinone into the dehydrated ethyl benzyl chloride for rectification;
(5) adding propylene oxide and a nitrogen protective agent into the rectification product;
the mass ratio of the ethylbenzene, the hydrochloric acid, the solid formaldehyde, the liquid formaldehyde, the zinc chloride, the hydrogen chloride gas and the modified molecular sieve water absorbent is 5: 6: 3.5: 2: 5: 7: 9;
the preparation method of the modified molecular sieve water absorbent comprises the following steps:
s1, weighing 3A type zeolite molecular sieve particles with the particle size within the range of 200-;
s2, sealing the zinc-rich yeast, heating at 65-70 ℃ for 20min for inactivation, adding water for dilution, filtering out impurities, standing and settling the filtrate, washing with 10-20% sodium chloride solution and deionized water respectively, dispersing in the deionized water according to the liquid-material ratio of 30ml/g, adding 1ml of tetraethoxysilane per g of yeast, adding 2mol/L hydrochloric acid solution with the same volume as the tetraethoxysilane, stirring and reacting for 1-2h under the water bath condition of 30-40 ℃, and filtering out precipitates to obtain a product B;
s3, weighing sodium silicate with the modulus of 2.5, 30% silica sol, sodium metaaluminate and sodium hydroxide, adding the sodium silicate, the silica sol, the sodium metaaluminate and the sodium hydroxide into deionized water, quickly stirring and mixing for 10min, sealing and standing for aging for 24h at room temperature, stirring again, dropwise adding a sulfuric acid solution with the concentration of 1-2mol/L, adjusting the pH value to 10-11, adding zinc-loaded bacterial cellulose, a product A and a product B under the condition of quick stirring, stirring for 0.5-1h in a constant-temperature water bath at 60 ℃, transferring the mixed solution into a polytetrafluoroethylene lining high-pressure reaction kettle, preserving the temperature for 48-96h at 150 ℃ under autogenous pressure, cooling, filtering out precipitates, washing with absolute ethyl alcohol and deionized water, drying for 12-24h under the vacuum condition of 100 ℃, placing in a muffle furnace for roasting for 1-2h at the temperature of 400 ℃ to prepare a product C;
wherein the mass ratio of the sodium silicate, the silica sol, the sodium metaaluminate, the sodium hydroxide, the deionized water, the bacterial cellulose, the product A and the product B is 1: 3.82: 3.93: 7.68: 45: 3.2: 19.6: 6.3;
s4, adding the product C into 1mol/L ammonium chloride solution, stirring for 10h under the condition of 80 ℃ water bath, filtering out precipitate, washing with deionized water, stirring for 2-3 times by repeating the water bath, and vacuum drying the precipitate for 48h at 100 ℃ to obtain the modified molecular sieve water absorbent, wherein the liquid-material ratio is 5 ml/g;
the preparation method of the zinc-loaded bacterial cellulose comprises the following steps:
weighing zinc acetate dihydrate, dissolving the zinc acetate dihydrate in absolute ethyl alcohol to prepare a solution with the concentration of 2g/L, dropwise adding (4mL/min) a sodium hydroxide ethanol solution with the concentration of 1.5g/L under the condition of rapid stirring, wherein the volume ratio of the zinc acetate solution to the sodium hydroxide solution is 8:1, continuously stirring and reacting for 30min after dropwise adding is finished, centrifugally separating and precipitating, washing the absolute ethyl alcohol, redispersing the solution in a 10% gamma-aminopropyltriethoxysilane ethanol solution, adding deionized water with the volume of 3% of the solution, rapidly stirring for 30min, centrifugally separating and precipitating, washing the absolute ethyl alcohol to obtain zinc oxide, and preparing the deionized water into a zinc oxide solution with the mass concentration of 0.1%; and (3) fully absorbing water and swelling the bacterial cellulose, extruding to remove water, soaking into the zinc oxide solution, and carrying out adsorption balance to obtain the zinc oxide.
Performance detection
The modified molecular sieve water absorbents prepared in examples 1 and 3 were subjected to a water absorption performance test using 3A type zeolite molecular sieve fine particles as a control, and the results were as follows:
| control | Example 1 | Example 3 | |
| Water absorption/%) | 18％ | 22％ | 21％ |
| Equilibrium water absorption time/min | 1875 | 426 | 471 |
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention, and not for limiting the protection scope of the present invention, although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (8)
1. The preparation method of the ethyl benzyl chloride is characterized by comprising the following steps:
(1) adding ethylbenzene, hydrochloric acid, solid formaldehyde and liquid formaldehyde into a reaction kettle, fully stirring and mixing, adding a Lewis acid catalyst, heating to 55-95 ℃, gradually introducing hydrogen chloride gas under 0-0.4MPa for reaction, simultaneously adding a small amount of modified molecular sieve water absorbent for multiple times, reacting for 4-14h, and keeping the temperature and pressure for 4-14h after the reaction is finished to prepare a crude product of the ethyl benzyl chloride;
(2) washing the prepared crude product of ethyl benzyl chloride with water and alkali until the pH value is 4-8;
(3) dehydrating the washed crude product of the ethyl benzyl chloride;
(4) adding a polymerization inhibitor into the dehydrated ethyl benzyl chloride for rectification;
(5) adding propylene oxide and a nitrogen protective agent into the rectification product.
2. The method for preparing ethylbenzyl chloride as claimed in claim 1, wherein the mass ratio of ethylbenzene, hydrochloric acid, solid formaldehyde, liquid formaldehyde, Lewis acid catalyst, hydrogen chloride gas and modified molecular sieve water absorbent is 5 (5-7) to 2-5 to 1-12 to 6-8 to 5-12.
3. The method for preparing ethylbenzyl chloride according to claim 1, wherein the modified molecular sieve water absorbent is prepared by the following steps:
s1, weighing 3A type zeolite molecular sieve particles with the particle size within the range of 200-;
s2, heating the sealed yeast at 65-70 ℃ for 20min for inactivation, adding water for dilution, filtering impurities, standing and settling the filtrate, washing with 10-20% sodium chloride solution and deionized water respectively, dispersing in the deionized water according to the liquid-material ratio of 30ml/g, adding 1ml of tetraethoxysilane per g of yeast, adding 2mol/L hydrochloric acid solution with the same volume as the tetraethoxysilane, stirring and reacting for 1-2h under the water bath condition of 30-40 ℃, and filtering out precipitates to obtain a product B;
s3, weighing sodium silicate with the modulus of 2.5, 30% silica sol, sodium metaaluminate and sodium hydroxide, adding the sodium silicate, the silica sol, the sodium metaaluminate and the sodium hydroxide into deionized water, quickly stirring and mixing for 10min, sealing and standing for aging for 24h at room temperature, stirring again, dropwise adding a sulfuric acid solution with the concentration of 1-2mol/L, adjusting the pH value to 10-11, adding bacterial cellulose, a product A and a product B under the condition of quick stirring, stirring for 0.5-1h in a constant-temperature water bath at 60 ℃, transferring the mixed solution into a polytetrafluoroethylene lining high-pressure reaction kettle, preserving the temperature for 48-96h at 150 ℃ under the autogenous pressure, filtering out precipitates after cooling, washing with absolute ethyl alcohol and deionized water, drying for 12-24h in vacuum at 100 ℃, placing in a muffle furnace for roasting for 1-2h at 400 ℃ to obtain a product C;
wherein the mass ratio of the sodium silicate, the silica sol, the sodium metaaluminate, the sodium hydroxide, the deionized water, the bacterial cellulose, the product A and the product B is as follows: 1 (3.80-3.86), (3.90-4.02), (7.60-7.80), (44-45), (3.2-3.3), (19.5-19.8), (6.2-6.4);
s4, adding the product C into 1mol/L ammonium chloride solution, stirring for 10h under the condition of 80 ℃ water bath, filtering out precipitate, washing with deionized water, stirring for 2-3 times by repeating the water bath, and vacuum drying the precipitate for 24-48h at 100 ℃ to obtain the modified molecular sieve water absorbent.
4. The method for preparing ethylbenzyl chloride as claimed in claim 1, wherein the Lewis acid catalyst is zinc chloride.
5. The method for preparing ethylbenzyl chloride as claimed in claim 1, wherein the Lewis acid catalyst is sulfated alumina solid acid doped with zinc ion.
6. The method for preparing ethylbenzyl chloride, according to claim 5, wherein the preparation method of the zinc ion doped sulfated titanium aluminum oxide solid acid is as follows:
weighing aluminum nitrate nonahydrate and zinc nitrate hexahydrate, adding the aluminum nitrate nonahydrate and the zinc nitrate hexahydrate into an 80% ethanol water solution for dissolving, adding citric acid, polyethylene glycol-2000 and ammonium sulfate, fully stirring and dissolving to obtain a clear solution, continuously stirring at normal temperature for 10-20min to obtain a precursor solution, heating to 65-70 ℃, stirring and reacting for 3-5h to obtain a foamy gel, drying at 110 ℃ for 12h, grinding, roasting in a muffle furnace at 400 ℃ and 500 ℃ for 4-6h, adding 1mol/L ammonium chloride solution for dispersing, standing for 6-8h, filtering, and drying to obtain the zinc nitrate/aluminum nitrate/zinc sulfate/aluminum nitrate composite material;
wherein the mass ratio of the aluminum nitrate nonahydrate to the zinc nitrate hexahydrate to the ethanol aqueous solution to the citric acid to the polyethylene glycol-2000 to the ammonium sulfate is 1: 2: (200-300): (5-6): (1-2): (1-2).
7. The method according to claim 1, wherein the polymerization inhibitor is hydroquinone.
8. The method for preparing ethylbenzyl chloride as claimed in claim 1, wherein the polymerization inhibitor is a tertiary amine, and the three hydrocarbon groups connected with the tertiary amine are alkyl groups of 1 to 14 carbons.
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