CN112723641B - Comprehensive utilization method of modified-methyl tributyl ketoxime silane production wastewater - Google Patents
Comprehensive utilization method of modified-methyl tributyl ketoxime silane production wastewater Download PDFInfo
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Abstract
The invention relates to the field of chemical industry, and provides a method for comprehensively utilizing modified-methyl-tributyrinoxime silane production wastewater, wherein the wastewater contains a large amount of butanone oxime hydrochloride; the invention uses an extraction layering auxiliary agent in the extraction operation, and the auxiliary agent is an active demulsification auxiliary agent, can accelerate the layering of an extracting agent, increase the extraction efficiency, ensure that the recovery rate of the butanone oxime is higher, and ensure that the content of organic matters in wastewater summary is less. The byproduct butanone oxime can be used as a reaction raw material, ammonium chloride is a byproduct with economic value, the content of organic matters in the obtained wastewater is greatly reduced, the cost of oxidizing the wastewater is greatly reduced, the pressure of wastewater treatment is reduced, the cost is saved, and the economic benefit is increased.
Description
Technical Field
The invention relates to the field of chemical industry, in particular to a comprehensive utilization method of modified-methyl-tributyl ketoxime silane production wastewater.
Background
The modified-methyl tributyl ketoxime silane is a cross-linking agent with better reaction activity, which is prepared by reacting butanone oxime, methyl trichlorosilane and silicon tetrachloride mixed liquor, and wastewater containing butanone oxime generated in the production process cannot be directly discharged and needs to be subjected to harmless treatment.
CN111875090A discloses a wastewater treatment method, which comprises the following steps: (a) Primarily filtering the wastewater stock solution to intercept large solid particle impurities to obtain primary filtrate, introducing the primary filtrate into a membrane clarification unit to intercept solid suspended matters and macromolecular impurities to obtain membrane clarified filtrate; (b) Intercepting the membrane clarified filtrate by a membrane separation device to obtain membrane separation liquid, then sequentially intercepting most of inorganic salt by the membrane separation liquid through a concentration desalting device in a membrane concentration unit, further intercepting the inorganic salt by a fine desalting device to obtain clear liquid reaching the standard, returning the concentrated liquid intercepted by the fine desalting device to the concentration desalting device, wherein the operating pressure of the concentration desalting device is more than or equal to 2.5MPa, and the operating pressure of the fine desalting device is less than 2.5MPa. Therefore, the wastewater treatment method solves the problem that the membrane concentration desalination process cannot discharge liquid, and also solves the technical problem that the effluent water has overproof salt content and cannot be reused for production. The optimal comprehensive treatment cost is obtained, and the purposes of energy conservation and consumption reduction are achieved.
CN111065605A relates to a wastewater treatment method, which comprises the following steps: step a, reacting waste water with ilmenite; and a step b of removing the metal complex generated in the step a. The wastewater treatment method of the present invention can remove nitrogen and fluorine components in wastewater simultaneously with excellent treatment efficiency using ilmenite, and is simple in overall process and industrially useful, and thus can be applied to various industrial fields.
CN108558101A relates to a wastewater treatment method, which comprises the following steps: pretreating high-salinity wastewater; carrying out liquid-solid separation on the pretreated high-salinity wastewater; removing the separated solid impurities, and carrying out gasification treatment on the separated wastewater to form waste gas; mixing the waste gas with the heated air, and then sending the mixture into a waste gas treatment system for incineration to generate high-temperature tail gas; cooling the high-temperature tail gas to form a liquid substance and a gaseous substance, and then sequentially or simultaneously carrying out the following treatments on the liquid substance and the gaseous substance: performing membrane separation on the liquid substance, directly discharging membrane produced water which reaches the standard after separation, and returning the rest part which does not reach the standard to continue treatment; further cooling the gaseous substances, washing the gaseous substances by the spray liquid to form absorption liquid, separating by a membrane, directly discharging membrane produced water which reaches the standard after separation, and returning the rest parts which do not reach the standard to continue treatment. The wastewater treatment method can efficiently degrade organic matters and can efficiently desalt the organic matters at the same time.
The above patents and the prior art for treating the waste water containing organic wastes adopt oxidation technology to decompose and then treat the organic matters, but the direct oxidation treatment not only has high energy consumption and high cost, but also causes resource waste for the butanone oxime organic matters contained in the modified-methyl-tributyl ketoxime silane production waste water as the raw materials for reaction.
Disclosure of Invention
In order to solve the problems, the invention provides a comprehensive utilization method of modified-methyl-tributyl ketoxime silane production wastewater.
A comprehensive utilization method of modified-methyl tributyl ketoxime silane production wastewater comprises the following operation steps:
step one, performing neutralization reaction, namely introducing extraction liquid wastewater for producing modified-methyl tributyl ketoxime silane into a neutralization tower, adding ammonia gas into the neutralization tower, and performing neutralization reaction on butanone oxime hydrochloride contained in the wastewater to generate butanone oxime, ammonium chloride and water, wherein the flow rate of the extraction liquid wastewater is 1000-1500kg/h, and the flow rate of the ammonia gas is 5-50kg/h; the reaction time is 5-10min, and the reaction temperature is 20-80 ℃;
step two, extraction, namely adding the neutralized waste liquid into an extraction tower, and extracting the neutralized waste liquid by using an extracting agent, wherein 0.01-0.05% of an extraction layering auxiliary agent is added into the extracting agent;
step three, distillation, namely guiding the organic phase separated in the extraction tower into a rectifying tower, rectifying the butanone oxime product from the tower top, and recycling the rectified extractant, wherein the number of theoretical plates of the rectifying tower is 30-38, the reflux ratio is 0.28-0.35, and the load of a reboiler is 2500-3500KW;
step four, evaporation crystallization, namely introducing the water phase separated in the extraction tower into a distillation still, cooling to 20-30 ℃ after 20-50% of water is evaporated, crystallizing out, and filtering to obtain an ammonium chloride byproduct;
and step five, wastewater treatment, namely discharging the wastewater subjected to evaporation crystallization and filtration to a sewage treatment station for further treatment.
The extraction layering auxiliary is an active demulsification auxiliary, and the preparation method comprises the following steps:
according to the mass portion of the components,
1) Adding 0.1-0.5 part of initiator, 20-50 parts of pure water, 5-12 parts of tert-butylaminoethyl methacrylate, 8-12 parts of 3-acrylamide-2-hydroxypropyl trimethyl ammonium chloride, 1-4 parts of diethylene glycol divinyl ether, 0.01-0.03 part of 4-vinylpyridine-nickel and 0.1-0.5 part of precursor into a reaction kettle, controlling the temperature to be 60-80 ℃ under the protection of nitrogen, stirring for reaction for 3-6h, then adding 3-5 parts of copper acrylate, continuing the reaction for 2-4h, cooling to normal temperature, and then precipitating in ethanol to obtain a cationic polymer;
2) Adding 2.5-6.2 parts of the obtained cationic polymer into 50-60 parts of deionized water, controlling the temperature to 40-60 ℃, stirring and mixing uniformly, then adding 2.5-6.2 parts of polyethylene glycol, continuously stirring for 60-120min, then cooling to room temperature, adding 0.5-1.2 parts of pentanone and 0.05-0.2 part of calcium chloride into the solution, and continuously stirring for 30-60min to obtain the active demulsification aid.
The initiator is potassium persulfate or ammonium persulfate or benzoyl peroxide.
The precursor is methyl cellulose, ethyl cellulose or hydroxypropyl cellulose.
The active demulsification auxiliary agent is a branched cationic polymer with multiple active points obtained by the random copolymerization reaction of monomer substances containing double bonds and active groups, and then is combined with polyethylene glycol to form the active demulsification auxiliary agent, so that the extraction layering auxiliary agent can be further prepared. The branched structure enables the butanone oxime wastewater to have good branching and multi-site, and can also provide corresponding coagulation charges for the separation of the butanone oxime wastewater, thereby promoting the rapid demulsification.
The extraction tower is a Kuhni high-efficiency rotating disc extraction tower or a spray-type extraction tower or a pulse sieve plate tower.
The extracting agent is n-octanol or isooctanol.
The wastewater after evaporation, crystallization and filtration is treated in a sewage station by adopting biochemical treatment.
The invention provides a method for comprehensively utilizing production wastewater of modified-methyl-tributyroximo silane, which contains a large amount of butanone oxime hydrochloride, and by-products of butanone oxime and ammonium chloride solid are obtained after neutralization, extraction, rectification and evaporative crystallization; the invention uses an extraction layering aid in the extraction operation, and the aid is an active demulsification aid, can accelerate layering of an extracting agent, increase the extraction efficiency, improve the recovery rate of the butanone oxime and reduce the content of wastewater summarized organic matters. The byproduct butanone oxime can be used as a reaction raw material, ammonium chloride is a byproduct with economic value, the content of organic matters in the obtained wastewater is greatly reduced, the cost of oxidizing the wastewater is greatly reduced, the pressure of wastewater treatment is reduced, the cost is saved, and the economic benefit is increased.
Drawings
FIG. 1 is a Fourier infrared spectrum of the reactive demulsification aid product prepared in example 1:
at 2940cm -1 The absorption peak of the carbon-hydrogen bond is as high as 1658cm -1 The telescopic absorption peak of carbonyl of amide exists nearby and is 1286cm -1 An absorption peak of a carbon-nitrogen single bond exists nearby, which indicates that the 3-acrylamide-2-hydroxypropyl trimethyl ammonium chloride participates in the reaction; at 1729cm -1 The absorption peak of ester carbonyl group is in 1049cm -1 An absorption peak of ester carbon-oxygen single bond at 3317cm -1 A stretching absorption peak of a nitrogen-hydrogen bond exists nearby, which indicates that tert-butylaminoethyl methacrylate participates in the reaction; at 1175cm -1 An absorption peak of ether bond exists nearby, which indicates that the polyethylene glycol participates in the reaction; at 1457cm -1 A symmetric telescopic absorption peak of carboxylate ions exists nearby, which indicates that copper acrylate participates in the reaction; at 1586cm -1 An absorption peak of carbon-nitrogen double bonds exists nearby, so that the 4-vinylpyridine-nickel participates in the reaction; at 1600cm -1 And no obvious absorption peak exists nearby, which indicates that the carbon-carbon double bond is fully reacted.
Detailed Description
The invention is further illustrated by the following specific examples:
the COD value of the wastewater is measured by adopting a method for measuring the chemical oxygen demand of national standard GB 11914-89, and the higher the COD value is, the higher the butanone oxime content in the wastewater is.
Example 1
A comprehensive utilization method of modified-methyl tributyl ketoxime silane production wastewater comprises the following operation steps:
step one, performing neutralization reaction, namely introducing extract liquor wastewater for producing modified-methyl tributyl ketoxime silane into a neutralization tower, adding ammonia gas into the neutralization tower, and performing neutralization reaction on butanone oxime hydrochloride contained in the wastewater to generate butanone oxime, ammonium chloride and water, wherein the flow rate of the extract liquor wastewater is 1000kg/h, and the flow rate of the ammonia gas is 5kg/h; the reaction time is 5min, and the reaction temperature is 20 ℃;
step two, extraction, namely adding the neutralized waste liquid into an extraction tower, and extracting the neutralized waste liquid by using an extracting agent, wherein 0.01% of an extraction layering auxiliary agent is added into the extracting agent;
step three, distillation, namely guiding the organic phase separated in the extraction tower into a rectifying tower, rectifying a butanone oxime product from the tower top, and recycling the rectified extractant, wherein the number of theoretical plates of the rectifying tower is 30, the reflux ratio is 0.28, and the load of a reboiler is 2500KW;
step four, evaporation crystallization, namely introducing the water phase separated in the extraction tower into a distillation kettle, evaporating 20% of water, cooling to 20 ℃, crystallizing and separating out, and then filtering to obtain an ammonium chloride byproduct;
and step five, wastewater treatment, namely discharging the wastewater subjected to evaporation crystallization and filtration to a sewage treatment station for further treatment.
The extraction layering auxiliary is an active demulsification auxiliary, and the preparation method comprises the following steps:
1) Adding 0.1g of initiator, 20g of pure water, 5g of tert-butylaminoethyl methacrylate, 8g of 3-acrylamide-2-hydroxypropyl trimethyl ammonium chloride, 1g of diethylene glycol divinyl ether, 0.01g of 4-vinylpyridine-nickel and 0.1g of precursor into a reaction kettle, controlling the temperature to be 60 ℃ under the protection of nitrogen, stirring for reaction for 3 hours, then adding 3g of copper acrylate, continuing the reaction for 2 hours, cooling to normal temperature, and then precipitating in ethanol to obtain a cationic polymer;
2) Adding 2.5g of the obtained cationic polymer into 50g of deionized water, controlling the temperature to 40 ℃, stirring and mixing uniformly, then adding 2.5g of polyethylene glycol, continuously stirring for 60min, then cooling to room temperature, adding 0.5g of pentanone and 0.05g of calcium chloride into the solution, and continuously stirring for 30min to obtain the active demulsification aid.
The initiator is potassium persulfate.
The precursor is methyl cellulose.
The extraction tower is a Kuhni high-efficiency rotating disc extraction tower.
The extractant is n-octanol.
The wastewater after evaporation, crystallization and filtration is treated in a sewage station by biochemical treatment.
Example 2
A comprehensive utilization method of modified-methyl tributyl ketoxime silane production wastewater comprises the following operation steps:
step one, performing neutralization reaction, namely introducing extract liquor wastewater for producing modified-methyl tributyl ketoxime silane into a neutralization tower, adding ammonia gas into the neutralization tower, and performing neutralization reaction on butanone oxime hydrochloride contained in the wastewater to generate butanone oxime, ammonium chloride and water, wherein the flow rate of the extract liquor wastewater is 1300kg/h, and the flow rate of the ammonia gas is 20kg/h; the reaction time is 8min, and the reaction temperature is 50 ℃;
step two, extraction, namely adding the neutralized waste liquid into an extraction tower, and extracting the neutralized waste liquid by using an extracting agent, wherein 0.03% of an extraction layering auxiliary agent is added into the extracting agent;
step three, distillation, namely guiding the organic phase separated in the extraction tower into a rectifying tower, rectifying the butanone oxime product from the tower top, and recycling the rectified extractant, wherein the theoretical plate number of the rectifying tower is 34, the reflux ratio is 0.32, and the load of a reboiler is 3000KW;
step four, evaporation crystallization, namely introducing the water phase separated in the extraction tower into a distillation kettle, evaporating 35% of water, cooling to 25 ℃, crystallizing and separating out, and then filtering to obtain an ammonium chloride byproduct;
and step five, wastewater treatment, namely discharging the wastewater subjected to evaporation crystallization and filtration to a sewage treatment station for further treatment.
The extraction layering auxiliary is an active demulsification auxiliary, and the preparation method comprises the following steps:
1) Adding 0.5g of initiator, 12g of tert-butylaminoethyl methacrylate in 50g of pure water, 12g of 3-acrylamide-2-hydroxypropyl trimethyl ammonium chloride, 4g of diethylene glycol divinyl ether, 0.03g of 4-vinylpyridine-nickel and 0.5g of precursor into a reaction kettle, controlling the temperature to 80 ℃ under the protection of nitrogen, stirring for reaction for 6 hours, then adding 5g of copper acrylate, continuing the reaction for 4 hours, cooling to normal temperature, and then precipitating in ethanol to obtain a cationic polymer;
2) And adding 6.2g of the obtained cationic polymer into 60g of deionized water, controlling the temperature to 60 ℃, stirring and mixing uniformly, then adding 6.2g of polyethylene glycol, continuously stirring for 120min, then cooling to room temperature, adding 1.2g of pentanone and 0.2g of calcium chloride into the solution, and continuously stirring for 60min to obtain the active demulsification aid.
The initiator is ammonium persulfate.
The precursor is ethyl cellulose.
The extraction tower is a spray-type extraction tower.
The extractant is isooctyl alcohol.
The wastewater after evaporation, crystallization and filtration is treated in a sewage station by adopting biochemical treatment.
Example 3
A comprehensive utilization method of modified-methyl tributyl ketoxime silane production wastewater comprises the following operation steps:
step one, performing neutralization reaction, namely introducing extract liquor wastewater for producing modified-methyl tributyl ketoxime silane into a neutralization tower, adding ammonia gas into the neutralization tower, and performing neutralization reaction on butanone oxime hydrochloride contained in the wastewater to generate butanone oxime, ammonium chloride and water, wherein the flow rate of the extract liquor wastewater is 1500kg/h, and the flow rate of the ammonia gas is 50kg/h; the reaction time is 10min, and the reaction temperature is 80 ℃;
step two, extraction, namely adding the neutralized waste liquid into an extraction tower, and extracting the neutralized waste liquid by using an extracting agent, wherein 0.05% of an extraction layering aid is added into the extracting agent;
step three, distillation, namely guiding the organic phase separated in the extraction tower into a rectifying tower, rectifying a butanone oxime product from the tower top, and recycling the rectified extractant, wherein the number of theoretical plates of the rectifying tower is 38, the reflux ratio is 0.35, and the load of a reboiler is 3500KW;
step four, evaporation crystallization, namely introducing the water phase separated in the extraction tower into a distillation kettle, evaporating 50% of water, cooling to 30 ℃, crystallizing and separating out, and then filtering to obtain an ammonium chloride byproduct;
and step five, wastewater treatment, namely discharging the wastewater subjected to evaporation crystallization and filtration to a sewage treatment station for further treatment.
The extraction layering auxiliary is an active demulsification auxiliary, and the preparation method comprises the following steps:
1) Adding 0.3g of initiator, 35g of pure water, 8g of tert-butylaminoethyl methacrylate, 9g of 3-acrylamide-2-hydroxypropyl trimethyl ammonium chloride, 3g of diethylene glycol divinyl ether, 0.02g of 4-vinylpyridine-nickel and 0.3g of precursor into a reaction kettle, controlling the temperature to 75 ℃ under the protection of nitrogen, stirring for reaction for 4 hours, then adding 4g of copper acrylate, continuing the reaction for 3 hours, cooling to normal temperature, and then precipitating in ethanol to obtain a cationic polymer;
2) Adding the obtained 4.8g of cationic polymer into 55g of deionized water, controlling the temperature to 55 ℃, stirring and mixing uniformly, then adding 4.8g of polyethylene glycol, continuously stirring for 90min, then cooling to room temperature, adding 0.8g of pentanone and 0.1g of calcium chloride into the solution, and continuously stirring for 45min to obtain the active demulsification aid.
The initiator is benzoyl peroxide.
The precursor is hydroxypropyl cellulose.
The extraction tower is a pulse sieve plate tower.
The extractant is isooctanol.
The wastewater after evaporation, crystallization and filtration is treated in a sewage station by adopting biochemical treatment.
COD value test results of wastewater and recovery of D/kg wastewater from the above examplesThe amounts of ketoxime are shown in the table below:
| chemical oxygen demand (mg/L) | Butanone oxime recovery (g/kg) | |
| Untreated waste water | 4462 | -- |
| Example 1 | 138 | 36.2 |
| Example 2 | 86 | 38.1 |
| Example 3 | 75 | 39.2 |
Comparative example 1
A comprehensive utilization method of modified-methyl tributyl ketoxime silane production wastewater comprises the following operation steps:
step one, performing neutralization reaction, namely introducing extraction liquid wastewater for producing modified-methyl tributyl ketoxime silane into a neutralization tower, adding ammonia gas into the neutralization tower, and performing neutralization reaction on butanone oxime hydrochloride contained in the wastewater to generate butanone oxime, ammonium chloride and water, wherein the flow rate of the extraction liquid wastewater is 1000kg/h, and the flow rate of the ammonia gas is 5kg/h; the reaction time is 5min, and the reaction temperature is 20 ℃;
step two, extraction, namely adding the neutralized waste liquid into an extraction tower, and extracting the neutralized waste liquid by using an extracting agent;
step three, distillation, namely guiding the organic phase separated in the extraction tower into a rectifying tower, rectifying the butanone oxime product from the tower top, and recycling the rectified extractant, wherein the theoretical plate number of the rectifying tower is 30, the reflux ratio is 0.28, and the load of a reboiler is 2500KW;
step four, evaporation crystallization, namely introducing the water phase separated in the extraction tower into a distillation kettle, evaporating 20% of water, cooling to 20 ℃, crystallizing and separating out, and then filtering to obtain an ammonium chloride byproduct;
and step five, wastewater treatment, namely discharging the wastewater subjected to evaporation crystallization and filtration to a sewage treatment station for further treatment.
The extraction tower is a Kuhni high-efficiency rotating disc extraction tower.
The extractant is n-octanol.
The wastewater after evaporation, crystallization and filtration is treated in a sewage station by adopting biochemical treatment.
Comparative example 2
A comprehensive utilization method of modified-methyl tributyl ketoxime silane production wastewater comprises the following operation steps:
step one, performing neutralization reaction, namely introducing extraction liquid wastewater for producing modified-methyl tributyl ketoxime silane into a neutralization tower, adding ammonia gas into the neutralization tower, and performing neutralization reaction on butanone oxime hydrochloride contained in the wastewater to generate butanone oxime, ammonium chloride and water, wherein the flow rate of the extraction liquid wastewater is 1000kg/h, and the flow rate of the ammonia gas is 5kg/h; the reaction time is 5min, and the reaction temperature is 20 ℃;
step two, extraction, namely adding the neutralized waste liquid into an extraction tower, and extracting the neutralized waste liquid by using an extracting agent, wherein 0.01% of an extraction layering auxiliary agent is added into the extracting agent;
step three, distillation, namely guiding the organic phase separated in the extraction tower into a rectifying tower, rectifying the butanone oxime product from the tower top, and recycling the rectified extractant, wherein the theoretical plate number of the rectifying tower is 30, the reflux ratio is 0.28, and the load of a reboiler is 2500KW;
step four, evaporation crystallization, namely introducing the water phase separated in the extraction tower into a distillation kettle, evaporating 20% of water, cooling to 20 ℃, crystallizing and separating out, and then filtering to obtain an ammonium chloride byproduct;
and step five, wastewater treatment, namely discharging the wastewater subjected to evaporation crystallization and filtration to a sewage treatment station for further treatment.
The extraction layering auxiliary is an active demulsification auxiliary, and the preparation method comprises the following steps:
1) Adding 0.1g of initiator, 20g of pure water, 5g of tert-butylaminoethyl methacrylate, 8g of 3-acrylamide-2-hydroxypropyl trimethyl ammonium chloride, 1g of diethylene glycol divinyl ether, 0.01g of 4-vinylpyridine-nickel and 0.1g of precursor into a reaction kettle, controlling the temperature to be 60 ℃ under the protection of nitrogen, stirring for reaction for 3 hours, then adding 3g of copper acrylate, continuing the reaction for 2 hours, cooling to normal temperature, and then precipitating in ethanol to obtain a cationic polymer;
2) Adding the obtained 2.5g of cationic polymer into 50g of deionized water, controlling the temperature to 40 ℃, stirring and mixing uniformly, then cooling to room temperature, adding 0.5g of pentanone and 0.05g of calcium chloride into the solution, and continuously stirring for 30min to obtain the active demulsification aid.
The initiator is potassium persulfate.
The precursor is methyl cellulose.
The extraction tower is a Kuhni high-efficiency rotating disc extraction tower.
The extractant is n-octanol.
The wastewater after evaporation, crystallization and filtration is treated in a sewage station by adopting biochemical treatment.
Comparative example 3
A comprehensive utilization method of modified-methyl tributyl ketoxime silane production wastewater comprises the following operation steps:
step one, performing neutralization reaction, namely introducing extract liquor wastewater for producing modified-methyl tributyl ketoxime silane into a neutralization tower, adding ammonia gas into the neutralization tower, and performing neutralization reaction on butanone oxime hydrochloride contained in the wastewater to generate butanone oxime, ammonium chloride and water, wherein the flow rate of the extract liquor wastewater is 1000kg/h, and the flow rate of the ammonia gas is 5kg/h; the reaction time is 5min, and the reaction temperature is 20 ℃;
step two, extraction, namely adding the neutralized waste liquid into an extraction tower, and extracting the neutralized waste liquid by using an extracting agent, wherein 0.01% of an extraction layering aid is added into the extracting agent;
step three, distillation, namely guiding the organic phase separated in the extraction tower into a rectifying tower, rectifying the butanone oxime product from the tower top, and recycling the rectified extractant, wherein the theoretical plate number of the rectifying tower is 30, the reflux ratio is 0.28, and the load of a reboiler is 2500KW;
step four, evaporation crystallization, namely introducing the water phase separated in the extraction tower into a distillation kettle, evaporating 20% of water, cooling to 20 ℃, crystallizing and separating out, and then filtering to obtain an ammonium chloride byproduct;
and step five, wastewater treatment, namely discharging the wastewater subjected to evaporation crystallization and filtration to a sewage treatment station for further treatment.
The extraction layering auxiliary is an active demulsification auxiliary, and the preparation method comprises the following steps:
1) Adding 0.1g of initiator, 20g of pure water, 5g of tert-butylaminoethyl methacrylate, 8g of 3-acrylamide-2-hydroxypropyl trimethyl ammonium chloride, 1g of diethylene glycol divinyl ether, 0.01g of 4-vinylpyridine-nickel and 0.1g of precursor into a reaction kettle, controlling the temperature to be 60 ℃ under the protection of nitrogen, stirring for reaction for 3 hours, then adding 3g of copper acrylate, continuing the reaction for 2 hours, cooling to normal temperature, and then precipitating in ethanol to obtain a cationic polymer;
2) And adding 2.5g of the obtained cationic polymer into 50g of deionized water, controlling the temperature to 40 ℃, stirring and mixing uniformly, then adding 2.5g of polyethylene glycol, continuously stirring for 60min, then cooling to room temperature, and continuously stirring for 30min to obtain the active demulsification aid.
The initiator is potassium persulfate.
The precursor is methyl cellulose.
The extraction tower is a Kuhni high-efficiency rotating disc extraction tower.
The extractant is n-octanol.
The wastewater after evaporation, crystallization and filtration is treated in a sewage station by adopting biochemical treatment.
Comparative example 4
A comprehensive utilization method of modified-methyl tributyl ketoxime silane production wastewater comprises the following operation steps:
step one, performing neutralization reaction, namely introducing extract liquor wastewater for producing modified-methyl tributyl ketoxime silane into a neutralization tower, adding ammonia gas into the neutralization tower, and performing neutralization reaction on butanone oxime hydrochloride contained in the wastewater to generate butanone oxime, ammonium chloride and water, wherein the flow rate of the extract liquor wastewater is 1000kg/h, and the flow rate of the ammonia gas is 5kg/h; the reaction time is 5min, and the reaction temperature is 20 ℃;
step two, extraction, namely adding the neutralized waste liquid into an extraction tower, and extracting the neutralized waste liquid by using an extracting agent, wherein 0.01% of an extraction layering auxiliary agent is added into the extracting agent;
step three, distillation, namely guiding the organic phase separated in the extraction tower into a rectifying tower, rectifying the butanone oxime product from the tower top, and recycling the rectified extractant, wherein the theoretical plate number of the rectifying tower is 30, the reflux ratio is 0.28, and the load of a reboiler is 2500KW;
step four, evaporation crystallization, namely introducing the water phase separated in the extraction tower into a distillation kettle, evaporating 20% of water, cooling to 20 ℃, crystallizing and separating out, and then filtering to obtain an ammonium chloride byproduct;
and step five, wastewater treatment, namely discharging the wastewater subjected to evaporation crystallization and filtration to a sewage treatment station for further treatment.
The extraction layering auxiliary is an active demulsification auxiliary, and the preparation method comprises the following steps:
1) Adding 0.1g of initiator, 20g of pure water, 5g of tert-butylaminoethyl methacrylate, 8g of 3-acrylamide-2-hydroxypropyl trimethylammonium chloride, 0.01g of 4-vinylpyridine-nickel and 0.1g of precursor into a reaction kettle, controlling the temperature to 60 ℃ under the protection of nitrogen, stirring for reaction for 3 hours, then adding 3g of copper acrylate, continuing the reaction for 2 hours, cooling to normal temperature, and then precipitating in ethanol to obtain a cationic polymer;
2) Adding 2.5g of the obtained cationic polymer into 50g of deionized water, controlling the temperature to 40 ℃, stirring and mixing uniformly, then adding 2.5g of polyethylene glycol, continuously stirring for 60min, then cooling to room temperature, adding 0.5g of pentanone and 0.05g of calcium chloride into the solution, and continuously stirring for 30min to obtain the active demulsification aid.
The initiator is potassium persulfate.
The precursor is methyl cellulose.
The extraction tower is a Kuhni high-efficiency rotating disc extraction tower.
The extractant is n-octanol.
The wastewater after evaporation, crystallization and filtration is treated in a sewage station by biochemical treatment.
Comparative example 5
A comprehensive utilization method of modified-methyl tributyl ketoxime silane production wastewater comprises the following operation steps:
step one, performing neutralization reaction, namely introducing extract liquor wastewater for producing modified-methyl tributyl ketoxime silane into a neutralization tower, adding ammonia gas into the neutralization tower, and performing neutralization reaction on butanone oxime hydrochloride contained in the wastewater to generate butanone oxime, ammonium chloride and water, wherein the flow rate of the extract liquor wastewater is 1000kg/h, and the flow rate of the ammonia gas is 5kg/h; the reaction time is 5min, and the reaction temperature is 20 ℃;
step two, extraction, namely adding the neutralized waste liquid into an extraction tower, and extracting the neutralized waste liquid by using an extracting agent, wherein 0.01% of an extraction layering aid is added into the extracting agent;
step three, distillation, namely guiding the organic phase separated in the extraction tower into a rectifying tower, rectifying the butanone oxime product from the tower top, and recycling the rectified extractant, wherein the theoretical plate number of the rectifying tower is 30, the reflux ratio is 0.28, and the load of a reboiler is 2500KW;
step four, evaporation crystallization, namely introducing the water phase separated in the extraction tower into a distillation kettle, evaporating 20% of water, cooling to 20 ℃, crystallizing and separating out, and then filtering to obtain an ammonium chloride byproduct;
and step five, wastewater treatment, namely discharging the wastewater subjected to evaporation crystallization and filtration to a sewage treatment station for further treatment.
The extraction layering auxiliary is an active demulsification auxiliary, and the preparation method comprises the following steps:
1) Adding 0.1g of initiator, 20g of pure water, 5g of tert-butylaminoethyl methacrylate, 8g of 3-acrylamide-2-hydroxypropyl trimethyl ammonium chloride, 1g of diethylene glycol divinyl ether, 0.01g of 4-vinylpyridine-nickel and 0.1g of precursor into a reaction kettle, controlling the temperature to be 60 ℃ under the protection of nitrogen, stirring for reacting for 3 hours, and then precipitating in ethanol to obtain a cationic polymer;
2) Adding 2.5g of the obtained cationic polymer into 50g of deionized water, controlling the temperature to 40 ℃, stirring and mixing uniformly, then adding 2.5g of polyethylene glycol, continuously stirring for 60min, then cooling to room temperature, adding 0.5g of pentanone and 0.05g of calcium chloride into the solution, and continuously stirring for 30min to obtain the active demulsification aid.
The initiator is potassium persulfate.
The precursor is methyl cellulose.
The extraction tower is a Kuhni high-efficiency rotating disc extraction tower.
The extractant is n-octanol.
The wastewater after evaporation, crystallization and filtration is treated in a sewage station by biochemical treatment.
The COD values of the waste waters obtained in the above examples and the amounts of butanone oxime recovered per kg of waste water are shown in the following table:
Claims (6)
1. a comprehensive utilization method of modified-methyl tributyl ketoxime silane production wastewater comprises the following operation steps:
step one, neutralization reaction, namely introducing extract liquor wastewater for producing modified-methyl tributyl ketoxime silane into a neutralization tower, adding ammonia gas into the neutralization tower, and performing neutralization reaction on butanone oxime hydrochloride contained in the wastewater to generate butanone oxime, ammonium chloride and water, wherein the flow rate of the extract liquor wastewater is 1000-1500kg/h, and the flow rate of the ammonia gas is 5-50kg/h; the reaction time is 5-10min, and the reaction temperature is 20-80 ℃;
step two, extraction, namely adding the neutralized waste liquid into an extraction tower, and extracting the neutralized waste liquid by using an extracting agent, wherein 0.01-0.05% of an extraction layering auxiliary agent is added into the extracting agent;
step three, distillation, namely introducing the organic phase separated in the extraction tower into a rectifying tower, rectifying the butanone oxime product from the tower top, and recycling the rectified extractant, wherein the theoretical plate number of the rectifying tower is 30-38, the reflux ratio is 0.28-0.35, and the load of a reboiler is 2500-3500kW;
step four, evaporation crystallization, namely introducing the water phase separated in the extraction tower into a distillation kettle, evaporating 20-50% of water, cooling to 20-30 ℃, crystallizing and separating out, and then filtering to obtain an ammonium chloride byproduct;
step five, wastewater treatment, wherein the wastewater after evaporation, crystallization and filtration is discharged to a sewage treatment station for further treatment;
the extraction layering auxiliary is an active demulsification auxiliary, and the preparation method comprises the following steps:
according to the mass portion of the components,
1) Adding 0.1-0.5 part of initiator, 20-50 parts of pure water, 5-12 parts of tert-butylaminoethyl methacrylate, 8-12 parts of 3-acrylamide-2-hydroxypropyl trimethyl ammonium chloride, 1-4 parts of diethylene glycol divinyl ether, 0.01-0.03 part of 4-vinylpyridine-nickel and 0.1-0.5 part of precursor into a reaction kettle, controlling the temperature to be 60-80 ℃ under the protection of nitrogen, stirring for reaction for 3-6h, then adding 3-5 parts of copper acrylate, continuing the reaction for 2-4h, cooling to normal temperature, and then precipitating in ethanol to obtain a cationic polymer;
2) Adding 2.5-6.2 parts of the obtained cationic polymer into 50-60 parts of deionized water, controlling the temperature to 40-60 ℃, stirring and mixing uniformly, then adding 2.5-6.2 parts of polyethylene glycol, continuously stirring for 60-120min, then cooling to room temperature, adding 0.5-1.2 parts of pentanone and 0.05-0.2 part of calcium chloride into the solution, and continuously stirring for 30-60min to obtain the active demulsification aid.
2. The comprehensive utilization method of the modified-methyl tributanoximosilane production wastewater according to claim 1, characterized in that: the initiator is potassium persulfate or ammonium persulfate or benzoyl peroxide.
3. The comprehensive utilization method of the modified-methyl-tributyl ketoxime silane production wastewater according to claim 1, characterized in that: the precursor is methyl cellulose, ethyl cellulose or hydroxypropyl cellulose.
4. The comprehensive utilization method of the modified-methyl tributanoximosilane production wastewater according to claim 1, characterized in that: the extraction tower is a Kuhni high-efficiency turntable extraction tower or a spray-type extraction tower or a pulse sieve plate tower.
5. The comprehensive utilization method of the modified-methyl-tributyl ketoxime silane production wastewater according to claim 1, characterized in that: the extracting agent is n-octanol or isooctanol.
6. The comprehensive utilization method of the modified-methyl-tributyl ketoxime silane production wastewater according to claim 1, characterized in that: the wastewater after evaporation, crystallization and filtration is treated in a sewage station by adopting biochemical treatment.
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