CN106517577B - The treatment process of acidic arsenic-containing waste water - Google Patents

The treatment process of acidic arsenic-containing waste water Download PDF

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CN106517577B
CN106517577B CN201611019998.5A CN201611019998A CN106517577B CN 106517577 B CN106517577 B CN 106517577B CN 201611019998 A CN201611019998 A CN 201611019998A CN 106517577 B CN106517577 B CN 106517577B
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arsenic
waste water
solution
containing waste
acidic
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CN106517577A (en
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王艳
朱刘
陈辉
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Kunming Forerunner New Material Technology Co ltd
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Vital Materials Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00Multistage treatment of water, waste water or sewage
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/42Treatment of water, waste water, or sewage by ion-exchange
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/52Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/5236Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/52Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/54Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
    • C02F1/56Macromolecular compounds
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/66Treatment of water, waste water, or sewage by neutralisation; pH adjustment
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/72Treatment of water, waste water, or sewage by oxidation
    • C02F1/76Treatment of water, waste water, or sewage by oxidation with halogens or compounds of halogens
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/10Inorganic compounds
    • C02F2101/103Arsenic compounds
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2301/00General aspects of water treatment
    • C02F2301/08Multistage treatments, e.g. repetition of the same process step under different conditions

Abstract

The present invention provides a kind for the treatment of process of acidic arsenic-containing waste water to be oxidized to pentavalent arsenic for trivalent arsenic using chlorate or/and perchlorate as oxidant, inorganic flocculating agent is successively added, organic flocculant carries out flocculation sedimentation dearsenification.The oxidant that the present invention uses keeps solution oxide more thorough, reduces the input amount of inorganic flocculating agent, and then reduce the amount of the slag containing arsenic, reduces the processing cost of the subsequent slag containing arsenic.Present invention process is simple, at low cost, and arsenic removal efficiency is high, has a wide range of application, treated waste water arsenic content < 50ppb, can meet the emission request of different discharge standards.

Description

The treatment process of acidic arsenic-containing waste water
Technical field
The invention belongs to heavy metal industrial effluent processing technology fields, especially a kind of to be suitable for arsenic chemical industry and arsenic smelting phase The treatment process of the arsenic concentration height, the industrial wastewater that acidity is big, water quality is complicated that close industry discharge, belongs to a kind of acidic arsenic-containing waste water Deep treatment method.
Background technique
Arsenic is a kind of carcinogen of generally acknowledged high poison, is widely used in and prepares the semiconductor materials such as GaAs, due to semiconductor Material is high to the purity requirement of arsenic, it is therefore desirable to carry out arsenic purification in front end, in purification process, a large amount of arsenic steam are inhaled through hydrochloric acid After receipts, acidic high-strength arsenic-containing waste water is formed, the arsenic content of this waste water is often up to 1 ~ 10g/L or more.
The processing method of arsenic-containing waste water mainly has chemical method, physical method, bioanalysis etc. at present.Bioanalysis mainly utilizes heat-resisting Acidophilus iron aoxidizes Gu Bu Shi acid bacterium and converts the high scorodite of arsenic content for arsenic, thus achieve the purpose that handle arsenic in waste water, it should Method requires reaction temperature high, must not have other impurities in waste water, and only to As5+There is preferable effect, therefore application range is big It is big to reduce.Physical method is mainly swapped the cation in the arsenic and resin in waste water using dedicated ion exchange resin, from And achieving the purpose that arsenic removal, this method is commonly used to the advanced treating of processing low concentration arsenic-containing waste water or arsenic-containing waste water.
Chemical method mainly includes lime precipitation, sulfurization-precipitation method, calcium-molysite jointly removing arsenic method, molysite deposition method etc..Stone The cardinal principle of the grey precipitation method: 4 ~ 10 times of arsenic mol of lime is added into waste water, wastewater pH is adjusted to 12 or more, makes waste water In As3+、As5+The precipitatings such as calcium arsenate, the calcium arsenite of slightly solubility are formed with the calcium of addition, so that the arsenic in water be effectively reduced Content adjusts wastewater pH finally by the methods of acid adding, and waste water is made to reach discharge or subsequent processing requirement;Sulphide precipitation master It wants principle: in acid condition, utilizing the As of different valence statem+It can be with S2-Form infusible precipitate As2Sm;Calcium-molysite, which is combined, to be removed Arsenic method cardinal principle: after waste water is pre-oxidized, molysite is added, adjusts pH, calcium precipitate agent is added, forms calcium arsenic slag.Sulfide is heavy The solid waste containing arsenic that shallow lake method and calcium-molysite jointly removing arsenic method obtain easily dissolves out, and there are hidden danger for outdoor stockpiling.Traditional molysite deposition method The disadvantages of waste residue of generation can stablize preservation, but that there are settling velocities is slow, and waste residue viscosity is big.Therefore the scum containing arsenic how is reduced Amount, improves the removal efficiency of arsenic, is the key that processing arsenic-containing waste water problem.
Patent CN103043812A discloses a kind of deep treatment method of arsenic-containing waste water, and this method is by aoxidizing trivalent arsenic It is oxidized to pentavalent arsenic, molysite and macromolecule organic flocculating agent precipitating arsenic is being added, is accelerating settling velocity, shortens the sedimentation time, The removal efficiency to arsenic is increased, but adds the amount of molysite, Fe/As molar ratio in solution is made to reach 5 ~ 50, what is obtained contains arsenic Scum amount is very big.
Therefore, it is necessary to provide a kind for the treatment of process of acidic arsenic-containing waste water, solve the problems, such as that the amount of scum containing arsenic is big.
Summary of the invention
To solve the above problems, that the present invention provides a kind of arsenic removals is high-efficient, waste residue amount is few and can stablize the acidity saved The treatment process of arsenic-containing waste water.
To realize foregoing purpose, the present invention adopts the following technical scheme: the treatment process of acidic arsenic-containing waste water comprising pre- Oxidation, level-one flocculation sedimentation:
Pre-oxidation: being added oxidant in oxytropism arsenic-containing waste water, carry out oxidation reaction, obtain the first solution;
Level-one flocculation sedimentation: the first inorganic flocculating agent being added into the first solution, is stirred to react, and adjusts pH to 7 ~ 12, then The first organic flocculant is added, is stirred to react, obtains the first mixed liquor, after the layering of the first mixed liquor natural subsidence, consolidate Liquid separation, obtains the second solution and the first slag containing arsenic, detects arsenic content in the second solution;
Dissociate H in the acidic arsenic-containing waste water+Concentration is greater than 0.1mol/L;
The oxidant is sodium perchlorate, sodium chlorate, any one or more in calcium chlorate.
As a further improvement of the present invention, second solution need to be through second level flocculation sedimentation, concrete operations are as follows: to second The second inorganic flocculating agent is added in solution, is stirred to react, adjusts pH to 7 ~ 13, adds the second organic flocculant, be stirred to react, The second mixed liquor is obtained, after the second mixed liquor natural subsidence, is separated by solid-liquid separation, obtains third solution and the second slag containing arsenic, Detect arsenic content in third solution.
As a further improvement of the present invention, the third solution need to be adsorbed by chelating ion exchange resin, absorption Rate is 0.1m3/h~2 m3/ h, waste water after being adsorbed discharge after detection reaches emission request.
As a further improvement of the present invention, second solution need to be adsorbed by chelating ion exchange resin, absorption Rate is 0.1m3/h~2 m3/ h, waste water after being adsorbed discharge after detection reaches emission request.
As a further improvement of the present invention, the molar ratio of the oxidant and arsenic of the addition is (0.2 ~ 0.9): 1.
As a further improvement of the present invention, first inorganic flocculating agent is bodied ferric sulfate, in iron chloride, ferric sulfate Any one or more;Second inorganic flocculating agent be bodied ferric sulfate, iron chloride, in ferric sulfate any one or it is more Kind.
As a further improvement of the present invention, mole of the first inorganic flocculating agent and arsenic is added in the level-one flocculation sedimentation Than for (0.8 ~ 1): 1.
As a further improvement of the present invention, the second inorganic flocculating agent dosage is 1 ~ 10g/L.
As a further improvement of the present invention, first organic flocculant is polyacrylamide, in Sodium Polyacrylate It is one or more;Second organic flocculant is one of polyacrylamide, Sodium Polyacrylate or a variety of.
As a further improvement of the present invention, the mass fraction of the first organic flocculant of the addition is 0.01 ~ 1.0%, Dosage is 1 ~ 10ml;The mass fraction of second organic flocculant of the addition is 0.01 ~ 1.0%, and dosage is 1 ~ 10ml/ L。
The present invention by using one of sodium perchlorate, sodium chlorate, calcium chlorate or it is a variety of be used as oxidant, in acid item It is more thorough compared with other oxidants and low in cost to the oxidation effectiveness of arsenic under part;The dosage of oxidant is only other oxidations of tradition The 1/3 ~ 1/2 of medicament (hydrogen peroxide, calcium hypochlorite, sodium hypochlorite, potassium permanganate etc.) dosage, relative to aerating oxidation and other changes Medicament oxidation is learned, energy consumption substantially reduces, and has saved cost;The inorganic flocculating agent dosage added reduces 1/2 ~ 2/3 times, arsenic removal rate Up to 99.998% or more, reduce the amount of scum containing arsenic, save the cost.This technique can handle various concentration acidic arsenic-containing waste water, technique Simply, arsenic removal is high-efficient, and the amount of scum containing arsenic is few, and waste residue, which saves, to be stablized, low in cost, is really achieved and economizes on resources with industry containing arsenic The purpose of the harmless treatment of waste water.
Specific embodiment
Technical solution is clearly and completely described below in conjunction with the embodiment of the present invention, it is clear that described implementation Example is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this field is common Technical staff's every other embodiment obtained without making creative work belongs to the model that the present invention protects It encloses.
The present invention adopts the following technical scheme: the treatment process of acidic arsenic-containing waste water comprising pre-oxidation, level-one flocculation are heavy It forms sediment:
Pre-oxidation: being added oxidant in oxytropism arsenic-containing waste water, carry out oxidation reaction, obtain the first solution;
Level-one flocculation sedimentation: the first inorganic flocculating agent being added into the first solution, is stirred to react, and adjusts pH to 7 ~ 12, then The first organic flocculant is added, is stirred to react, obtains the first mixed liquor, after the layering of the first mixed liquor natural subsidence, consolidate Liquid separation, obtains the second solution and the first slag containing arsenic, detects arsenic content in the second solution;
Dissociate H in the acidic arsenic-containing waste water+Concentration is greater than 0.1mol/L;
The oxidant is sodium perchlorate, sodium chlorate, any one or more in calcium chlorate.
In technique provided by the invention, oxidant is added in oxytropism arsenic-containing waste water first, carries out 0.5 ~ 4h of oxidation reaction, Trivalent arsenic in waste water is oxidized to pentavalent arsenic, obtains the first solution.The oxidant is sodium perchlorate, sodium chlorate, calcium chlorate In any one or more;The molar ratio of oxidant and arsenic is preferably (0.2 ~ 0.9): 1, more preferably (0.3 ~ 0.7): 1;Oxidation Time is preferably 0.5 ~ 4h, more preferably 1 ~ 2h.Dissociate H in acidic arsenic-containing waste water handled by the present invention+Concentration is greater than 0.1mol/L can also contain Cu other than arsenic removal2+、Ni2+Deng.
In the present invention, the first inorganic flocculating agent is added into the first solution, is stirred to react, adjusting pH to 7 ~ 12, then plus Enter the first organic flocculant, be stirred to react, obtain the first mixed liquor, after the layering of the first mixed liquor natural subsidence, carries out solid-liquid Separation obtains the second solution and the first slag containing arsenic, detects the arsenic content in the second solution.First inorganic flocculating agent is preferably Bodied ferric sulfate, iron chloride, any one or more in ferric sulfate, more preferably ferric polysulfate solid;First nothing The molar ratio of machine flocculant and arsenic is (0.8 ~ 1): 1;The adjusting pH value is preferably 7 ~ 12, and more preferably 7 ~ 8;First nothing Machine flocculant is stirred to react time, preferably 10 ~ 60min, more preferably 30 ~ 60min;First organic flocculant is preferred For one of polyacrylamide, Sodium Polyacrylate or a variety of, more preferably polyacrylamide;First organic flocculant Mass fraction is preferably 0.01 ~ 1.0%, and more preferably 0.1 ~ 0.3%;The first organic flocculant dosage is preferably 1 ~ 10ml/L, more preferably 2 ~ 5ml/L.
It is further depth dearsenification in the present invention, the second solution can be subjected to second level flocculating setting, i.e., into the second solution The second inorganic flocculating agent is added, is stirred to react 10 ~ 60min, adjusts pH to 7 ~ 13, adds the second organic flocculant, stirring is anti- 1 ~ 30min is answered, the second mixed liquor is obtained, after the second mixed liquor natural subsidence, is separated by solid-liquid separation, third solution and are obtained Two slags containing arsenic detect arsenic content in third solution.Second inorganic flocculating agent is preferably bodied ferric sulfate, iron chloride, sulfuric acid Any one or more in iron, more preferably ferric polysulfate solid;The second inorganic flocculating agent dosage is preferably 1 ~ 10g/L, more preferably 4 ~ 8g/L;The adjusting pH value is preferably 7 ~ 13, and more preferably 7.5 ~ 9;Second organic flocculant Preferably one of polyacrylamide, Sodium Polyacrylate or a variety of, more preferably polyacrylamide;Second organic-flocculation The mass fraction of agent is preferably 0.01 ~ 1.0%, and more preferably 0.1 ~ 0.3%;The dosage of second organic flocculant is preferably 1 ~ 10ml/L, more preferably 2 ~ 5ml/L.
It is further depth dearsenification in the present invention, also the second solution or third solution can be passed through the dedicated chela of arsenic removal Mould assembly ion exchange resin, rate of adsorption 0.1m3/h~2 m3/ h, waste water can be arranged directly after detection is up to standard after obtained absorption It puts.
In the present invention, the chelating ion exchange resin is suitable for adsorbing the waste water of arsenic concentration 0.05mg/L ~ 1mg/L, It is particularly suitable for the low concentration arsenic-containing waste water of absorption arsenic concentration 0.05mg/l ~ 0.1mg/L, the common dedicated chelating ion of arsenic Exchanger resin, there is DTMA-200, MIEX-DOC (R), 201*7 etc., and following embodiment uses DTMA-200.
Technique provided by the invention can handle the acidic arsenic-containing waste water of various concentration, work as acidic arsenic-containing under field conditions (factors) As < 0.5g/L in waste water, and require that treated that waste water reaches first kind pollutant emission mark in " industrial wastewater discharge standard " Quasi- (As < 0.5mg/L) or when reaching As < 0.1mg/L, it can carry out pre-oxidizing-flocculation sedimentation process dearsenification;Work as acidic arsenic-containing As > 0.5g/L in waste water, and require that treated that waste water reaches first kind pollutant emission mark in " industrial wastewater discharge standard " Quasi- (As < 0.5mg/L) or when reaching As < 0.1mg/L, it can carry out pre-oxidizing-level-one flocculation sedimentation-second level flocculation sedimentation process de- Arsenic;As As > 0.5g/L in acidic arsenic-containing waste water, and requires that treated waste water reaches " water environment quality standard " GB3838-2002 it) when standard (As < 0.05mg/L) of Group III water, can carry out aoxidizing-level-one flocculation sedimentation-second level and flocculating sinking Shallow lake-resin adsorption process dearsenification;As As < 0.5g/L in acidic arsenic-containing waste water, and requires that treated waste water reaches " earth's surface water ring Border quality standard " GB3838-2002) Group III water standard (As < 0.05mg/L) when, can carry out pre-oxidizing-level-one flocculation is heavy Shallow lake-resin adsorption process dearsenification.
In the present invention, under identical other conditions, using above-mentioned oxidant, reduce the theoretical amount for the oxidant being added 2/3, the amount of inorganic flocculating agent reduces 1/2 ~ 2/3, and obtained the first slag containing arsenic and the second slag containing arsenic, the quantity of slag is less, waste residue is stable Property it is high, be not easy anti-molten, be conducive to the dangerous waste processing of the subsequent slag containing arsenic, reduce cost.
Embodiment 1.
Generated arsenic-containing waste water in certain Usiminas's production process is handled using the present invention, handles water 2m3, arsenic is dense Spend 1.87g/L, free acid concentration 1.19mol/L.
1) it pre-oxidizes: the sodium chlorate solid 2.6554kg of 0.5 times of arsenic mol being added into arsenic-containing waste water, aoxidize anti- 2h is answered, the first solution is obtained.
2) into the first solution, the solid ferric polysulfate of 0.90 times of arsenic mol level-one flocculation sedimentation: is added 8.976kg after being stirred to react 30min, is added solid sodium hydroxide and adjusts pH to 7.5, be sufficiently mixed 20min, add quality The polyacrylamide solution 4L that score is 0.3% is stirred to react 5min, forms a large amount of wadding body of slag containing arsenic, forms the first mixing Liquid.
3) level-one is separated by solid-liquid separation: will be layered after the first mixed liquor natural subsidence 2h, supernatant and lower layer's slag are used respectively Bag type filtering machine is filtered, and after filter residue forced air drying, requires to be stored according to dangerous waste;It is molten that second is formed after filtrate mixing Liquid, using ICP-MS analysis detection, measuring As concentration in filtrate is 27.4ppm.
4) second level flocculation sedimentation: adding ferric polysulfate solid by 1g/L into the second solution, after being stirred to react 20min, Solid sodium hydroxide is added and adjusts pH to 8.3, is sufficiently mixed 10min, it is molten to add the polyacrylamide that mass fraction is 0.3% Liquid 5L is stirred to react 3min, a large amount of wadding body of slag containing arsenic occurs, forms the second mixed liquor.
5) second level is separated by solid-liquid separation: will be layered after the second mixed liquor natural subsidence 0.5h, supernatant and lower layer's slag are made respectively It is filtered with bag type filtering machine, after filter residue forced air drying, requires to be stored according to dangerous waste;It is molten that third is formed after filtrate mixing Liquid, using ICP-MS analysis detection, measuring As concentration in filtrate is 95ppb.
6) third solution resin adsorption: is passed through into 1.5 tons of DTMA-200 chelating ion exchange resins, through-rate 1m3/ H, the waste water after adsorbing use ICP-MS analysis detection, and measuring As concentration in waste water is 9.4ppb.
Embodiment 2.
Generated arsenic-containing waste water in certain Usiminas's production process is handled using the present invention, handles water 2.5m3, arsenic Concentration 5.93g/L, free acid concentration 1.95mol/L.
1) it pre-oxidizes: the sodium perchlorate 12.1071kg of 0.5 times of arsenic mol being added into arsenic-containing waste water, aoxidize anti- 2.5h is answered, the first solution is obtained.
2) level-one flocculation sedimentation: into the first solution, the iron chloride solid 30.515kg of 0.95 times of arsenic mol is added, stirs After mixing reaction 40min, solid sodium hydroxide is added and adjusts pH to 7.8, is sufficiently mixed 20min, adding mass fraction is 0.5% Polyacrylamide solution 5.5L, be stirred to react 8min, form a large amount of wadding body of slag containing arsenic, the first mixed liquor of formation.
3) level-one is separated by solid-liquid separation: will be layered after the first mixed liquor natural subsidence 2.5h, supernatant and lower layer's slag are made respectively It is filtered with bag type filtering machine, after filter residue forced air drying, requires to be stored according to dangerous waste;It is molten that second is formed after filtrate mixing Liquid, using ICP-MS analysis detection, measuring arsenic concentration in filtrate is 57.2ppm.
4) second level flocculation sedimentation: adding ferric polysulfate solid by 3g/L into the second solution, after being stirred to react 30min, Solid sodium hydroxide is added and adjusts pH to 7.7, is sufficiently mixed 10min, it is molten to add the polyacrylamide that mass fraction is 0.3% Liquid 5L is stirred to react 3min, a large amount of wadding body of slag containing arsenic occurs, forms the second mixed liquor.
5) second level is separated by solid-liquid separation: will be layered after the second mixed liquor natural subsidence 1h, supernatant and lower layer's slag are used respectively Bag type filtering machine is filtered, and after filter residue forced air drying, requires to be stored according to dangerous waste;It is molten that third is formed after filtrate mixing Liquid, using ICP-MS analysis detection, measuring arsenic concentration in filtrate is 91ppb.
6) resin adsorption: by third solution by 1.5 tons of DTMA-200 chelating ion exchange resins, through-rate is 1.2m3/ h, the waste water after adsorbing use ICP-MS analysis detection, and measuring arsenic in waste water concentration is 8.2ppb.
Embodiment 3.
Generated arsenic-containing waste water in certain Usiminas's production process is handled using the present invention, handles water 5m3, arsenic is dense Spend 8.75g/L, free acid concentration 2.41mol/L.
1) it pre-oxidizes: the sodium chlorate solid 43.49kg of 0.7 times of arsenic mol being added into arsenic-containing waste water, aoxidize anti- 3.5h is answered, the first solution is obtained.
2) into the first solution, the ferric polysulfate solid of 1.0 times of arsenic mols level-one flocculation sedimentation: is added 116.67kg after being stirred to react 60min, is added solid sodium hydroxide and adjusts pH to 7.3, be sufficiently mixed 30min, add quality The polyacrylamide solution 15L that score is 0.8% is stirred to react 6min, forms a large amount of wadding body of slag containing arsenic, forms the first mixing Liquid.
3) level-one is separated by solid-liquid separation: will be layered after the first mixed liquor natural subsidence 3h, supernatant and lower layer's slag are used respectively Bag type filtering machine is filtered, and after filter residue forced air drying, requires to be stored according to dangerous waste;It is molten that second is formed after filtrate mixing Liquid, using ICP-MS analysis detection, measuring arsenic concentration in filtrate is 98.5ppm.
4) second level flocculation sedimentation: adding ferric polysulfate solid by 2g/L into the second solution, after being stirred to react 30min, Solid sodium hydroxide is added and adjusts pH to 8.6, is sufficiently mixed 10min, it is molten to add the Sodium Polyacrylate that mass fraction is 0.3% Liquid 15L is stirred to react 2min, a large amount of wadding body of slag containing arsenic occurs, forms the second mixed liquor.
5) second level is separated by solid-liquid separation: will be layered after the second mixed liquor natural subsidence 1.5h, supernatant and lower layer's slag are made respectively It is filtered with bag type filtering machine, after filter residue forced air drying, requires to be stored according to dangerous waste;It is molten that third is formed after filtrate mixing Liquid, using ICP-MS analysis detection, measuring arsenic concentration in filtrate is 87ppb.
6) resin adsorption: by third solution by 1.5 tons of DTMA-200 chelating ion exchange resins, through-rate is 0.9m3/ h, the waste water after adsorbing use ICP-MS analysis detection, and measuring As concentration in waste water is 11.1ppb.
Embodiment 4.
Generated arsenic-containing waste water in certain Usiminas's production process is handled using the present invention, handles water 5m3, arsenic is dense Spend 0.17g/L, free acid concentration 0.8mol/L.
1) it pre-oxidizes: the sodium chlorate solid 0.423kg of 0.35 times of arsenic mol being added into arsenic-containing waste water, aoxidize anti- 2h is answered, the first solution is obtained.
2) level-one flocculation sedimentation: into the first solution, being added the ferric polysulfate solid 2.15kg of 0.95 times of arsenic mol, After being stirred to react 30min, solid sodium hydroxide is added and adjusts pH to 9.4, is sufficiently mixed 20min, adding mass fraction is 0.7% polyacrylamide solution 15L is stirred to react 2min, forms a large amount of wadding body of slag containing arsenic, forms the first mixed liquor.
3) level-one is separated by solid-liquid separation: will be layered after the first mixed liquor natural subsidence 1h, supernatant and lower layer's slag are used respectively Filter press carries out filters pressing, after filter residue forced air drying, requires to be stored according to dangerous waste;The second solution is formed after filtrate mixing, is adopted With ICP-MS analysis detection, measuring arsenic concentration in filtrate is 73ppb.
4) resin adsorption: by the second solution by 1.5 tons of DTMA-200 chelating ion exchange resins, through-rate is 1.1m3/ h, the waste water after adsorbing use ICP-MS analysis detection, and measuring arsenic in waste water concentration is 9.6ppb.
This technique can handle various concentration acidic arsenic-containing waste water, and simple process, arsenic removal is high-efficient, and the amount of scum containing arsenic is few, give up Slag, which saves, to be stablized, low in cost, is really achieved the purpose to economize on resources with the harmless treatment of industrial arsenic-containing waste water.The technique is not Only to arsenic removal rate height, while heavy metal ion most in waste water can be removed, process flow is simple, small investment, processing The arsenic content in waste water, which is stablized, afterwards is lower than 20ppb, meets " water environment quality standard " (GB3838-2002) Group III water Standard is the processing of enterprise's arsenic-containing waste water, provides an approach economically and efficiently.
Although for illustrative purposes, the preferred embodiment of the present invention is had been disclosed, but the ordinary skill people of this field Member will realize without departing from the scope and spirit of the invention as disclosed by the appended claims, various to change Into, increase and replace be possible.

Claims (6)

1. a kind for the treatment of process of acidic arsenic-containing waste water, which is characterized in that flocculate including pre-oxidation, level-one flocculation sedimentation, second level Precipitating;
Pre-oxidation: being added oxidant in oxytropism arsenic-containing waste water, carry out oxidation reaction, obtain the first solution;
Level-one flocculation sedimentation: the first inorganic flocculating agent being added into the first solution, is stirred to react, and adjusts pH to 7~12, adds First organic flocculant, is stirred to react, and obtains the first mixed liquor, after the layering of the first mixed liquor natural subsidence, carries out solid-liquid point From obtaining the second solution and the first slag containing arsenic, detect arsenic content in the second solution;
Dissociate H in the acidic arsenic-containing waste water+Concentration is greater than 0.1mol/L;
The oxidant is sodium perchlorate, sodium chlorate, any one or more in calcium chlorate;
The oxidant of the addition and the molar ratio of arsenic are (0.2~0.9): 1;
First inorganic flocculating agent is bodied ferric sulfate, iron chloride, any one or more in ferric sulfate;
The molar ratio that the first inorganic flocculating agent and arsenic are added in the level-one flocculation sedimentation is (0.8~1): 1;
Second solution need to be through second level flocculation sedimentation, concrete operations are as follows:
The second inorganic flocculating agent is added into the second solution, is stirred to react, adjusts pH to 7~13, adds the second organic-flocculation Agent is stirred to react, and obtains the second mixed liquor, after the second mixed liquor natural subsidence, is separated by solid-liquid separation, obtain third solution and Second slag containing arsenic detects arsenic content in third solution;Second inorganic flocculating agent is bodied ferric sulfate, iron chloride, ferric sulfate In any one or more.
2. the treatment process of acidic arsenic-containing waste water according to claim 1, which is characterized in that the third solution need by Chelating ion exchange resin absorption, rate of adsorption 0.1m3/ h~2m3/ h, waste water after being adsorbed reach discharge through detection It is discharged after it is required that.
3. the treatment process of acidic arsenic-containing waste water according to claim 1, which is characterized in that second solution need by Chelating ion exchange resin absorption, rate of adsorption 0.1m3/ h~2m3/ h, waste water after being adsorbed reach discharge through detection It is discharged after it is required that.
4. the treatment process of any acidic arsenic-containing waste water according to claim 1~3, which is characterized in that second nothing Machine flocculant dosage is 1~10g/L.
5. the treatment process of acidic arsenic-containing waste water according to claim 1, which is characterized in that first organic flocculant For one of polyacrylamide, Sodium Polyacrylate or a variety of;Second organic flocculant is polyacrylamide, polyacrylic acid One of sodium is a variety of.
6. the treatment process of any acidic arsenic-containing waste water according to claim 1~3, which is characterized in that the addition The mass fraction of first organic flocculant is 0.01~1.0%, and dosage is 1~10ml;Second organic-flocculation of the addition The mass fraction of agent is 0.01~1.0%, and dosage is 1~10ml/L.
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CN112299588A (en) * 2019-07-25 2021-02-02 东泰高科装备科技有限公司 Method for treating industrial wastewater with high content of organic matters and arsenic
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