CN110117118B - Method for treating chlorosulfonated acidic wastewater - Google Patents
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Abstract
A method for treating chlorosulfonated acidic wastewater comprises the following steps: (1) cooling chlorosulfonated acidic wastewater to 0-15 ℃, cooling and crystallizing for 1-24 h, and filtering to obtain a filter cake and a filtrate; (2) adjusting the pH of the filtrate obtained in the step (1) to 1-6, adding an extracting agent for extraction, and standing for layering after extraction is finished to obtain an oil phase and a water phase; the extractant is an amine complexing extractant; (3) adjusting the pH value of the water phase obtained in the step (2) to 6-8, adding an adsorbent for adsorption, and filtering after adsorption is finished; (4) evaporating, crystallizing and drying the filtrate obtained in the step (3) to obtain mixed salt; (5) and (4) analyzing the composition of the mixed salt obtained in the step (4), adding aqueous hydrogen peroxide solution, a stabilizer, sodium sulfate and sodium chloride to react according to the requirement of preparing the sodium sulfate-hydrogen peroxide-sodium chloride adduct, filtering after the reaction is finished, and drying to obtain the sodium sulfate-hydrogen peroxide-sodium chloride adduct. The method does not need to separate mixed salt, and realizes changing waste into valuable.
Description
(I) technical field
The invention relates to a method for treating chlorosulfonated acidic wastewater, in particular to a method for treating aromatic compound chlorosulfonated acidic wastewater.
(II) background of the invention
Chlorosulfonation of aromatic compounds generally uses chlorosulfonic acid as the chlorosulfonating agent, which produces an acidic wastewater containing sulfuric acid, hydrochloric acid, organics, and a small amount of sulfurous acid. The common method for treating chlorosulfonated acidic wastewater in the production process of para-ester generally applies the acidic wastewater in the subsequent hydroxyethylation reaction, but the applied wastewater is only 3-5%, most of the acidic wastewater is evaporated and crystallized after neutralization, the obtained mixed salt is difficult to separate and can only be used as solid waste for landfill treatment, so that resource waste is caused, and the environment is polluted.
Patent CN107522336A describes a method for treating acidic wastewater generated in the production process of para-ester: the acidity of the acidic wastewater is firstly improved, then aniline is added, and finally the sulfanilic acid is obtained by distillation and dehydration. The method has the advantages that the reaction temperature is as high as 170-190 ℃, only a part of sulfuric acid in the acidic wastewater is treated finally, and hydrochloric acid and sulfurous acid in the acidic wastewater are not effectively treated. The patent CN107473488A is that the para-ester production wastewater is firstly partially evaporated and crystallized, pH value is adjusted for flocculation, nanofiltration, ozone oxidation and other steps, and only single salt sodium chloride and mixed salt are finally recovered without complete treatment, and the process is complex.
Disclosure of the invention
In order to solve the problems, the invention provides a method for treating chlorosulfonated acidic wastewater, which does not need to separate mixed salt and obtains a sodium sulfate-hydrogen peroxide-sodium chloride adduct (4 NaSO) by adding sodium sulfate, sodium chloride and hydrogen peroxide4·2H2O2NaCl) to change waste into valuable.
The technical scheme adopted by the invention is as follows:
a method for treating chlorosulfonated acidic wastewater comprises the following steps:
(1) cooling chlorosulfonated acidic wastewater to 0-15 ℃, cooling and crystallizing for 1-24 h, and filtering to obtain a filter cake which is sulfonic acid corresponding to organic matters;
(2) adjusting the pH of the filtrate obtained in the step (1) to 1-6, adding an extracting agent for extraction, and standing for layering after extraction is finished to obtain an oil phase and a water phase; the extractant is an amine complexing extractant; the purpose of this step is to remove organic impurities from the wastewater;
(3) adjusting the pH value of the water phase obtained in the step (2) to 6-8, adding an adsorbent for adsorption, further removing organic impurities in the wastewater, and filtering after adsorption is finished;
(4) evaporating, crystallizing and drying the filtrate obtained in the step (3) to obtain mixed salt;
(5) and (4) analyzing the composition of the mixed salt obtained in the step (4), adding a proper amount of aqueous hydrogen peroxide solution, a stabilizer, sodium sulfate and sodium chloride to react according to the requirement of preparing the sodium sulfate-hydrogen peroxide-sodium chloride adduct, and filtering and drying after the reaction is finished to obtain the sodium sulfate-hydrogen peroxide-sodium chloride adduct.
The chlorosulfonation in the invention is preferably chlorosulfonation of aromatic compounds, such as chlorosulfonation reaction in the production processes of para-ester, clinicutidine para-ester, N-ethyl meta-ester, 2, 5-dimethoxy para-ester and the like. The chlorosulfonated acidic wastewater in the step (1) is acidic wastewater obtained by performing ice precipitation and filtration on reaction liquid after chlorosulfonation.
Preferably, in the step (2), the pH of the acidic wastewater is adjusted to 1-6 by using an alkaline agent, wherein the alkaline agent is caustic soda flakes, sodium carbonate solid or sodium bicarbonate solid.
Preferably, in step (2), the amine complex extractant is selected from at least one of the following: trioctyl decyl tertiary amine (N235), trialkyl methylamine chloride (N236), secondary primary amine extractant (N1923), trioctyl amine (TOA), tridecylamine, trialkylamine (Alamine 336), and more preferably trioctyl decyl tertiary amine (N235) or trioctyl amine (TOA). The mass ratio of the chlorosulfonated acidic wastewater to the extractant is preferably 1-20: 1.
preferably, in the step (2), the extracting agent is added, then the diluent is added to facilitate extraction layering, and then extraction is carried out, wherein the mass ratio of the diluent to the extracting agent is 1:1 to 20. As a further preference, the diluent is selected from at least one of the following: benzene, n-octane, n-hexane, carbon tetrachloride, n-octanol, isooctanol, chloroform, sulfonated kerosene, and more preferably sulfonated kerosene or n-octanol.
Preferably, in the step (2), the extraction temperature is 10-80 ℃ (more preferably 15-50 ℃), and the extraction time is 0.5-10 h.
Preferably, in the step (2), the standing and layering temperature is 10-80 ℃ (more preferably 15-50 ℃), and the standing and layering time is 0.5-10.0 h.
Preferably, the oil phase obtained in step (2) is treated in the following way: and (3) adjusting the pH of the oil phase obtained in the step (2) to be neutral by using an aqueous alkali solution, heating to 25-80 ℃ for back extraction, evaporating and crystallizing the water phase obtained by the back extraction, recovering the oil phase which is the extracting agent, and returning to the step (2) for recycling. The aqueous alkali solution is preferably an aqueous sodium hydroxide solution.
Preferably, in step (3), the pH of the aqueous phase is adjusted to neutral by using an alkaline agent, wherein the alkaline agent is caustic soda flakes or liquid caustic soda.
Preferably, in step (3), the adsorbent is activated carbon. The mass of the adsorbent is preferably 1-10 per mill of the mass of the water phase adjusted to be neutral.
Preferably, in the step (3), the adsorption temperature is 10-80 ℃ (preferably 15-50 ℃), and the adsorption time is 0.5-10 h.
In the step (5) of the present invention, the requirement for preparing the sodium sulfate-hydroperoxide-sodium chloride adduct refers to the requirement for selection of the stabilizer, raw material charge ratio, reaction temperature, reaction time, etc. in the existing method for preparing the sodium sulfate-hydroperoxide-sodium chloride adduct.
Preferably, in the step (5), the stabilizer is one or more of ethylenediaminetetraacetic acid (EDTA), sodium polyphosphate, sodium polyacrylate, hydroxyethylidene diphosphonic acid, aminotrimethylene phosphonic acid, ethylenediaminetetramethylenephosphonic acid organic phosphoric acid or sodium salt thereof, and polyacrylamide, preferably, ethylenediaminetetraacetic acid and sodium salt thereof, and the mass of the stabilizer is 0.2-1% of that of sodium sulfate.
Preferably, in the step (5), the mass fraction of sodium sulfate in the reaction solution is controlled to be 20-60%, the mass fraction of hydrogen peroxide is controlled to be 10-40%, and the mass fraction of sodium chloride is controlled to be 2-10%; further preferably, the mass fraction of sodium sulfate in the reaction solution is controlled to be 27.3-55.0%, the mass fraction of hydrogen peroxide is controlled to be 13.6-34.5%, and the mass fraction of sodium chloride is controlled to be 4.5-8.0%.
Preferably, in the step (5), the reaction temperature is controlled to be 0-35 ℃, and the reaction time is 0.5-4.0 h.
Preferably, the mixed salt obtained in the step (4) is added into the filtrate obtained in the step (5), sodium sulfate, hydrogen peroxide, sodium chloride and a stabilizing agent are added for continuous reaction according to the requirement of preparing the sodium sulfate-hydrogen peroxide-sodium chloride adduct, and the filtrate is recycled.
Compared with the prior art, the method for treating chlorosulfonated acidic wastewater has the beneficial effects that: (1) the mixed salt obtained by evaporating and crystallizing the acidic wastewater is not required to be separated and can be directly used for producing a sodium sulfate-hydrogen peroxide-sodium chloride adduct; (2) the filtrate after the reaction can be recycled, so that the wastewater discharge is reduced; (3) the sodium sulfate-hydrogen peroxide-sodium chloride adduct has the dual properties of sodium sulfate and hydrogen peroxide, is a neutral and nontoxic oxygen-based washing aid, changes acidic waste water into valuable, and has remarkable social and economic benefits.
(IV) detailed description of the preferred embodiments
The invention will be further described with reference to specific examples, but the scope of the invention is not limited thereto.
Example 1
(1) Taking 1000g of acidic wastewater (obtained in the production process of cleisidine para-ester) obtained by performing chlorosulfonation, ice-out and filtration on acetyl cleisidine, cooling to 15-20 ℃, preserving heat for 3h, and filtering to obtain 8g of filter cake which is acetyl cleisidine sulfonic acid crystals.
(2) Adding 165g of caustic soda flakes into the filtrate obtained in the step (1) to adjust the pH value to 6, adding 289g of extracting agent N235 and 289g of diluent sulfonated kerosene, stirring, heating to 20-25 ℃, and keeping the temperature for 0.5h for extraction. And pouring the mixture into a separating funnel after extraction is finished, standing for layering, keeping the temperature of 20-25 ℃ for 0.5h, and separating after standing is finished.
(3) And (3) adjusting the pH of the oil phase obtained in the step (2) to be equal to 7.0 by using a 5% sodium hydroxide solution, and then preserving heat for 0.5h for back extraction, wherein the obtained oil phase is an extracting agent N235 and can be recycled.
(4) And (3) dropwise adding a small amount of liquid caustic soda into the water phase obtained in the step (2) to adjust the pH value to 8.0, adding 3.5g of activated carbon, stirring, heating to 20-25 ℃, keeping the temperature for 0.5h for adsorption, filtering after adsorption is finished, and evaporating, crystallizing and drying the filtrate to obtain 235g of mixed salt.
(5) Adding the mixed salt obtained in the step (4) into 330g of 27.5% hydrogen peroxide, measuring 203.50g of sodium sulfate and 21.49g of sodium chloride in the reaction solution, fully stirring and dissolving, adding 0.8g of EDTA, and supplementing 46.50g of sodium sulfate and 21.51g of sodium chloride to ensure that Na in the reaction solution2SO4、H2O2And the mass fractions of NaCl are 39.7%, 14.4% and 7.9%, the temperature is kept at 20-25 ℃ for 1h, then the filtration is carried out, and the filter cake is dried at 120 ℃ for 1h to obtain 211g of the sodium sulfate-hydrogen peroxide-sodium chloride adduct. Analysis of the adduct by Na2SO4、H2O2The NaCl contents of 81.17%, 9.43% and 9.40%, respectively, and a sodium sulfate-hydroperoxide-sodium chloride adduct (4 NaSO)4·2H2O2NaCl) the contents of the respective substances in the molecular structural formula were substantially the same.
(6) 367.40g of the filtrate obtained in step (5) was collected and analyzed for Na2SO4、H2O2The NaCl content was 14.26%, 16.17% and 8.17%, respectively. Then adding 150.00g of mixed salt obtained in the step (4) into the filtrate, and respectively adding 67.72g of sodium sulfate and 45.01g of 60% hydrogen peroxide to ensure that Na in the reaction solution2SO4、H2O2And the mass fractions of NaCl are 39.7%, 14.4% and 7.9%, the mixture is subjected to heat preservation at the temperature of 20-25 ℃ for 1 hour, then filtered and dried to obtain 208g of a sodium sulfate-hydrogen peroxide-sodium chloride adduct, and the adduct is analyzed by Na2SO4、H2O2The NaCl content is 81.38%, 9.35% and 9.27%, respectively, and the filtrate is recycled.
Example 2
(1) 1000g of acidic wastewater (in the production process of para-ester) obtained by performing chlorosulfonation on acetanilide, performing ice precipitation and filtration is cooled to 5-10 ℃ and is kept for 24 hours, and then filtration is performed to obtain 10g of filter cake which is acetanilide sulfonic acid crystals.
(2) And (2) adding 144g of caustic soda flakes into the filtrate obtained in the step (1) to adjust the pH value to 1.5, continuously adding 226g of N235 and 113g of sulfonated kerosene, stirring, heating to 30-35 ℃, and keeping the temperature for 1h for extraction. And pouring the mixture into a separating funnel after extraction is finished, standing for layering, keeping the temperature of 30-35 ℃ for 0.5h, and separating after standing is finished.
(3) Adjusting the pH value of the solution obtained in the step (2) to 7.0 by using a 5% sodium hydroxide solution, and then preserving the temperature for 1h for back extraction, wherein the oil phase is an extracting agent N235 which can be recycled.
(4) And (3) dropwise adding a small amount of liquid caustic soda into the water phase obtained in the step (2) to adjust the pH value to 7.5, adding 3.0g of activated carbon, stirring, then keeping the temperature at 30-35 ℃ for 0.5h for adsorption, filtering after adsorption is finished, and evaporating, crystallizing and drying the filtrate to obtain 184.0g of mixed salt.
(5) Adding the mixed salt obtained in the step (4) into 222g of 30% hydrogen peroxide, measuring 166.4g of sodium sulfate and 17.6g of sodium chloride in the reaction solution, fully stirring and dissolving, adding 0.65g of EDTA, and supplementing 73.6g of sodium sulfate and 14.4g of sodium chloride to ensure that Na in the reaction solution2SO4、H2O2And the mass fractions of NaCl are 50.2%, 14.1% and 6.3%, the temperature is kept at 10-15 ℃ for 1h, then the filtration is carried out, and the filter cake is dried at 100 ℃ for 2h to obtain 234g of the sodium sulfate-hydrogen peroxide-sodium chloride adduct. Analysis of the adduct by Na2SO4、H2O2NaCl contents of 81.08%, 9.36% and 9.45%, respectively, with sodium sulfate-hydroperoxide-sodium chloride adduct (4 NaSO)4·2H2O2NaCl) was substantially uniform in content in the molecular structural formula.
(6) 234.7g of the filtrate obtained in step (5) was collected and analyzed for Na2SO4、H2O2And NaCl contents of 21.28%, 16.40% and 4.20%, respectively. Then 184g of the mixed salt obtained in the step (4) is added into the filtrate, 23.65g of sodium sulfate, 4.55g of sodium chloride and 47.12g of 60% hydrogen peroxide are respectively added, so that Na in the reaction solution is obtained2SO4、H2O2NaCl and NaCl in the mass fractions of 50.2%, 14.1% and 6.3%, preserving the heat at 10-15 ℃ for 1h, filtering and drying to obtain 171g of sodium sulfate-hydrogen peroxide-sodium chloride adduct, and analyzing the adduct to obtain Na2SO4、H2O2The NaCl content is 81.44%, 9.38% and 9.18%, respectively, and the filtrate can be recycled.
Example 3
(1) Taking 1000g of acidic wastewater (obtained in the production process of cleisidine para-ester) obtained by performing chlorosulfonation, ice-out and filtration on acetyl cleisidine, cooling to 15-20 ℃, preserving heat for 3h, and filtering to obtain 8g of filter cake which is acetyl cleisidine sulfonic acid crystals.
(2) Adding 165g of caustic soda flakes into the filtrate obtained in the step (1) to adjust the pH value to 6, adding 480g of extractant TOA, stirring, heating to 20-25 ℃, and keeping the temperature for 0.5h for extraction. And pouring the mixture into a separating funnel after extraction is finished, standing for layering, keeping the temperature of 20-25 ℃ for 0.5h, and separating after standing is finished.
(3) And (3) adjusting the pH of the oil phase obtained in the step (2) to be equal to 7.0 by using a 5% sodium hydroxide solution, and then preserving heat for 0.5h for back extraction, wherein the obtained oil phase is an extractant TOA and can be recycled.
(4) And (3) dropwise adding a small amount of liquid caustic soda into the water phase obtained in the step (2) to adjust the pH value to 8.0, adding 3.5g of activated carbon, stirring, heating to 20-25 ℃, keeping the temperature for 0.5h for adsorption, filtering after adsorption is finished, and evaporating, crystallizing and drying the filtrate to obtain 238g of mixed salt.
(5) Adding the mixed salt obtained in the step (4) into 300g of 30% hydrogen peroxide, measuring 202.81g of sodium sulfate and 21.64g of sodium chloride in the reaction solution, fully stirring and dissolving, adding 0.8g of EDTA, and supplementing 51.85g of sodium sulfate and 19.96g of sodium chloride to ensure that Na in the reaction solution2SO4、H2O2And the mass fractions of NaCl are 42.65%, 15.07% and 6.97%, the temperature is kept at 20-25 ℃ for 1h, then the filtration is carried out, and the filter cake is dried at 120 ℃ for 1h to obtain 217g of the sodium sulfate-hydrogen peroxide-sodium chloride adduct. Analysis of the adduct by Na2SO4、H2O2NaCl contents of 81.32%, 9.31% and 9.39%, respectively, and sodium sulfate-hydroperoxide-sodium chloride adduct (4 Na)2SO4·2H2O2NaCl) the contents of the respective substances in the molecular structural formula were substantially the same.
(6) 326.32g of the filtrate obtained in step (5) was collected and analyzed for Na2SO4、H2O2The NaCl content was 23.26%, 21.39% and 6.50%, respectively. Then adding 120.0g of mixed salt obtained in the step (4) into the filtrate, and respectively supplementing 50.21g of sodium sulfate and 30% of double45.01g of oxygen water, to make Na in the reaction solution2SO4、H2O2NaCl in the mass fraction of 42.16%, 15.37% and 5.93%, preserving the temperature at 20-25 ℃ for 1h, filtering and drying to obtain 187g of sodium sulfate-hydrogen peroxide-sodium chloride adduct, and analyzing the adduct by Na2SO4、H2O2The NaCl content is 85.1 percent, 9.27 percent and 5.63 percent respectively, and the filtrate is recycled.
Claims (10)
1. A method for treating chlorosulfonated acidic wastewater comprises the following steps:
(1) cooling chlorosulfonated acidic wastewater to 0-15 ℃, cooling and crystallizing for 1-24 h, and filtering to obtain a filter cake and a filtrate;
(2) adjusting the pH of the filtrate obtained in the step (1) to 1-6 by using an alkaline agent A, then sequentially adding an extracting agent and a diluting agent for extraction, and standing for layering after extraction is finished to obtain an oil phase and a water phase; the extractant is an amine complexing extractant; the alkaline agent A is flake caustic soda, sodium carbonate solid or sodium bicarbonate solid;
(3) adjusting the pH of the water phase obtained in the step (2) to 6-8 by using an alkaline agent B, adding an adsorbent to adsorb organic matters in the wastewater, and filtering after adsorption is finished; the alkaline agent B is flake alkali or liquid alkali;
(4) evaporating, crystallizing and drying the filtrate obtained in the step (3) to obtain mixed salt;
(5) analyzing the composition of the mixed salt obtained in the step (4), adding a proper amount of aqueous hydrogen peroxide solution, a stabilizer, sodium sulfate and sodium chloride to react according to the requirement of preparing the sodium sulfate-hydrogen peroxide-sodium chloride adduct, filtering after the reaction is finished, and drying to obtain the sodium sulfate-hydrogen peroxide-sodium chloride adduct;
the chlorosulfonated acidic wastewater is chlorosulfonated acidic wastewater generated in the production process of para-ester, clinicidin para-ester, N-ethyl meta-ester or 2, 5-dimethoxy para-ester.
2. The process of claim 1, wherein: in the step (2), the diluent is selected from at least one of the following: benzene, n-octane, n-hexane, carbon tetrachloride, n-octanol, isooctanol, chloroform and sulfonated kerosene; the mass ratio of the diluent to the extractant is 1: 1-20.
3. The process of claim 1, wherein: in the step (2), the amine complex extractant is selected from at least one of the following: trioctyl decyl tertiary amine, chloride trialkyl methylamine, secondary carbon primary amine extractant, trioctyl amine, tridecyl amine, trialkyl amine; the mass ratio of the chlorosulfonated acidic wastewater to the extracting agent is 1-20: 1.
4. The process of claim 1, wherein: in the step (2), the extraction temperature is 10-80 ℃, and the extraction time is 0.5-10 h; the standing and layering temperature is 10-80 ℃, and the standing and layering time is 0.5-10.0 h.
5. The process of claim 1, wherein: in the step (2), the extraction temperature and the standing and layering temperature are both 15-50 ℃.
6. The process of claim 1, wherein: and (3) adjusting the pH of the oil phase obtained in the step (2) to be neutral by using an aqueous alkali solution, heating to 25-80 ℃ for back extraction, evaporating and crystallizing the water phase obtained by the back extraction, recovering the oil phase which is the extracting agent, and returning to the step (2) for recycling.
7. The process of claim 1, wherein: in the step (3), the adsorbent is activated carbon; the mass of the adsorbent is 1-10 per mill of the mass of the water phase adjusted to be neutral.
8. The process of claim 1, wherein: in the step (3), the adsorption temperature is 10-80 ℃, and the adsorption time is 0.5-10 h.
9. The process of claim 1, wherein: in the step (3), the adsorption temperature is 15-50 ℃.
10. The process of claim 1, wherein: and (4) adding the filtrate obtained in the step (5) into the mixed salt obtained in the step (4), supplementing sodium sulfate, hydrogen peroxide, sodium chloride and a stabilizing agent according to the requirement of preparing the sodium sulfate-hydrogen peroxide-sodium chloride adduct, and continuously reacting to realize the recycling of the filtrate.
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