CN110117118A - A kind of processing method of chlorosulfonation acid waste water - Google Patents

A kind of processing method of chlorosulfonation acid waste water Download PDF

Info

Publication number
CN110117118A
CN110117118A CN201910341965.XA CN201910341965A CN110117118A CN 110117118 A CN110117118 A CN 110117118A CN 201910341965 A CN201910341965 A CN 201910341965A CN 110117118 A CN110117118 A CN 110117118A
Authority
CN
China
Prior art keywords
extractant
processing method
hydrogen peroxide
obtains
filtrate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201910341965.XA
Other languages
Chinese (zh)
Other versions
CN110117118B (en
Inventor
何旭斌
李海锋
徐伟
张桂香
吴建伟
屠昌盛
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ZHEJIANG LONGSHENG CHEMICALS CO Ltd
Original Assignee
ZHEJIANG LONGSHENG CHEMICALS CO Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by ZHEJIANG LONGSHENG CHEMICALS CO Ltd filed Critical ZHEJIANG LONGSHENG CHEMICALS CO Ltd
Priority to CN201910341965.XA priority Critical patent/CN110117118B/en
Publication of CN110117118A publication Critical patent/CN110117118A/en
Application granted granted Critical
Publication of CN110117118B publication Critical patent/CN110117118B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00—Multistage treatment of water, waste water or sewage
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3942—Inorganic per-compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/02—Treatment of water, waste water, or sewage by heating
    • C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
    • C02F1/048—Purification of waste water by evaporation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/22—Treatment of water, waste water, or sewage by freezing
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/26—Treatment of water, waste water, or sewage by extraction
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/36—Organic compounds containing halogen
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/40—Organic compounds containing sulfur

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Hydrology & Water Resources (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Water Treatment By Sorption (AREA)

Abstract

A kind of processing method of chlorosulfonation acid waste water, comprising the following steps: (1) chlorosulfonation acid waste water is cooled to 0~15 DEG C of crystallisation by cooling 1~for 24 hours, filtering obtains filter cake and filtrate；(2) the filtrate tune pH to 1~6 for obtaining step (1), is added extractant extraction, and stratification after extraction obtains oily phase and water phase；The extractant is amine complexing extractant；(3) the water phase tune pH to 6-8 for obtaining step (2) is added adsorbent absorption, filters after absorption；(4) by filtrate evaporative crystallization that step (3) obtains, be dried to obtain mixed salt；(5) composition for the mixed salt that analytical procedure (4) obtains, then aqueous hydrogen peroxide solution, stabilizer, sodium sulphate and sodium chloride is added according to the requirement for preparing adduct sodium sulphate-hydrogen peroxide-sodium chloride to be reacted, reaction terminates filtering, is dried to obtain adduct sodium sulphate-hydrogen peroxide-sodium chloride.The method of the present invention is not required to mixed salt to be separated, and realizing turns waste into wealth.

Description

A kind of processing method of chlorosulfonation acid waste water
(1) technical field
The present invention relates to a kind of processing method of chlorosulfonation acid waste water, especially a kind of aromatic compound chlorosulfonation acid The processing method of property waste water.
(2) background technique
The chlorosulfonation of aromatic compound can generate sulfur acid, hydrochloric acid, organic generally using chlorosulfonic acid as chlorosulfonation reagent The acid waste water of object and a small amount of sulfurous acid.The processing method of chlorosulfonation acid waste water in common contraposition ester production process, one As be that acid waste water set is used in subsequent ethoxyl etherification, but is applied waste water also only has 3~5%, it is most of acid Evaporative crystallization after waste water is neutralized, obtained mixed salt are difficult to separate, and can only be used as solid waste landfill disposal, not only result in waste of resources And pollution environment.
Patent CN107522336A introduces a kind of processing method of acid waste water for aligning and generating in ester production process: acid Waste water first improves acidity, adds aniline, and last distillation dehydration obtains p-aminobenzene sulfonic acid.Not only reaction temperature is up to this method 170~190 DEG C, final only to have handled a part of sulfuric acid in acid waste water, the hydrochloric acid and sulfurous acid in water do not obtain effectively Processing.Patent CN107473488A is then that para-ester is produced to waste water elder generation part evaporative crystallization, adjusts pH flocculation, nanofiltration and ozone Oxidation and etc., it is finally only recovered to mono-salt sodium chloride and mixed salt, not all processing, and complex process.
(3) summary of the invention
To solve the above-mentioned problems, the present invention provides a kind of processing method of chlorosulfonation acid waste water, and this method does not need Mixed salt is separated, obtains adduct sodium sulphate-hydrogen peroxide-sodium chloride by the way that sodium sulphate, sodium chloride and hydrogen peroxide is added (4NaSO4·2H2O2NaCl), realization is turned waste into wealth.
The technical solution adopted by the invention is as follows:
A kind of processing method of chlorosulfonation acid waste water, comprising the following steps:
(1) chlorosulfonation acid waste water is cooled to 0~15 DEG C of crystallisation by cooling 1~for 24 hours, filtering, filter cake is corresponding organic matter Sulfonic acid；
(2) the filtrate tune pH to 1~6 for obtaining step (1), is added extractant extraction, and stratification after extraction obtains To oily phase and water phase；The extractant is amine complexing extractant；The purpose of this step is the organic impurities removed in waste water；
(3) the water phase tune pH to 6-8 for obtaining step (2), is added adsorbent absorption, further removes organic in waste water Impurity filters after absorption；
(4) by filtrate evaporative crystallization that step (3) obtains, be dried to obtain mixed salt；
(5) composition for the mixed salt that analytical procedure (4) obtains, then according to preparing sodium sulphate-hydrogen peroxide-sodium chloride adduction The requirement of object is added suitable aqueous hydrogen peroxide solution, stabilizer, sodium sulphate and sodium chloride and is reacted, reaction end filtering, It is dried to obtain adduct sodium sulphate-hydrogen peroxide-sodium chloride.
Chlorosulfonation of the present invention is preferably the chlorosulfonation of aromatic compound, such as para-ester, Ke Lixiding para-ester, N- Chlorosulfonation in the production processes such as ethyl meta position ester, 2,5- dimethoxy para-ester.Chlorosulfonation acid in above-mentioned steps (1) Property waste water refer to that reaction solution is through ice analysis, filtered acid waste water after chlorosulfonation.
Preferably, acid waste water pH is adjusted to 1~6 using alkaline agent, the alkaline agent is piece alkali, sodium carbonate in step (2) Solid or sodium bicarbonate solid.
Preferably, the amine complexing extractant is selected from following at least one: three pungent decyl uncles in step (2) Amine (N235), chlorination trialkyl methylamine (N236), secondary carbon primary amine extractant (N1923), trioctylamine (TOA), tridecylamine, trialkyl Amine (Alamine 336), more preferably three pungent decyl tertiary amines (N235) or trioctylamine (TOA).The chlorosulfonation acid waste water It is preferably 1~20:1 with extractant mass ratio.
Preferably, adding diluent in step (2) after extractant is added, facilitating extracting and demixing, then extracted It takes, the diluent and extractant mass ratio are 1:1~20.As a further preference, the diluent be selected from it is following extremely Few one kind: benzene, normal octane, n-hexane, carbon tetrachloride, n-octyl alcohol, isooctanol, chloroform, sulfonated kerosene are still more preferably sulphur Change kerosene or n-octyl alcohol.
Preferably, in step (2), extraction temperature is 10~80 DEG C (more preferable 15-50 DEG C), extraction time is 0.5~ 10h。
Preferably, stratification temperature is 10~80 DEG C (more preferable 15-50 DEG C) in step (2), the stratification time For 0.5~10.0h.
Preferably, mutually handling the oil that step (2) obtains in the following manner: by oil obtained in step (2) Phase aqueous alkali tune pH to neutrality, then be warming up to 25~80 DEG C and be stripped, the water phase evaporative crystallization being stripped, oil recovery It is mutually extractant, return step (2) recycled.The aqueous alkali is preferably sodium hydrate aqueous solution.
Preferably, water phase pH is adjusted to neutrality using alkaline agent, the alkaline agent is piece alkali or liquid alkaline in step (3).
Preferably, adsorbent is active carbon in step (3).Adsorbent mass is preferably to be adjusted to neutral water phase quality 1~10 ‰.
Preferably, in step (3), adsorption temp is 10~80 DEG C (preferably 15-50 DEG C), adsorption time is 0.5~ 10h。
In step (5) of the present invention, the requirement for preparing adduct sodium sulphate-hydrogen peroxide-sodium chloride refers to existing Prepare in the method for adduct sodium sulphate-hydrogen peroxide-sodium chloride for stabilizer selection, raw material feed ratio, reaction temperature, The requirement in reaction time etc..
Preferably, the stabilizer is ethylenediamine tetra-acetic acid (EDTA), sodium polyphosphate, polypropylene in step (5) Sour sodium, hydroxy ethylene diphosphonic acid, aminotrimethylenephosphonic acid, ethylenediamine tetramethylene phosphonic acid organic phosphoric acid or its sodium salt and poly- One or more of several mixtures of bright acrylamide, preferably edta and its sodium salt, stabilizer quality are sulfuric acid The 0.2~1% of sodium quality.
Preferably, the mass fraction for controlling sodium sulphate in reaction solution is 20%~60%, hydrogen peroxide in step (5) Mass fraction be 10%~40%, the mass fraction of sodium chloride is 2%~10%；Still more preferably control sulphur in reaction solution The mass fraction of sour sodium is 27.3%~55.0%, and the mass fraction of hydrogen peroxide is 13.6%~34.5%, the matter of sodium chloride Measuring score is 4.5%~8.0%.
Preferably, controlling 0~35 DEG C of reaction temperature, the reaction time is 0.5~4.0h in step (5).
Preferably, the mixed salt that step (4) obtain is added in the obtained filtrate of step (5), according to preparing sodium sulphate-peroxidating Sodium sulphate, hydrogen peroxide, sodium chloride and stabilizer are added in the requirement of hydrogen-sodium chloride adduct, and the reaction was continued, and filtrate cycle is applied.
Compared with prior art, the processing method of chlorosulfonation acid waste water of the present invention, its advantages are embodied in: (1) mixed salt that acid waste water evaporative crystallization obtains does not have to separation, is directly available in production sodium sulphate-hydrogen peroxide-sodium chloride and adds Close object；(2) filtrate after reaction is recyclable applies, and reduces discharge of wastewater；(3) sodium sulphate-hydrogen peroxide-sodium chloride adduction Object has the double properties of sodium sulphate and hydrogen peroxide, is a kind of neutral, nontoxic oxygen system washing assisant, and acid waste water is become useless For treasured, there is significant Social benefit and economic benefit.
(4) specific embodiment
The present invention is described further combined with specific embodiments below, but protection scope of the present invention is not limited to This.
Embodiment 1
(1) acid waste water 1000g (the Ke Lixiding para-ester that take ice analysis after acetyl Ke Lixiding chlorosulfonation, is obtained by filtration In production process), 15~20 DEG C of heat preservation 3h are cooled to, are filtered, the filter cake for obtaining 8g is acetyl Ke Lixiding sulfonic acid crystal.
(2) in the filtrate obtained to step (1) be added 165g piece alkali adjust pH to 6, be added 289g extractant N235 and 289g diluent sulfonated kerosene, unlatching stirring are warming up to 20~25 DEG C of heat preservation 0.5h and are extracted.Liquid separation is poured into after extraction Stratification in funnel, 20~25 DEG C of heat preservation 0.5h, liquid separation after standing.
(3) obtained to step (2) oil mutually with 5% sodium hydroxide solution adjust to pH be equal to 7.0 after keep the temperature 0.5h into Row back extraction, obtained oil is mutually extractant N235, recyclable to apply.
(4) a small amount of liquid adjusting PH with base is added dropwise in the water phase obtained to step (2) to 8.0,3.5g active carbon is added, opens stirring Afterwards and be warming up to 20~25 DEG C of heat preservation 0.5h and adsorbed, filtered after absorption, filtrate evaporative crystallization, it is dry after obtain mixed salt 235g。
(5) mixed salt that step (4) obtains is added in 27.5% hydrogen peroxide of 330g, measures sodium sulphate in reaction solution 203.50g, sodium chloride 21.49g are added 0.8gEDTA after dissolution is sufficiently stirred, then add 46.50g sodium sulphate and 21.51g chlorine Change sodium, makes Na in reaction solution2SO4、H2O2, NaCl mass fraction be 39.7%, 14.4%, 7.9%, 20~25 DEG C of heat preservation 1h After filter, 120 DEG C of filter cake dry 1h obtain adduct sodium sulphate-hydrogen peroxide-sodium chloride 211g.Adduct is through analyzing Na2SO4、H2O2, NaCl content be respectively 81.17%, 9.43% and 9.40%, add with sodium sulphate-hydrogen peroxide-sodium chloride Close object (4NaSO4·2H2O2NaCl) content of each substance is almost the same in molecular structural formula.
(6) the filtrate 367.40g that collection step (5) obtains, is analyzed wherein Na2SO4、H2O2, NaCl content be respectively 14.26%, 16.17% and 8.17%.Then the mixed salt 150.00g that step (4) obtain is added into filtrate, adds sulfuric acid respectively Sodium 67.72g, 60% hydrogen peroxide 45.01g, make Na in reaction solution2SO4、H2O2, NaCl mass fraction be 39.7%, 14.4%, It filtered after 7.9%, 20~25 DEG C of heat preservation 1h, be dried to obtain adduct sodium sulphate-hydrogen peroxide-sodium chloride 208g, adduct warp Analyze Na2SO4、H2O2, NaCl content be respectively 81.38%, 9.35% and 9.27%, filtrate, which continues cycling through, applies.
Embodiment 2
(1) the acid waste water 1000g (in contraposition ester production process) for taking ice analysis after antifebrin chlorosulfonation, being obtained by filtration, It cools to 5~10 DEG C and keeps the temperature 24 hours, filtering, the filter cake for obtaining 10g is antifebrin sulfonic acid crystal.
(2) in the filtrate obtained to step (1) be added 144g piece alkali adjust pH to 1.5, continuously add 226gN235 and 113g sulfonated kerosene, unlatching stirring are warming up to 30~35 DEG C of heat preservation 1h and are extracted.It is poured into after extraction quiet in separatory funnel Set layering, 30~35 DEG C of heat preservation 0.5h, liquid separation after standing.
(3) step (2) is obtained heat preservation 1h after being equal to 7.0 to pH with 5% sodium hydroxide solution adjusting to be stripped, oil Mutually it is that extractant N235 is recyclable to apply.
(4) a small amount of liquid alkaline will be added dropwise in water phase that step (2) obtains and adjusts pH to 7.5,3.0g active carbon is added, unlatching is stirred 30~35 DEG C of heat preservation 0.5h are adsorbed after mixing, and are filtered after absorption, after filtrate evaporative crystallization, drying, obtain mixed salt 184.0g。
(5) mixed salt that step (4) obtains is added in 30% hydrogen peroxide of 222g, measures sodium sulphate in reaction solution 166.4g, sodium chloride 17.6g are added 0.65gEDTA after dissolution is sufficiently stirred, then add 73.6g sodium sulphate and 14.4g chlorination Sodium makes Na in reaction solution2SO4、H2O2, NaCl mass fraction be 50.2%, 14.1% and 6.3%, after 10~15 DEG C of heat preservation 1h Filtering, 100 DEG C of filter cake dry 2h obtain adduct sodium sulphate-hydrogen peroxide-sodium chloride 234g.Adduct is through analyzing Na2SO4、 H2O2, NaCl content be respectively 81.08%, 9.36% and 9.45%, with adduct sodium sulphate-hydrogen peroxide-sodium chloride (4NaSO4·2H2O2NaCl the content in molecular structural formula) is almost the same.
(6) the filtrate 234.7g that collection step (5) obtains, is analyzed wherein Na2SO4、H2O2Content with NaCl is respectively 21.28%, 16.40% and 4.20%.Then the mixed salt 184g that above-mentioned steps (4) obtain is added into filtrate, adds sulphur respectively Sour sodium 23.65g, sodium chloride 4.55g, 60% hydrogen peroxide 47.12g, make Na in reaction solution2SO4、H2O2With the mass fraction of NaCl It is 50.2%, 14.1% and 6.3%, is filtered after 10~15 DEG C of heat preservation 1h, is dried to obtain sodium sulphate-hydrogen peroxide-sodium chloride and adds Object 171g is closed, adduct is through analyzing Na2SO4、H2O2, NaCl content be respectively 81.44%, 9.38% and 9.18%, filtrate after Continuous recycled.
Embodiment 3
(1) acid waste water 1000g (the Ke Lixiding para-ester that take ice analysis after acetyl Ke Lixiding chlorosulfonation, is obtained by filtration In production process), 15~20 DEG C of heat preservation 3h are cooled to, are filtered, the filter cake for obtaining 8g is acetyl Ke Lixiding sulfonic acid crystal.
(2) 165g piece alkali is added in the filtrate obtained to step (1) and adjusts pH to 6,480g extractant TOA is added, open Stirring is warming up to 20~25 DEG C of heat preservation 0.5h and is extracted.Pour into stratification in separatory funnel after extraction, 20~25 DEG C Keep the temperature 0.5h, liquid separation after standing.
(3) obtained to step (2) oil mutually with 5% sodium hydroxide solution adjust to pH be equal to 7.0 after keep the temperature 0.5h into Row back extraction, obtained oil is mutually extractant TOA, recyclable to apply.
(4) a small amount of liquid adjusting PH with base is added dropwise in the water phase obtained to step (2) to 8.0,3.5g active carbon is added, opens stirring Afterwards and be warming up to 20~25 DEG C of heat preservation 0.5h and adsorbed, filtered after absorption, filtrate evaporative crystallization, it is dry after obtain mixed salt 238g。
(5) mixed salt that step (4) obtains is added in 30% hydrogen peroxide of 300g, measures sodium sulphate in reaction solution 202.81g, sodium chloride 21.64g are added 0.8gEDTA after dissolution is sufficiently stirred, then add 51.85g sodium sulphate and 19.96g chlorine Change sodium, makes Na in reaction solution2SO4、H2O2, NaCl mass fraction be 42.65%, 15.07%, 6.97%, 20~25 DEG C heat preservation It is filtered after 1h, 120 DEG C of filter cake dry 1h obtain adduct sodium sulphate-hydrogen peroxide-sodium chloride 217g.Adduct is through analyzing Na2SO4、H2O2, NaCl content be respectively 81.32%, 9.31% and 9.39%, add with sodium sulphate-hydrogen peroxide-sodium chloride Close object (4Na2SO4·2H2O2NaCl) content of each substance is almost the same in molecular structural formula.
(6) the filtrate 326.32g that collection step (5) obtains, is analyzed wherein Na2SO4、H2O2, NaCl content be respectively 23.26%, 21.39% and 6.50%.Then the mixed salt 120.0g that step (4) obtain is added into filtrate, adds sulfuric acid respectively Sodium 50.21g, 30% hydrogen peroxide 45.01g, make Na in reaction solution2SO4、H2O2, NaCl mass fraction be 42.16%, 15.37%, it filtered after 5.93%, 20~25 DEG C of heat preservation 1h, be dried to obtain adduct sodium sulphate-hydrogen peroxide-sodium chloride 187g, Adduct is through analyzing Na2SO4、H2O2, NaCl content be respectively 85.1%, 9.27% and 5.63%, filtrate continues cycling through set With.

Claims (10)

1. a kind of processing method of chlorosulfonation acid waste water, comprising the following steps:
(1) chlorosulfonation acid waste water is cooled to 0~15 DEG C of crystallisation by cooling 1~for 24 hours, filtering obtains filter cake and filtrate；
(2) the filtrate tune pH to 1~6 for obtaining step (1), is added extractant extraction, and stratification after extraction obtains oil Phase and water phase；The extractant is amine complexing extractant；
(3) the water phase tune pH to 6-8 for obtaining step (2) is added adsorbent absorption, filters after absorption；
(4) by filtrate evaporative crystallization that step (3) obtains, be dried to obtain mixed salt；
(5) composition for the mixed salt that analytical procedure (4) obtains, then according to preparing adduct sodium sulphate-hydrogen peroxide-sodium chloride It is reacted it is required that suitable aqueous hydrogen peroxide solution, stabilizer, sodium sulphate and sodium chloride is added, reaction terminates filtering, drying Obtain adduct sodium sulphate-hydrogen peroxide-sodium chloride.
2. processing method as described in claim 1, it is characterised in that: in step (2), add dilution after extractant is added Then agent is extracted；The diluent is selected from following at least one: benzene, normal octane, n-hexane, carbon tetrachloride, just pungent Alcohol, isooctanol, chloroform, sulfonated kerosene；The diluent and extractant mass ratio are 1:1~20.
3. processing method as claimed in claim 1 or 2, it is characterised in that: in step (2), using alkaline agent A by acid waste water pH It is adjusted to 1~6, the alkaline agent A is piece alkali, sodium carbonate solid or sodium bicarbonate solid；In step (3), using alkaline agent B by water phase pH It is adjusted to neutrality, the alkaline agent B is piece alkali or liquid alkaline.
4. processing method as claimed in claim 1 or 2, it is characterised in that: in step (2), the amine complexing extractant Selected from following at least one: three pungent decyl tertiary amines, chlorination trialkyl methylamine, secondary carbon primary amine extractant, trioctylamine, tridecylamine, Trialkylamine；The chlorosulfonation acid waste water and extractant mass ratio are 1~20:1.
5. processing method as claimed in claim 1 or 2, it is characterised in that: in step (2), extraction temperature is 10~80 DEG C, extraction Taking the time is 0.5~10h；Stratification temperature is 10~80 DEG C, and the stratification time is 0.5~10.0h.
6. processing method as claimed in claim 5, it is characterised in that: in step (2), extraction temperature and stratification temperature are equal It is 15-50 DEG C.
7. processing method as claimed in claim 1 or 2, it is characterised in that: the oily phase obtained in the following manner to step (2) It is handled: by the phase aqueous alkali tune pH to neutrality of oil obtained in step (2), then being warming up to 25~80 DEG C and be stripped, It is stripped obtained water phase evaporative crystallization, oil recovery is mutually extractant, return step (2) recycled.
8. processing method as claimed in claim 1 or 2, it is characterised in that: in step (3), the adsorbent is active carbon；Institute Stating adsorbent mass is be adjusted to neutral water phase quality 1~10 ‰.
9. processing method as claimed in claim 8, it is characterised in that: in step (3), adsorption temp be 10~80 DEG C (preferably 15-50 DEG C), adsorption time is 0.5~10h.
10. processing method as claimed in claim 1 or 2, it is characterised in that: the filtrate that step (5) obtains is added step (4) and obtains The mixed salt arrived adds sodium sulphate, hydrogen peroxide, sodium chloride according to the requirement for preparing adduct sodium sulphate-hydrogen peroxide-sodium chloride The reaction was continued with stabilizer, realizes that filtrate cycle is applied.
CN201910341965.XA 2019-04-26 2019-04-26 Method for treating chlorosulfonated acidic wastewater Active CN110117118B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910341965.XA CN110117118B (en) 2019-04-26 2019-04-26 Method for treating chlorosulfonated acidic wastewater

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910341965.XA CN110117118B (en) 2019-04-26 2019-04-26 Method for treating chlorosulfonated acidic wastewater

Publications (2)

Publication Number Publication Date
CN110117118A true CN110117118A (en) 2019-08-13
CN110117118B CN110117118B (en) 2022-01-14

Family

ID=67521559

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910341965.XA Active CN110117118B (en) 2019-04-26 2019-04-26 Method for treating chlorosulfonated acidic wastewater

Country Status (1)

Country Link
CN (1) CN110117118B (en)

Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006038999A1 (en) * 2004-09-30 2006-04-13 Illinois Tool Works Inc. Surface activated adhesive systems
CN101058408A (en) * 2007-06-07 2007-10-24 浙江闰土股份有限公司 High-pollution low-concentration waste acid recycling method
CN101428921A (en) * 2008-12-04 2009-05-13 安吉豪森药业有限公司 Method for treating wastewater discharged from p-toluene sulfonyl chloride production
CN102504587A (en) * 2011-10-18 2012-06-20 褚平忠 Method for recovering waste acid from sulfonation of para-ester
CN104030529A (en) * 2014-06-18 2014-09-10 泰兴锦汇化工有限公司 Treatment method for dye intermediate para-ester production wastewater
CN105347624A (en) * 2015-11-20 2016-02-24 新乡市汇丰染化有限公司 Integrated treatment method of p-(beta-sulfatoethylsulfonyl)aniline production wastewater
CN106006799A (en) * 2016-05-17 2016-10-12 江苏亿尔等离子体科技有限公司 Method and device for carbonizing production wastewater of printing and dyeing intermediates through superheated steam
CN106145102A (en) * 2016-07-25 2016-11-23 华侨大学 A kind of method preparing expanded graphite or Graphene
CN107522336A (en) * 2017-09-08 2017-12-29 江苏明盛化工有限公司 The processing method of caused acid waste water in a kind of contraposition ester production process
CN108440342A (en) * 2018-03-15 2018-08-24 新乡市锦源化工有限公司 Environment-friendly type is to the production method of beta-sulfuric ester ethyl sulfonyl aniline and to beta-sulfuric ester ethyl sulfonyl aniline
CN108569737A (en) * 2018-04-23 2018-09-25 新乡市锦源化工有限公司 The wastewater treatment method of the antifebrin route of para-ester
CN109205921A (en) * 2017-06-29 2019-01-15 开封市隆兴化工有限公司 Align treatment method for high-salinity wastewater in ester production process

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006038999A1 (en) * 2004-09-30 2006-04-13 Illinois Tool Works Inc. Surface activated adhesive systems
CN101058408A (en) * 2007-06-07 2007-10-24 浙江闰土股份有限公司 High-pollution low-concentration waste acid recycling method
CN101428921A (en) * 2008-12-04 2009-05-13 安吉豪森药业有限公司 Method for treating wastewater discharged from p-toluene sulfonyl chloride production
CN102504587A (en) * 2011-10-18 2012-06-20 褚平忠 Method for recovering waste acid from sulfonation of para-ester
CN104030529A (en) * 2014-06-18 2014-09-10 泰兴锦汇化工有限公司 Treatment method for dye intermediate para-ester production wastewater
CN105347624A (en) * 2015-11-20 2016-02-24 新乡市汇丰染化有限公司 Integrated treatment method of p-(beta-sulfatoethylsulfonyl)aniline production wastewater
CN106006799A (en) * 2016-05-17 2016-10-12 江苏亿尔等离子体科技有限公司 Method and device for carbonizing production wastewater of printing and dyeing intermediates through superheated steam
CN106145102A (en) * 2016-07-25 2016-11-23 华侨大学 A kind of method preparing expanded graphite or Graphene
CN109205921A (en) * 2017-06-29 2019-01-15 开封市隆兴化工有限公司 Align treatment method for high-salinity wastewater in ester production process
CN107522336A (en) * 2017-09-08 2017-12-29 江苏明盛化工有限公司 The processing method of caused acid waste water in a kind of contraposition ester production process
CN108440342A (en) * 2018-03-15 2018-08-24 新乡市锦源化工有限公司 Environment-friendly type is to the production method of beta-sulfuric ester ethyl sulfonyl aniline and to beta-sulfuric ester ethyl sulfonyl aniline
CN108569737A (en) * 2018-04-23 2018-09-25 新乡市锦源化工有限公司 The wastewater treatment method of the antifebrin route of para-ester

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
崔林: "4-氨基苯基-β-羟乙基砜硫酸酯(对位酯)工艺改进研究 ", 《染料工业》 *
王鸿显等: "硫酸钠-过氧化氢-氯化钠加合物合成研究", 《海湖盐与化工》 *
赵国生等: "磺化对位酯的清洁生产工艺", 《化工管理》 *

Also Published As

Publication number Publication date
CN110117118B (en) 2022-01-14

Similar Documents

Publication Publication Date Title
CN103757425B (en) A kind of clean process method being produced vanadic acid sodium and chromium acid sodium alkaline liquid by high chrome alum slag
WO2011120272A1 (en) Method for preparing manganese sulfate monohydrate
CN103922416A (en) Method for separating and recovering iron from red mud
CN1297847A (en) Comprehensive utilization method of waste ammonia sode liquid and sodium sulfate containing waste liquid
CN102910676B (en) Preparation method of high-purity vanadium pentoxide
CN113874322B (en) Method for purifying sodium sulfate residue
CN101774557A (en) Method for producing phosphoric acid with titanium white waste
NO840973L (en) PROCEDURE FOR THE PREPARATION OF ANNUAL ALUMINUM CHLORIDE FROM ALUMINUM CHLORIDE HEXHYDRATE WRITTEN FROM ACID EXCLUSION
CN102674468B (en) Method for preparing barium sulfate while purifying manganese sulfate
DE2625248A1 (en) METHOD FOR TREATMENT OF BRINE SLUDGE
CN107140660B (en) A kind of preparation method of potassium carbonate
CN110117118A (en) A kind of processing method of chlorosulfonation acid waste water
WO2024051103A1 (en) Phosphogypsum recovery method
AU2003300719A1 (en) Process for recovery of sulphate of potash
US4196172A (en) Hemihydrate type phosphoric acid process
CN109534369A (en) A kind of film is integrated to prepare lithium chloride device and method thereof
CN101663241A (en) Porous iron oxide, process for producing the same, and method of treating water
RU2627431C1 (en) Method for producing calcium fluoride from fluorocarbon-containing waste of aluminium production
NO841402L (en) PROCEDURE FOR THE PRODUCTION OF ZEOLITE A
CN115650243A (en) Method for separating and recovering fluorine and silicon in fluorine-containing silicon slag in one step
CN105837431B (en) A kind of method that sodium acetate is detached in sodium acetate and sodium sulphate mixed system
CN103687848A (en) Sustainable chemical process for isolation of naphthalene sulphonic acid compounds with inherent recycle of all acidic streams generated during isolation and washing
DE2915129C2 (en) Process for the industrial production of high-purity magnesium oxide
CN101760642B (en) Process for recovering magnesium from magnesium sulfate solution
CN105585233A (en) Reduction and recycling method for evaporation salty mud

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant