CN105884108B - A kind for the treatment of process of ammonolysis waste water - Google Patents

A kind for the treatment of process of ammonolysis waste water Download PDF

Info

Publication number
CN105884108B
CN105884108B CN201610407029.0A CN201610407029A CN105884108B CN 105884108 B CN105884108 B CN 105884108B CN 201610407029 A CN201610407029 A CN 201610407029A CN 105884108 B CN105884108 B CN 105884108B
Authority
CN
China
Prior art keywords
waste water
ammonolysis
treatment
obtains
water
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.)
Active
Application number
CN201610407029.0A
Other languages
Chinese (zh)
Other versions
CN105884108A (en
Inventor
丁超
杨绮联
赵文超
吴勇前
陈磊
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 Qicai Eco Technology Co Ltd
Original Assignee
Zhejiang Qicai Eco Technology 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 Qicai Eco Technology Co Ltd filed Critical Zhejiang Qicai Eco Technology Co Ltd
Priority to CN201610407029.0A priority Critical patent/CN105884108B/en
Publication of CN105884108A publication Critical patent/CN105884108A/en
Application granted granted Critical
Publication of CN105884108B publication Critical patent/CN105884108B/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
    • C01—INORGANIC CHEMISTRY
    • C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
    • C01C1/00—Ammonia; Compounds thereof
    • C01C1/02—Preparation, purification or separation of ammonia
    • C01C1/08—Preparation of ammonia from nitrogenous organic substances
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
    • C01C1/00—Ammonia; Compounds thereof
    • C01C1/24—Sulfates of ammonium
    • C01C1/242—Preparation from ammonia and sulfuric acid or sulfur trioxide
    • 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
    • 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
    • C02F1/30—Treatment of water, waste water, or sewage by irradiation
    • 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
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/442—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
    • 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
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
    • 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
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C02F1/46176—Galvanic cells
    • 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
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
    • C02F1/4693—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis electrodialysis
    • 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
    • C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
    • 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
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/722—Oxidation by peroxides
    • 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
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
    • 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
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/727—Treatment of water, waste water, or sewage by oxidation using pure oxygen or oxygen rich gas
    • 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
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/74—Treatment of water, waste water, or sewage by oxidation with air
    • 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
    • C02F2101/10—Inorganic compounds
    • C02F2101/16—Nitrogen compounds, e.g. ammonia
    • 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
    • C02F2101/38—Organic compounds containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2301/00—General aspects of water treatment
    • C02F2301/04—Flow arrangements
    • C02F2301/046—Recirculation with an external loop
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2301/00—General aspects of water treatment
    • C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Water Treatment By Electricity Or Magnetism (AREA)
  • Physical Water Treatments (AREA)

Abstract

The invention discloses a kind for the treatment of process of ammonolysis waste water to make the amino on organic molecule fall off by light electrolysis and/or photocatalysis Decomposition organic matter, form free ammonia, it is dissolved in water in the form of inorganic ammonium salt, then free ammonia is collected or absorbed by membrane distillation, obtains ammonium hydroxide or ammonium salt.The present invention recycles ammonia using membrane distillation, and equipment is simple to operation.

Description

A kind for the treatment of process of ammonolysis waste water
Technical field
The present invention relates to a kind of field of waste water treatment, and in particular to a kind for the treatment of process of ammonolysis waste water.
Background technique
Ammonolysis waste water refers to the waste water generated when ammonolysis reaction occurs for organic matter, contains in ammonolysis waste water and mainly contains inorganic trip From ammonia, a small amount of reaction raw materials or product (including organic amine compound).Such as: paranitrochlorobenzene ammonolysis waste water, 2,4- dinitros Chlorobenzene ammonolysis waste water.Waste water similar to its nature further includes that T acid neutralizes waste water, in tobias acid and waste water, diallyl ammonolysis Waste water etc. is a kind of to neutralize waste water.
The prior art to the processing of ammonolysis waste water be usually in and/or blow ammonia, condensing crystallizing or burning, above method cost High, processing is not thorough, waste of resource.
Summary of the invention
The present invention provides a kind for the treatment of process of ammonolysis waste water, by light electrolysis and photocatalysis Decomposition organic matter, forms trip From ammonia.Then free ammonia is collected or is absorbed by membrane distillation, obtain ammonium hydroxide or ammonium salt.
The technical solution adopted by the present invention is that:
A kind for the treatment of process of ammonolysis waste water, the described method comprises the following steps:
(1) it pre-processes: ammonolysis waste water is pre-processed, the pretreatment is the processing of decomposing organic matter, the decomposition The processing step of organic matter includes one or both of Fe-C light electrolysis, photocatalysis；Preferably, by ammonolysis waste water successively into Row Fe-C light electrolysis, photochemical catalytic oxidation；Obtain pretreated waste water；
The operating procedure of the Fe-C light electrolysis is:
The pH value of waste water to be processed is adjusted to 2-3.5, Fe powder and active carbon dosage are respectively the 0.5- of wastewater quality 3.0% and 0.1-0.3%, stirring at normal temperature react 1-5h, then pH value are adjusted to flocculate to 8-10, the micro- electricity of Fe-C is obtained after filtering Solution treated waste water；
The operating procedure of the photochemical catalytic oxidation is:
Waste water to be processed is adjusted into pH value to 3-6, hydrogen peroxide, the matter for adding quality and waste water of hydrogen peroxide are added thereto The ratio between amount is (0.2-1%) × (the COD numerical value ÷ 1000 in waste water), under mercury lamp prolonged exposure, is kept for 20-50 DEG C of temperature, Aeration reaction 2-5 hours, the waste water after obtaining Treatment by Photocatalysis Oxidation；The unit of COD numerical value in waste water is mg/L.Hydrogen peroxide Mass percentage concentration be generally 30~35%.
(2) membrane distillation
The pretreated waste water that step (1) obtains is adjusted to alkalinity (preferably tune pH 9-12), is warming up to 15- after filtering It 60 DEG C (preferably 40~60 DEG C), is handled by membrane distillation and removes free ammonia, in membrane distillation processing, the flow velocity of preferably waste water is 0.01-0.5m/s, absorbent are water or the sulfuric acid or hydrochloric acid of 5%-10%, the flow velocity 0.01-0.5m/s of absorbent, membrane distillation mistake Cheng Zhong, free ammonia reach by distillation film and absorb side；Absorbent in membrane distillation for absorbing free ammonia is water or mass fraction The sulfuric acid or hydrochloric acid of 5%-10%；Further, when the absorbent is water, obtained absorbing liquid is ammonium hydroxide, absorbent 5%- When 10% sulfuric acid or hydrochloric acid, obtained absorbing liquid is ammonium sulfate or ammonium chloride solution.
It is preferred that absorbent is the sulfuric acid or hydrochloric acid of mass fraction 5%-10%, and during membrane distillation, keep absorbent Mass percentage concentration is 5% or more.
After membrane distillation is handled, the NH of membrane distillation water outlet3- N concentration can be down to 50mg/L or less；
Ammonolysis waste water of the present invention refers to the waste water generated when ammonolysis reaction occurs for organic matter, mainly contains in ammonolysis waste water There are inorganic free ammonia, a small amount of reaction raw materials and/or the product containing organic amine compound.Ammonolysis waste water of the present invention includes Paranitrochlorobenzene ammonolysis waste water, 2,4-dinitrochlorobenzene ammonolysis waste water.Waste water similar to its nature further includes that the neutralization of T acid is useless In water, tobias acid and waste water, diallyl ammonolysis waste water etc. are a kind of neutralizes waste water.
Further preferably, the present invention is to the waste water containing aniline, chloronitrobenzene, nitroaniline, chloronitrobenzene amine etc. With preferable treatment effect.
In above-mentioned processing step, by micro-electrolysis reaction, organic matter chain rupture is decomposed, and amino is fallen down from organic matter chain Come, forms free ammonia；Photocatalysis can decompose organic matter, and amino falls down from organic matter chain, form free ammonia.By locating in advance It manages in obtained treatment fluid and is substantially free of organic object, treatment fluid is adjusted to alkalinity, free ammonia is overflowed from water, passes through distillation Film reaches the other side of film, is collected or absorbs, and obtains ammonium hydroxide or ammonium salt.
Amino can be reduced to by the nitro in organic matter, after reduction by micro-electrolysis reaction for the organic matter containing nitro The difficulty of continuous processing improves the ammonia nitrogen rate of recovery；In photocatalysis, by light electrolysis generate small molecule further decompose, make amino from It is split away off on organic matter, becomes free ammonia；It is substantially free of organic object in waste water after photocatalysis, by distilling film, can be recycled To ammonium hydroxide or ammonium salt.
The waste water more complex for organic components humidification-type can aoxidize in pretreatment, improve the decomposition effect of organic matter Rate obtains cleaner liquid containing ammonia treatment.
For the removal rate for improving metal ion, can be filtered blooming before membrane distillation, generally two step mistake of ultrafiltration-nanofiltration Filter.
So preferably, processing method of the present invention can also be implemented by following steps:
(1) processing that the pretreatment is decomposing organic matter is pre-processed, the processing of the decomposing organic matter includes Fe-C micro- Ammonolysis waste water is successively carried out Fe-C light electrolysis, photochemical catalytic oxidation or successively by ammonolysis by electrolysis, one of photochemical catalytic oxidation Waste water carries out Fe-C light electrolysis, wet oxidation processing, photochemical catalytic oxidation or ammonolysis waste water is successively carried out wet oxidation processing, light Catalysis oxidation；Pretreatment stage needs to handle the COD of waste water to 500mg/L or less；
Further, the pretreatment is successively by ammonolysis waste water progress Fe-C light electrolysis, wet oxidation processing, photocatalytic-oxidation When change, the pre-treatment step includes following three step:
(1-a) Fe-C light electrolysis
The pH of waste water is adjusted to 3 or so, reaction process adds acid, keeps pH constant, Fe powder and active carbon dosage are each From the 0.5-3.0% and 0.1-0.3% for wastewater quality, 3-5h is reacted, after then adjusting pH to 9-10 flocculation, filtering, filtrate adds 0.02-0.2% activated carbon adsorption, filtering, obtains treatment fluid 1；
(1-b) wet oxidation
Treatment fluid 1 carries out wet oxidation, and the organic amine that step (1) reduction obtains is decomposed, obtained by oxygenolysis organic matter Ammonium salt, and larger molecular organics are resolved into small molecule；Wet oxidation conditions: temperature is 200-300 DEG C, pressure 1- 10MPa is oxidant with air or oxygen；
(1-c) photochemical catalytic oxidation
Wet oxidation treatment fluid adjusts pH to 3-6, and hydrogen peroxide, the matter for adding quality and waste water of hydrogen peroxide are added thereto The ratio between amount is (0.2-1%) × (the COD numerical value ÷ 1000 in waste water), under mercury lamp prolonged exposure, is kept for 20-50 DEG C of temperature, Aeration reaction 2-5 hours, obtain treatment fluid 2；
(2) film filters
Treatment fluid 2 is adjusted to alkalinity, is filtered by two step of ultrafiltration-nanofiltration, obtains clean treatment fluid；
(3) membrane distillation
The treatment fluid that step (2) obtains carries out membrane distillation, recycles free ammonia, and the temperature that treatment fluid is arranged is 15-60 DEG C, flows Fast 0.01-0.5m/s, pH 9-12 obtain ammonium hydroxide with the cooling ammonia and/or vapor for passing through film of air, and membrane distillation goes out Water is treatment fluid 3.
Preferably, photochemical catalytic oxidation of the invention can be light Fenton, using Fe-C light electrolysis generate it is ferrous from Son is used as catalyst, can also add ferrous ion, under the irradiation of ultraviolet lamp, while hydrogen peroxide is added in right amount thereto, may be used also To add the photochemical catalyst such as TiO of synthesis2Deng.
Preferably, when being used in conjunction with light electrolysis, can be carried out using following mode of operation when photocatalytic-oxidation turns to light Fenton Pretreatment:
(1-A) light electrolysis: it is respectively waste water that the pH of waste water to be processed, which is adjusted to 2~3.5, Fe powder and active carbon dosage, The 0.5-3.0% and 0.1-0.3% of quality, stirring at normal temperature react 1-5h, adsorbent absorption (one are added in the filtrate being obtained by filtration As plus plus 0.01-0.2% activated carbon adsorption), the waste water after Fe-C microelectrolysis processing is obtained after filtering；
(1-B) light Fenton: the waste water after Fe-C microelectrolysis processing is adjusted into pH to 3-6, hydrogen peroxide, dioxygen are added thereto The add quality and the mass ratio of waste water of water are 0.2-1% × (the COD numerical value in waste water is divided by 1000), are persistently shone in mercury lamp It penetrates down, is kept for 20-50 DEG C of temperature, aeration reaction 2-5 hours, then pH value is adjusted to flocculate to 8-10, filtrate matter is added in filtering, filtrate The 0.01-0.2% active carbon of amount is adsorbed, the waste water after Treatment by Photocatalysis Oxidation is obtained after filtering；
Preferably, catalyst can be added in wet oxidation, catalytic wet oxidation is carried out；It can also be using normal temperature and pressure Catalytic wet oxidation adds heavy metal catalyst using hydrogen peroxide as oxidant.
Preferably, before ultrafiltration-nanofiltration, conventional filtration can be done in the present invention, the gold generated during adjusting pH is avoided Belong to clogging deposits fenestra.
Preferably, deamination film can be used in membrane distillation of the present invention, by the ammonia of air purging abjection, led to It is absorbed in absorbent, when absorbent is water, ammonium hydroxide can be obtained, when absorbent is acid solution, ammonium salt is can be obtained in absorbing liquid.
Preferably, the water outlet of membrane distillation can be mixed further with raw wastewater, it is circulated back to step (1) and is handled.Film In distillation water outlet when saliferous, concentration and recovery salt or bronsted lowry acids and bases bronsted lowry can be recycled by bipolar membrane electrodialysis.
The beneficial effects of the present invention are:
1, the ammonia in ammonolysis waste water is recycled, the cost of wastewater treatment is reduced；
2, method is simple to operation, and the removal rate of organic matter and ammonia nitrogen is all up to 90% or more.
3, the more conventional method for concentration temperature of distillation film is low, is not easy to bring remaining low-boiling-point organic compound in absorbing liquid into, The quality of obtained ammonium hydroxide or ammonium salt is high.
Four, specific embodiment
Embodiment one
The paranitroanilinum waste water that paranitrochlorobenzene ammonolysis obtains, COD=29000mg/L, reddish brown, opaque, tool There are strong pungent smell, pH=8.6, ammonia nitrogen 647mg/L, total nitrogen 3351mg/L.
(1) Fe-C light electrolysis: taking paranitroanilinum waste water, is absorbed with 10% sulfuric acid solution in step (3) deamination film process The pH of waste water is adjusted to 3, Fe powder to the acid absorbing liquid generated after ammonia and active carbon dosage is respectively the 3.0% of wastewater quality With 0.3%, 3h is reacted, 0.1% active carbon (on the basis of filtrate quality) is added after filtering in filtrate, after being stirred to react 0.5h Filtering, obtained filtrate are treatment fluid 1, measure its water quality: COD=3700mg/L, NH3-N=1900mg/L, pH=6.81.
(2) photocatalysis: the treatment fluid 1 that step (1) obtains adjusts pH to 5, and at the uniform velocity the 4.0% of the quality of addition waste water is double Oxygen water (mass concentration of hydrogen peroxide is 30%), rate of addition 0.01%/min keep reaction temperature under mercury lamp prolonged exposure Degree is 25 DEG C, and aeration reaction 3 hours, it was 10 that liquid feeding alkali (sodium hydroxide solution that mass concentration is 30%), which adjusts pH, and flocculate 0.5h It filters, to filtrate plus 0.02% activated carbon adsorption 0.5h of filtrate quality, photocatalysis water outlet is obtained by filtration.Photocatalysis is discharged water Matter: COD=250mg/L, NH3- N=2800mg/L, pH=6.81.
(3) deamination film: liquid alkaline is added in photocatalysis water outlet and adjusts pH to 11.3, waste water flow velocity is 0.21m/s, configuration 10% Sulfuric acid solution absorbs ammonia, absorbs flow velocity 0.07m/s.Treatment fluid temperature is set as 50 DEG C, and absorbent is room temperature, film The concentrated sulfuric acid is added to guarantee 5% or more the mass percentage concentration of sulfuric acid in absorbent in distillation processing, and 30min measures NH3-N Concentration is reduced to 37mg/L, pH=9.84, and absorbing liquid obtains more pure ammonium salt, and is acidity, can be used for the waste water of step (1) In the step of adjusting pH to 3.
It is discharged COD=220mg/L, NH3- N=37mg/L, the bottom water that can be used for paranitrochlorobenzene ammonolysis technique use
Embodiment two
Amino benzene analog waste water, deep blue purple color, COD=5100mg/L, TOC=2400mg/L, pH=9.1, ammonia nitrogen 2100mg/ L, total nitrogen 4600mg/L.
(1) photocatalysis: taking amino benzene analog waste water to adjust pH to 5, and the dioxygen of wastewater quality 5.0% is added thereto in batches Water, under mercury lamp prolonged exposure, keeping reaction temperature is 25 DEG C, aeration reaction 4 hours.Photocatalysis effluent quality: COD= 110mg/L, NH3- N=3900mg/L, pH=5.8.
(2) deamination film: be added in photocatalysis water outlet liquid alkaline (mass concentration be 30% sodium hydroxide solution) adjust pH to 11.5, waste water flow velocity is 0.25m/s, and 10% sulfuric acid solution of configuration absorbs gaseous free ammonia, absorbs flow velocity 0.1m/s. Waste water temperature is 60 DEG C, and absorbent is room temperature, to add the concentrated sulfuric acid in membrane distillation processing to guarantee the quality of sulfuric acid in absorbent 5% or more percentage concentration, 40min measures NH3- N concentration is reduced to 28mg/L, pH=9.5, and absorbing liquid obtains more pure ammonium Salt.
It is discharged COD=121mg/L, NH3- N=28mg/L can be used for production.
Embodiment three
Certain ammonolysis mother liquor waste water, main component NH3·H2O、NH4Cl, 2,4- dinitroaniline, chloro dinitroaniline Compound etc., deep isabelline relatively transparent liquid, distributes pungent ammonia taste.Its pH=9.38, COD=1941mg/L, NH3- N= 2985mg/L, TN=4800mg/L, solid content 3.11%.
(1) Fe-C light electrolysis: the pH of waste water is adjusted to 2, Fe powder and active carbon dosage is respectively wastewater quality 2.0% and 0.2%, react 3h.Adding alkali to adjust wastewater pH is 8.5, and effluent quality is obtained by filtration: COD=in stirring flocculation 0.5h 400mg/L, NH3- N=4400mg/L.
(2) ultrafiltration-nanofiltration: step (1) water outlet adjusts pH to 11.7, passes sequentially through ultrafiltration membrane and nanofiltration membrane under room temperature, obtains To water outlet in COD about 50mg/L, ammonia nitrogen about 4310mg/L.
(3) deamination film: being heated to 50 DEG C for the water outlet of step (2), passes through deamination film, 10% sulfuric acid with the flow velocity of 0.3m/s Solution (room temperature, 25 DEG C) is flowed through with the speed of 0.1m/s in the deamination film other side, absorbs gaseous free ammonia.It is detected in absorption process The concentration of sulfuric acid adds the concentrated sulfuric acid when concentration is lower than 5%, keeps the sulfuric acid concentration of absorbent 5% or more, reaction 30min is surveyed NH must be discharged3- N concentration is reduced to 59mg/L, pH=9.2, and absorbing liquid obtains more pure ammonium salt.
It is discharged COD=67mg/L, NH3- N=59mg/L can be used for production.
Example IV
H acid neutralizes in waste water, containing naphthalene sulfonic acids Ammonia organic matter and ammonium sulfate, pH=10, COD=21941mg/L, NH3- N=10785mg/L, TN=4800mg/L, solid content 17.11%.
(1) wet oxidation: waste water is heated to 230 DEG C, pressure 3MPa, using oxygen as oxidant, high-temperature high-voltage reaction 1h, It is added 0.2% diatomite in obtained water outlet, after agitation and filtration, obtains filtrate, the COD of filtrate is 3860mg/L, and ammonia nitrogen is 13377mg/L, total nitrogen 120mg/L.
(2) light Fenton: the liquid that step (1) obtains adjusts pH to 4, and after 0.2% ferrous sulfate is added thereto, dioxygen is added Water, the dosage of hydrogen peroxide and the mass ratio of waste water are 3% (on the basis of the quality of waste water), under mercury lamp prolonged exposure, are protected 30 DEG C of temperature are held, aeration reaction 2 hours, obtains treatment fluid 1.
(3) ultrafiltration-nanofiltration: step (2) water outlet pH is adjusted to 11.7, after simple filtration, passes sequentially through ultrafiltration membrane under room temperature And nanofiltration membrane, COD about 50mg/L in obtained water outlet, ammonia nitrogen about 14310mg/L, total nitrogen are less than 10mg/L.
(4) deamination film: being heated to 40 DEG C for the water outlet of step (3), passes through deamination film, 10% sulfuric acid with the flow velocity of 0.3m/s Solution (room temperature, 25 DEG C) is flowed through with the speed of 0.1m/s in the deamination film other side, absorbs gaseous free ammonia.It is detected in absorption process The concentration of sulfuric acid adds the concentrated sulfuric acid when concentration is lower than 5%, keeps the sulfuric acid concentration of absorbent 5% or more, reaction 30min is surveyed NH must be discharged3- N concentration is reduced to 59mg/L, pH=9.2, and absorbing liquid obtains more pure ammonium salt.
(5) salt recycles: the aobvious acidity of deamination film water outlet, COD 61mg/L.After the water outlet of deamination film is by distillation film concentration Treatment fluid in salt content be 30%, by bipolar membrane electrodialysis treatment, obtain 10% sulfuric acid and 9% sodium hydroxide.

Claims (4)

1. a kind for the treatment of process of ammonolysis waste water, the ammonolysis waste water refers to the waste water generated when ammonolysis reaction occurs for organic matter, Characterized by comprising the following steps:
(1) it pre-processes: ammonolysis waste water is pre-processed, the pretreatment is the processing of decomposing organic matter, and the decomposition is organic Ammonolysis waste water is successively carried out Fe-C light electrolysis, wet oxidation processing, photochemical catalytic oxidation by the processing of object；
The pre-treatment step includes following three step:
(1-a) Fe-C light electrolysis
The pH of waste water is adjusted to 2-3.5, reaction process adds acid, keeps pH constant, Fe powder and active carbon dosage are respectively The 0.5-3.0% and 0.1-0.3% of wastewater quality react 3-5h, and after then adjusting pH to 9-10 flocculation, filtering, filtrate adds 0.02- 0.2% activated carbon adsorption, filtering, obtains treatment fluid 1；
(1-b) wet oxidation
Treatment fluid 1 carries out wet oxidation, and the organic amine that step (1) reduction obtains is decomposed, obtains ammonium by oxygenolysis organic matter Salt, and larger molecular organics are resolved into small molecule；Wet oxidation conditions: temperature is 200-300 DEG C, pressure 1-10MPa, It is oxidant with air or oxygen；
(1-c) photochemical catalytic oxidation
Wet oxidation treatment fluid adjusts pH to 3-6, is added hydrogen peroxide thereto, the quality for adding quality and waste water of hydrogen peroxide it Than being kept for 20-50 DEG C of temperature, aeration under mercury lamp prolonged exposure for (0.2-1%) × (the COD numerical value ÷ 1000 in waste water) Reaction 2-5 hours, obtains treatment fluid 2；
(2) film filters: treatment fluid 2 is adjusted to alkalinity, is filtered by two step of ultrafiltration-nanofiltration, obtains clean treatment fluid；
(3) membrane distillation: being adjusted to alkalinity for the pretreated waste water that step (2) obtains, be warming up to 40-60 DEG C after filtering, leads to Membrane distillation processing removal free ammonia is crossed, the absorbent for being used to absorb free ammonia in membrane distillation is water or mass fraction 5%-10% Sulfuric acid or hydrochloric acid.
2. treatment process as described in claim 1, which is characterized in that in the step (2), when the absorbent is water, obtain The absorbing liquid arrived is ammonium hydroxide；When absorbent is the sulfuric acid or hydrochloric acid of mass fraction 5%-10%, obtained absorbing liquid is ammonium sulfate Or ammonium chloride solution.
3. treatment process as described in claim 1, which is characterized in that in the step (3), in the membrane distillation processing, give up The flow velocity of water is 0.01-0.5m/s, the flow velocity 0.01-0.5m/s of absorbent.
4. treatment process as described in claim 1, which is characterized in that in the step (1), the pretreatment stage is by waste water COD handle to 500mg/L or less.
CN201610407029.0A 2016-06-08 2016-06-08 A kind for the treatment of process of ammonolysis waste water Active CN105884108B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610407029.0A CN105884108B (en) 2016-06-08 2016-06-08 A kind for the treatment of process of ammonolysis waste water

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610407029.0A CN105884108B (en) 2016-06-08 2016-06-08 A kind for the treatment of process of ammonolysis waste water

Publications (2)

Publication Number Publication Date
CN105884108A CN105884108A (en) 2016-08-24
CN105884108B true CN105884108B (en) 2019-06-18

Family

ID=56730154

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610407029.0A Active CN105884108B (en) 2016-06-08 2016-06-08 A kind for the treatment of process of ammonolysis waste water

Country Status (1)

Country Link
CN (1) CN105884108B (en)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106336055B (en) * 2016-10-27 2019-04-30 浙江奇彩环境科技股份有限公司 A kind of processing of acid-bearing wastewater utilizes technique
CN106673175A (en) * 2016-10-28 2017-05-17 浙江奇彩环境科技股份有限公司 Method for advanced treatment of organic wastewater through oxidation of chlorine
CN109133539A (en) * 2018-10-17 2019-01-04 苏州艾吉克膜科技有限公司 The processing unit and treatment process of coal chemical industry gasification burner waste water
CN109824199B (en) * 2019-03-22 2021-08-17 盛隆资源再生（无锡）有限公司 Method for treating high COD (chemical oxygen demand) membrane production wastewater containing sodium hypochlorite and PVP (polyvinyl pyrrolidone)
CN111533348A (en) * 2020-05-22 2020-08-14 云南云铜锌业股份有限公司 Method and device for removing ammonia nitrogen in zinc smelting wastewater
CN112441689B (en) * 2020-09-29 2022-12-13 武汉天源环保股份有限公司 Membrane concentrate harmless treatment system and method
CN113087296B (en) * 2021-04-07 2021-12-07 江苏瑞恒新材料科技有限公司 Method for treating nitrochlorobenzene wastewater

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102757149A (en) * 2012-08-06 2012-10-31 哈尔滨工业大学 Multi-stage membrane distillation treating method for ammonia nitrogen wastewater
CN104211246A (en) * 2013-06-03 2014-12-17 洁海瑞泉膜技术（北京）有限公司 Method for treating low-concentration ammonia-nitrogen wastewater or feed liquid
CN105152421A (en) * 2015-09-11 2015-12-16 东莞市绿巨人环境科技有限公司 Treatment method of distillation extraction waste liquid in fine chemical engineering production

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8216445B2 (en) * 2006-10-31 2012-07-10 Wisconsin Alumni Research Foundation Nanoporous insulating oxide deionization device having asymmetric electrodes and method of use thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102757149A (en) * 2012-08-06 2012-10-31 哈尔滨工业大学 Multi-stage membrane distillation treating method for ammonia nitrogen wastewater
CN104211246A (en) * 2013-06-03 2014-12-17 洁海瑞泉膜技术（北京）有限公司 Method for treating low-concentration ammonia-nitrogen wastewater or feed liquid
CN105152421A (en) * 2015-09-11 2015-12-16 东莞市绿巨人环境科技有限公司 Treatment method of distillation extraction waste liquid in fine chemical engineering production

Also Published As

Publication number Publication date
CN105884108A (en) 2016-08-24

Similar Documents

Publication Publication Date Title
CN105884108B (en) A kind for the treatment of process of ammonolysis waste water
CN105800886B (en) The resource utilization of high-concentration hardly-degradable salt-containing organic wastewater utilizes treatment process
Han et al. Trihalomethanes (THMs) precursor fractions removal by coagulation and adsorption for bio-treated municipal wastewater: molecular weight, hydrophobicity/hydrophily and fluorescence
CN105800885B (en) The resource utilization of high-concentration hardly-degradable salt-containing organic wastewater utilizes processing system
CN110117115B (en) Treatment method and equipment for recycling industrial waste salt
CN104876380B (en) A kind of processing of organic copper-containing wastewater of high concentration and the recovery method of copper
CN104556521A (en) Treatment method for condensed wastewater in disperse blue 56 production process
TW201942073A (en) Process for the work-up and reuse of salt-containing process water
CN104829027A (en) Technology for processing disperse blue 56 reduction mother liquor waste water
CN105236611A (en) Processing method of benzene waste water
CN105419383A (en) Improved dye synthesis process
CN104591449A (en) Method for removing bromine from disperse dye wastewater
WO2019159197A1 (en) Method and apparatus for regenerating a working salt solution in salt purification
CN105906100B (en) A kind of processing method of methyl sulfur bacterium panacen waste water
CN105645634B (en) A kind of processing method of epoxy resin synthetic wastewater
CN106167332A (en) A kind of aniline intermediate produces the recycling processing method of waste water
CN108793558B (en) Method for treating wastewater generated in activated carbon production by phosphoric acid activation method
CN105110545B (en) The handling process of double cyanogen waste water in disperse blue 60 production process
CN106315916A (en) Deep treatment method of antibiotic wastewater
CN104692576B (en) A kind of processing method of isatin wastewater
Mugwili et al. An update on sustainabilities and challenges on the removal of ammonia from aqueous solutions: A state-of-the-art review
CN105217863B (en) A kind of handling process of disperse blue 60 production waste water
CN209322659U (en) A kind of waste water recycling treatment system
CN105110515A (en) Treatment method of DSD (4, 4'-Diaminostilbene-2, 2'-disulfonic) acid wastewater
CN113880217B (en) Method for treating pesticide wastewater containing nitrogen heterocycles

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant