CN107417010A - A kind for the treatment of high-concentration saline organic wastewater catalytic oxidation process for treating and system - Google Patents

A kind for the treatment of high-concentration saline organic wastewater catalytic oxidation process for treating and system Download PDF

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CN107417010A
CN107417010A CN201710736826.8A CN201710736826A CN107417010A CN 107417010 A CN107417010 A CN 107417010A CN 201710736826 A CN201710736826 A CN 201710736826A CN 107417010 A CN107417010 A CN 107417010A
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salt
organic wastewater
containing organic
reaction
iron
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CN107417010B (en
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陈润华
王平
陈舒婷
毛思沩
朱健
徐海音
杨雄
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Central South University of Forestry and Technology
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Central South University of Forestry and Technology
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    • 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
    • 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
    • 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
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/5281—Installations for water purification using chemical agents
    • 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
    • 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
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds
    • 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
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/005—Processes using a programmable logic controller [PLC]
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/08—Chemical Oxygen Demand [COD]; Biological Oxygen Demand [BOD]
    • 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
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00—Use of specific compounds during water treatment
    • C02F2305/02—Specific form of oxidant
    • C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00—Use of specific compounds during water treatment
    • C02F2305/04—Surfactants, used as part of a formulation or alone

Abstract

For the wastewater treatment of caused saliferous, high concentration organic pollution in plating, hydrometallurgy, extraction processing industry technical process, the invention discloses a kind of salt-containing organic wastewater high-efficient contact oxidation processing technique and system, comprise the following steps：（1）Salt-containing organic wastewater is subjected to separation of solid and liquid, regulation wastewater pH is 35（2）, surface promoter is added into waste water and is filled with oxygen generation homogenizing reaction；（3）Homogenizing after completion of the reaction, adds contact break agent, oxidant so that oxidation contact break reaction occurs for organic coordination compound；（4）Oxidation contact break reaction, which finishes, to be adjusted to 89 by salt-containing organic wastewater pH value and is co-precipitated the floccule body of generation；（5）Reaction finishes carry out separation of solid and liquid, is purified water discharge or classification reuse.The present invention proposes new way for the treating high-concentration saline organic wastewater processing of microorganism difficult degradation with recycling.

Description

A kind for the treatment of high-concentration saline organic wastewater catalytic oxidation process for treating and system
Technical field
The present invention relates to organic wastewater degraded process field, and in particular to a kind for the treatment of high-concentration saline organic wastewater catalysis oxidation Handling process and system.
Background technology
Caused waste water has salinity height, organic pollution more in plating, hydrometallurgy, extraction processing industry technical process The characteristics of, traditional biochemical method can not be handled.Fenton oxidation method utilizes Fe2+Catalyzing and decomposing H2O2Produce OH pollution degradations Thing, and the Fe generated3+Generation coagulating sedimentation organics removal, can handle organic wastewater, but due to H2O2Stability is not strong, Waste is big in the aqueous solution, the defects of utilization rate is relatively low, treatment effeciency is low, H be present2O2Utilization rate is relatively low so that H2O2Dosage is big, So that the processing cost of organic wastewater is high.
The content of the invention
It is an object of the present invention to provide a kind of organic wastewater treatment process and system of the difficult degradation of high salinity microorganism, efficiently Contact-catalytic oxidation handling process.
General principle of the technique based on hydroxyl radical free radical degradation of organic substances, comprises the following steps：（1）By saliferous organic waste Water（Salt-containing organic wastewater salt content is high and contains substantial amounts of heavy metal）Separation of solid and liquid is carried out, the saliferous after separation of solid and liquid is organic PH value of waste water（Acidic ph modifier is adjusted, and acidic ph modifier is dilute sulfuric acid or dust technology）It is adjusted to 3-5；（2）Contain to described Salt organic waste water is filled with oxygen, and adds surface promoter so that homogenizing reaction occurs for the salt-containing organic wastewater（Surface promotes Agent surface and organic matter absorption, decomposition）；（3）Homogenizing adds contact break agent, oxidation after completion of the reaction, to the salt-containing organic wastewater Agent is so that contact break reaction and oxidation reaction occur for the salt-containing organic wastewater（Contact break reaction and oxidation reaction are carried out simultaneously, contact break Reaction destroys organic coordination compound, and condition is provided for oxidation reaction）；（4）After oxidation reaction, by the salt-containing organic wastewater pH Value（Alkaline pH adjusting agent is adjusted, and alkaline pH adjusting agent is sodium hydroxide solution or sodium carbonate liquor）8-9 is adjusted to so that saliferous Precipitation reaction occurs for organic wastewater, can be filled with air to salt-containing organic wastewater simultaneously.（5）After precipitation reaction, by saliferous Organic wastewater carries out separation of solid and liquid, is purified water and precipitation（Major part is precipitated as iron hydroxide, ferrous hydroxide, hydroxide Aluminium and heavy metal hydroxide）, raw material of the precipitation resourcebility processing recovery for surface promoter；By purified water pH value（Acid Property pH adjusting agent regulation, acidic ph modifier is dilute sulfuric acid or dust technology）It is adjusted to 7-8 and obtains recycle-water, recycle-water can be used for The recirculated water or washing slag water of handling process.Needs according to technique to recirculated water, recycle-water can be further processed, first Desalting processing is carried out to recycle-water, desalting processing includes primary concentration processing and secondary concentration processing, and recycle-water passes through membranous system Carry out primary concentration to handle to obtain one-level concentrated water and softening recirculated water, one-level concentrated water carries out secondary concentration by membranous system and handled To two level concentrated water and softening recirculated water, two level concentrated water is distilled to obtain salinity, primary concentration processing is handled with secondary concentration Obtained softening recirculated water salt content is low.Wherein, in the homogenizing reaction, contact break reaction, the oxidation reaction and described In precipitation reaction, salt-containing organic wastewater is stirred all the time；The surface promoter is the iron carbon composite containing group, institute State carbon or carbon compound containing ferrous ion and with microcosmic hexagonal structure, described carbon table in surface promoter Face or the carbon compound area load carboxyl, hydroxyl, sulfydryl, ferrous ion and Zero-valent Iron.The homogenizing reaction bag Include absorption and decomposition of the surface promoter to organic matter in salt-containing organic wastewater.Wherein, the COD contents of the purified water are small It is less than 1.0mg/L in 60mg/L, heavy metal total content.
Preferably, iron and the mass ratio of carbon content are 1 in the surface promoter:3-1:5.
Preferably, carrying out desalting processing to the recycle-water, it is dense with two level that the desalting processing includes primary concentration processing Contracting is handled, and the recycle-water obtains one-level concentrated water and softening recirculated water by membranous system, and this process is primary concentration processing； The one-level concentrated water obtains two level concentrated water and softening recirculated water by membranous system, and this process is secondary concentration processing.Obtain It is low to soften recirculated water salt content.
Preferably, when the COD of the salt-containing organic wastewater is less than or equal to 1000mg/L, the surface promotes Agent addition is 1 g/L -5g/L, the contact break agent addition is 1mL/L-4mL/L, the oxidant addition is 3 mL/L -8 mL/L.That is surface promoter 1g-5g is added in every liter of salt-containing organic wastewater;Contact break agent 1 is added in every liter of salt-containing organic wastewater mL-4 mL;Oxidant 3mL-8mL is added in every liter of salt-containing organic wastewater.
Preferably, the contact break agent mass fraction is 10%-20%, the oxidant mass fraction is 15%-30%.
Preferably, the contact break agent add before acidified processing, acid used in acidification is dust technology, the contact break agent For the one or more in liquor natrii hypochloritis, postassium hypochlorite solution, sodium chlorate solution, potassium chlorate solution or perchloric acid solution； Acidified processing before the oxidant adds, acid used in acidification are dilute sulfuric acid, and the oxidant is hydrogen peroxide, permanganic acid One or more in potassium solution.Contact break agent is alternatively other hypochlorite solutions, solution of chlorate.Liquor natrii hypochloritis, Postassium hypochlorite solution, sodium chlorate solution, potassium chlorate solution, perchloric acid solution, hydrogen peroxide and liquor potassic permanganate are technical grade Reagent.
Preferably, the preparation method of the surface promoter comprises the following steps：
S1:One or more in ferrous nitrate, ferrous sulfate heptahydrate, bodied ferric sulfate, potassium ferrate are placed in deionized water It is middle to obtain iron-containing liquor through dissolving, the iron-containing liquor is heated and stirred, and controls the temperature of the iron-containing liquor For 413K-433K, control stir speed (S.S.) to be 60 r/min -120r/min, stirring when a length of 30-60min, stirring terminate after To the iron-based mother liquor that iron-holder is 150g/L-250g/L；Ferrous nitrate, ferrous sulfate heptahydrate, bodied ferric sulfate, potassium ferrate are equal For technical grade reagent；
S2：One or more add in deionized water of CNT, graphene, graphene oxide, reduction graphite powder is obtained Suspension, the suspension pH value is adjusted to 1-4, the suspension is carried out to obtain after ultrasonic wave disperses 20min-40min The carbon-based dispersion liquids of 100g/L-250g/L；
S3：By the iron-based mother liquor and the carbon-based dispersion liquid with 2:1-5:1 mass ratio is mixed to get iron carbon mixed liquor, to institute State iron carbon mixed liquor to be stirred, and it is 60 r/min -120r/min to control stir speed (S.S.), to the iron carbon mixed liquor is added Enter reducing agent, the reducing agent contains the one or more of citric acid, ascorbic acid, sodium sulfite, aluminium borohydride, treats the iron Carbon mixed liquor bubble-free produces, and stops adding the reducing agent and stopping stirring obtaining surface promoter suspension, to the table Face accelerator suspension carries out ultrasonic wave and disperses after 30min-60min to be filtered, washs to obtain the surface promoter；Lemon Acid, ascorbic acid, sodium sulfite, aluminium borohydride are technical grade reagent, and reducing agent provides carboxyl, carboxylic for surface promoter Base, sulfydryl.
Second object of the present invention is to provide a kind of be used at above-mentioned salt-containing organic wastewater high-efficient contact catalysis oxidation The salt-containing organic wastewater efficient oxidation processing system of science and engineering skill, including retort and pharmaceutical supply system, the pharmaceutical supply system System include being connected to the surface promoter charging device of the retort, contact break agent charging device, oxidant charging device, PH adjusting agent charging device.
Preferably, the salt-containing organic wastewater efficient oxidation processing system also includes PLC and aerator, it is described Aerator includes the air compressor machine being connected with the retort gas circuit, and the air compressor machine is connected with the PLC circuit.
Preferably, the top in the retort is provided with liquid level gauge, middle part is provided with dividing plate, bottom is provided with mixed bed separator； The dividing plate is fixed in the retort by support, and filter separator, aeration tube and pH meter are provided with above the dividing plate；Institute Filter separator is stated close to the dividing plate；The dividing plate is provided with outlet conduit, and the outlet conduit connects water-locator, the water outlet Pipeline is provided with valve；The aeration tube is connected with the air compressor machine, and the liquid level gauge, the pH meter control with the PLC respectively Device signal is connected；The retort top is provided with exhaust outlet, waterwater entrance, and the reaction pot bottom is provided with wastewater outlet.
The invention has the advantages that：
（1）Fe (0) in surface promoter Fe (II) can produce very high electrical potential difference with the carbon with hexagonal structure so that The hexagonal structure edge of carbon generates OH and O2, OH and O2Organic matter can be decomposed, so reduce handling process The dosage of middle hydrogen peroxide improves treatment effeciency, so as to reduce the processing cost of technique；
（2）OH and O2In surface promoter the hexagonal structure edge of carbon, Fe (0) Fe (II) be carried on carbon so that The oxidation reaction of organic matter complex in salt-containing organic wastewater, contact break reaction are carried out on surface promoter surface, are organic matter Reacting environment is provided, meanwhile, complex function group such as carboxyl, hydroxyl, the sulfydryl that surface promoter contains can also adsorb poly- Collect organic coordination compound so that organic coordination compound is gathered in surface promoter so as to improve the speed of chemical reaction so that saliferous Treatment of Organic Wastewater efficiency high；Surface promoter can also assemble oxidant and be reacted with organic matter simultaneously, improve oxidant Utilization rate, so as to reduce processing cost.
To sum up, the processing cost of salt-containing organic wastewater high-efficient contact catalytic oxidation process for treating provided by the invention is low, locates Manage efficiency high.
Brief description of the drawings
Fig. 1 is the preferable process chart of the salt-containing organic wastewater high-efficient contact catalytic oxidation process for treating of the present invention；
Fig. 2 is the processing system structural representation that the salt-containing organic wastewater efficient oxidation of the embodiment of the present invention 5 contacts；
Fig. 3 is the processing system structural representation that the salt-containing organic wastewater efficient oxidation of the embodiment of the present invention 7 contacts；
Fig. 4 is the partial enlarged drawing A of embodiment 7；
Fig. 5 is the partial enlarged drawing B of embodiment 7；
Fig. 6 is the partial enlarged drawing C of embodiment 7；
In Fig. 2：
100：Retort 110：Liquid level gauge 120：Dividing plate
121：Outlet conduit 122：Water-locator 130：Mixed bed separator
140：Support 150：Aeration tube 160：PH meter
170：Exhaust outlet 180：Waterwater entrance 190：Wastewater outlet
200：Pharmaceutical supply system 210：Surface promoter charging device
220：Contact break agent charging device 230：Oxidant charging device
240：PH adjusting agent charging device 300：PLC
400：Aerator 410：Air compressor machine
In Fig. 3：
100：Retort 100 '：The retort of retort 100 "
211：Surface promoter storage tank 221：Contact break agent holding vessel
231：Contact break agent holding vessel 241：Acidic ph modifier holding vessel
242：Alkaline pH adjusting agent holding vessel 410：Air compressor machine
500：Handle cell system 510：Wastewater disposal basin
520：Regulating reservoir 530：Purification water pool
540：Sedimentation basin 550：Emergency lagoon
600：First filter press 700：Second filter press.
Embodiment
The present invention is described in detail with reference to the accompanying drawings and examples.If it should be noted that do not conflicted, this hair Each feature in bright embodiment and embodiment can be combined with each other, within protection scope of the present invention.
Embodiment 1
The present invention provide surface promoter preparation method, comprise the following steps：
S1:By ferrous nitrate（Technical pure）It is placed in deionized water and obtains iron-containing liquor through dissolving, iron-containing liquor is heated And stir, and control iron-containing liquor temperature be 433K, control stir speed (S.S.) to be 60 r/min, stirring when a length of 60min, stir Mix the iron-based mother liquor for obtaining that iron-holder is 200g/L after terminating.
S2：Graphene is added in deionized water and obtains suspension, regulation suspension pH value is 2, and suspension is surpassed Sound wave disperses 30min and obtains 200g/L carbon-based dispersion liquid.
S3：By iron-based mother liquor and carbon-based dispersion liquid with 5:1 mass ratio is mixed to get iron carbon mixed liquor, to iron carbon mixed liquor It is stirred, and it is 120r/min to control stir speed (S.S.), is added to iron carbon mixed liquor by being gone back containing citric acid, ascorbic acid etc. Former agent, treat that iron carbon mixed liquor bubble-free produces, stop adding reducing agent and stopping stirring obtaining surface promoter suspension, to table Face accelerator suspension filtered after ultrasonic disperse 30min, washs to obtain surface promoter, is added to surface promoter Surface promoter suspended dispersed liquid is obtained in deionized water.
Iron carbon mass ratio is 1 in obtained surface promoter:4, surface promoter area load has ferrous ion, zeroth order Iron, carboxyl, hydroxyl and sulfydryl.
Embodiment 2
The present invention provide surface promoter preparation method, comprise the following steps：
S1:By ferrous nitrate（Technical pure）It is placed in deionized water and obtains iron-containing liquor through dissolving, iron-containing liquor is heated And stir, and control iron-containing liquor temperature be 433K, control stir speed (S.S.) to be 60 r/min, stirring when a length of 60min, stir Mix the iron-based mother liquor for obtaining that iron-holder is 150g/L after terminating.
S2：Graphene is added in deionized water and obtains suspension, regulation suspension pH value is 2, and suspension is surpassed Sound wave disperses 30min and obtains 100g/L carbon-based dispersion liquid.
S3：By iron-based mother liquor and carbon-based dispersion liquid with 2:1 mass ratio is mixed to get iron carbon mixed liquor, to iron carbon mixed liquor It is stirred, and it is 120r/min to control stir speed (S.S.), and the reducing agent contained is added to iron carbon mixed liquor, treats iron carbon mixed liquor Bubble-free, which produces, to be stopped adding reducing agent and stopping stirring obtaining surface promoter suspension, and surface promoter suspension is carried out Filtered after ultrasonic disperse 30min, wash to obtain surface promoter, added to surface promoter in deionized water and obtain surface Accelerator suspended dispersed liquid.
Iron carbon mass ratio is 1 in obtained surface promoter:5, surface promoter area load has ferrous ion, zeroth order Iron, carboxyl, hydroxyl and sulfydryl.
Embodiment 3
The present invention provide surface promoter preparation method, comprise the following steps：
S1:By ferrous nitrate（Technical pure）It is placed in deionized water and obtains iron-containing liquor through dissolving, iron-containing liquor is heated And stir, and control iron-containing liquor temperature be 433K, control stir speed (S.S.) to be 60 r/min, stirring when a length of 60min, stir Mix the iron-based mother liquor for obtaining that iron-holder is 250g/L after terminating.
S2：Graphene is added in deionized water and obtains suspension, regulation suspension pH value is 2, and suspension is surpassed Sound wave disperses 30min and obtains 250g/L carbon-based dispersion liquid.
S3：By iron-based mother liquor and carbon-based dispersion liquid with 5:1 mass ratio is mixed to get iron carbon mixed liquor, to iron carbon mixed liquor It is stirred, and it is 120r/min to control stir speed (S.S.), adds the reducing agent containing aluminium borohydride to iron carbon mixed liquor, treats iron Carbon mixed liquor bubble-free, which produces, to be stopped adding reducing agent and stopping stirring obtaining surface promoter suspension, and surface promoter is hanged Supernatant liquid filtered after ultrasonic disperse 30min, washs to obtain surface promoter, is added to surface promoter in deionized water Obtain surface promoter suspended dispersed liquid.
Iron carbon mass ratio is 1 in obtained surface promoter:3, surface promoter area load has ferrous ion, zeroth order Iron, carboxyl, hydroxyl and sulfydryl.
Embodiment 4
With reference to Fig. 1, salt-containing organic wastewater high-efficient contact catalytic oxidation process for treating provided by the invention is described in detail：
A kind of salt-containing organic wastewater high-efficient contact catalytic oxidation process for treating, comprises the following steps：
（1）Salt-containing organic wastewater is subjected to separation of solid and liquid, by the salt-containing organic wastewater pH value after separation of solid and liquid（With dilute sulfuric acid or dilute Nitre acid for adjusting pH value）It is adjusted to 4；
（2）Air is filled with to salt-containing organic wastewater, and adds surface promoter so that homogenizing reaction occurs for salt-containing organic wastewater； Changing reaction includes absorption and decomposition of the surface promoter to organic matter in salt-containing organic wastewater；In surface promoter ferrous iron from The mass ratio of son and graphene is 1:3, ferrous ion is carried on graphene, and the surface promoter of addition is in salt-containing organic wastewater In initial concentration be 3g/L, i.e., the initial concentration in surface promoter in salt-containing organic wastewater is 3g/L；
（3）Homogenizing adds liquor natrii hypochloritis after completion of the reaction, to salt-containing organic wastewater（Contact break agent）, hydrogen peroxide（Oxidant）With Make salt-containing organic wastewater that contact break reaction and oxidation reaction occur；Initial concentration of the contact break agent of addition in salt-containing organic wastewater be 2mL liquor natrii hypochloritises are added in 2mL/L, i.e. every liter of salt-containing organic wastewater, liquor natrii hypochloritis's mass fraction is 12%；Add Initial concentration of the oxidant in salt-containing organic wastewater be 5 mL/L, i.e. add 5mL dioxygens in every liter of salt-containing organic wastewater Water, the mass fraction of hydrogen peroxide is 25%；Contact break agent obtains the organic coordination compound destruction decomposition in salt-containing organic wastewater organic Thing, organic matter is by hydroxyl radical free radical and superoxide radical（Surface promoter can produce hydroxyl radical free radical and superoxide radical, surface Ferrous ion oxygen reduction agent in accelerator produces hydroxyl radical free radical）Oxidation Decomposition is into harmless material；
（4）After oxidation reaction, by salt-containing organic wastewater pH value（PH is adjusted with 10%-30% sodium hydroxide solution）It is adjusted to 8 so that precipitation reaction occurs for the metal ion of salt-containing organic wastewater, the coagulating absorption salt-containing organic wastewater that iron ion occurs In suspension, can simultaneously to salt-containing organic wastewater be aerated 60min；
（5）After precipitation reaction, salt-containing organic wastewater is subjected to separation of solid and liquid, is purified water and precipitation（Most of precipitation For iron hydroxide and ferrous hydroxide）, precipitate the raw material that surface promoter is can be used as by recycling recovery；Purified water pH value is adjusted Save and obtain recycle-water for 7, recycle-water can be used for the recirculated water of handling process.Needs according to technique to recirculated water, can be to reuse Water is further processed, and desalting processing is first carried out to recycle-water, and desalting processing includes primary concentration processing and secondary concentration Processing, recycle-water carry out primary concentration by membranous system and handle to obtain one-level concentrated water and softening recirculated water, and one-level concentrated water passes through film System carries out secondary concentration and handles to obtain two level concentrated water and softening recirculated water, and two level concentrated water is distilled to obtain salinity, one-level Concentration is low with the softening recirculated water salt content that secondary concentration handles to obtain.Wherein, in homogenizing reaction, contact break reaction, oxidation In reaction and precipitation reaction, salt-containing organic wastewater is stirred all the time.Wherein, the COD contents of purified water are less than 60mg/L, again Total metal content is less than 1.0mg/L.
Preferably, the COD of salt-containing organic wastewater is less than or equal to 1000mg/L.
Preferably, liquor natrii hypochloritis passes through dust technology acidification before adding；Hydrogen peroxide is sour by dilute sulfuric acid before adding Change is handled.
Embodiment 5
With reference to Fig. 2, salt-containing organic wastewater efficient oxidation processing system provided by the invention is described in detail：
A kind of salt-containing organic wastewater efficient oxidation processing system, including retort 100 and pharmaceutical supply system 200, pharmaceutical supply System 200 includes being connected to 100 surface promoter charging devices 210 of retort, contact break agent charging device 220, oxidation Agent charging device 230, pH adjusting agent charging device 240.Surface promoter charging device 210 includes surface promoter holding vessel, Surface promoter holding vessel is connected by the pipeline with measuring pump with retort 100；Contact break agent charging device 220 includes contact break Agent holding vessel, contact break agent holding vessel are connected by the pipeline with measuring pump with retort 100；Oxidant charging device 230 wraps Oxidant holding vessel is included, oxidant holding vessel is connected by the pipeline with measuring pump with retort 100；PH adjusting agent feeds intake dress Putting 240 includes acidic ph modifier holding vessel and alkaline pH adjusting agent holding vessel, and acidic ph modifier holding vessel is adjusted with alkaline pH Section agent holding vessel is connected by the pipeline with measuring pump with retort 100 respectively.All measuring pumps all with PLC 300 signals or circuit are connected.
Preferably, salt-containing organic wastewater efficient oxidation processing system includes PLC 300 and aerator 400, aeration Device 400 includes the air compressor machine 410 being connected with the gas circuit of retort 100, and air compressor machine 410 is connected with the signal of PLC 300, empty Press 410 can also connect PLC 300 by circuit or wireless signal.
Preferably, the top in retort 100 is provided with liquid level gauge 110, middle part is provided with dividing plate 120, bottom is provided with mixed bed point From device 130.Dividing plate 120, mixed bed separator 130 divide retort 100 for three warehouses.Dividing plate 120 is fixed on by support 140 In retort 100, the top of dividing plate 120 is provided with filter separator, aeration tube 150 and pH meter 160；Dividing plate 120 is provided with outlet conduit 121, outlet conduit 121 connects water-locator 122, and outlet conduit 121 is provided with valve, preferably, outlet pipe 121 and retort 100 The treated water outlet of side wall（Do not mark）Connection, treated water outlet collect the purified water that need not carry out desalting processing；Aeration tube 150 are connected with air compressor machine 410, and liquid level gauge 110, pH meter 160 are connected with the circuit of PLC 300 respectively；Filter separator is close Dividing plate 120；The top of retort 100 is provided with exhaust outlet 170, waterwater entrance 180, and the bottom of retort 100 is provided with wastewater outlet 190, Wastewater outlet 190 is provided with valve.Filter separator is sand core filter, and sand core filter aperture can use according to general standard G1-G6（1.5μm-30μm）, mixed bed separator 130 is for the cation bed of hydrogen type cation exchange resin and equipped with the friendship of hydrogen-oxygen type anion Change the ion exchange system of the anion bed composition of resin；Pipeline of the connection of waterwater entrance 180 with intake pump, wastewater outlet 190 connect Tape splicing has the pipeline of water pump, goes out water pump, intake pump connects respectively at the circuit of PLC 300 or signal.In retort 100 It is additionally provided with agitating paddle.
Embodiment 6
With reference to figure 1, Fig. 2, and the processing system for combining salt-containing organic wastewater high-efficient contact provided by the invention oxidation has to saliferous Machine waste water high-efficiency contact-catalytic oxidation handling process is described in detail：
By salt-containing organic wastewater（Through filter）Entered by intake pump conveying through waterwater entrance 180 in retort 100, when anti- When answering that salt-containing organic wastewater liquid level reaches precalculated position in tank 100, liquid level gauge 110 feeds back signal to PCL controllers 300 to stop The conveying of salt-containing organic wastewater, meanwhile, PCL controllers 300 send instruction and open the meter being connected with acidic ph modifier holding vessel Measure pump and convey acidic ph modifier to retort 100（Dilute sulfuric acid or dust technology）, as the pH of salt-containing organic wastewater in retort 100 For 4 when, pH meter 160 feeds back signal to PLC 300 to stop the addition of acidic ph modifier, and PLC 300 is opened Air compressor machine 410 and the measuring pump being connected with surface promoter holding vessel so that every liter of salt-containing organic wastewater adds 3g surface Accelerator, surface promoter continue to close air compressor machine 410 after being filled with air 10min to salt-containing organic wastewater after adding, so PLC 300 is separately turned on storing tank connected measuring pump toward defeated in retort 100 with contact break agent holding vessel, oxidant afterwards Send hydrogen peroxide solution（Oxidant）And liquor natrii hypochloritis（Contact break agent）So that every liter of salt-containing organic wastewater adds the 25% of 5mL Hydrogen peroxide so that every liter of salt-containing organic wastewater adds 2mL 12% liquor natrii hypochloritis；After contact break agent adds with oxidant After stirring salt-containing organic wastewater 120min alkaline pH adjusting agent is added to retort 100（10%-30% potassium hydroxide solutions）, when containing When the pH of salt organic waste water is 8, pH meter 160 feeds back signal to PLC 300 to stop the addition of alkaline pH adjusting agent, together When PLC 300 open air compressor machine 410 air is filled with to salt-containing organic wastewater by aeration tube 150, air compressor machine 410 starts Closed after closing air compressor machine 410 after 60min, then open the valve of outlet conduit 121, salt-containing organic wastewater passes through water-locator 122, which flow through the desalination of mixed bed separator 130, is purified water, and purified water is gone out water pump collection through wastewater outlet 190 to be completed once to contain The processing of salt organic waste water.Obtained purified water pH is tuned into 7 and obtains recirculated water.
Suspended dispersed liquid is made to surface promoter addition water to be stored in surface promoter holding vessel.
The salt-containing organic wastewater of processing for the production of certain company waste water, the COD of salt-containing organic wastewater for 728mg/L, again Total metal content is 200mg/L, salt content 21g/L（Nickel content is about 150mg/L, other content of beary metal are about 50mg/ L, salinity is mainly sodium sulphate）, after testing, its COD is 56.64mg/L, nickel content to the purified water that waste water obtains after treated For 0.8 mg/L.Processing salt-containing organic wastewater reaches outer row after discharging standards.
The saliferous that the handling process adapting device of this set salt-containing organic wastewater efficient oxidation contact can complete 100m3/d has The processing of machine waste water.It should be noted that salt-containing organic wastewater is stirred all the time in the system processing procedure, at the system The salt-containing organic wastewater COD of reason is less than or equal to 1000mg/L.
Embodiment 7
According to the output of waste water, the quantity of retort 100 can be increased.The intermittent addition saliferous of the retort in parallel to three Organic wastewater, saliferous organic waste colleges and universities oxidation contact processing system can complete 100m3/d-400m3/d salt-containing organic wastewaters Processing；The successional addition salt-containing organic wastewater of the retort in parallel to three, saliferous organic waste colleges and universities oxidation contact processing system System can complete the processing of 400m3/d-600m3/d salt-containing organic wastewaters.The system is entered with reference to Fig. 2, Fig. 3, Fig. 4, Fig. 5, Fig. 6 Row detailed description：（Fig. 4, Fig. 5, Fig. 6 are the pipeline enlarged drawing of salt-containing organic wastewater high-efficient contact oxidization processing system.）
A kind of processing system of salt-containing organic wastewater efficient oxidation contact, including pharmaceutical supply system and reaction unit, reaction dress Put including retort 100, retort 100 ', retort 100 ", retort 100, retort 100 ', the structure phase of retort 100 " Together；Pharmaceutical supply system, which includes being connected to the 100 of retort, retort 100 ', the surface promoter of retort 100 ", to feed intake Device, contact break agent charging device, oxidant charging device, pH adjusting agent charging device；Surface promoter charging device includes table Face accelerator holding vessel 211, surface promoter holding vessel by the pipeline with measuring pump respectively with retort 100, retort 100 ', retort 100 " connects；Contact break agent charging device includes contact break agent holding vessel 221, contact break agent holding vessel 221 by with The pipeline of measuring pump is connected with retort 100, retort 100 ', retort 100 " respectively；Oxidant charging device includes oxidation Agent holding vessel 231, oxidant holding vessel 231 by the pipeline with measuring pump respectively with retort 100, retort 100 ', anti- Tank 100 " is answered to connect；PH adjusting agent charging device includes acidic ph modifier holding vessel 241 and alkaline pH adjusting agent holding vessel 241, acidic ph modifier holding vessel 241 by the pipeline with measuring pump respectively with retort 100, retort 100 ', reaction Tank 100 " connect, alkaline pH adjusting agent holding vessel 242 by the pipeline with measuring pump respectively with retort 100, retort 100 ', retort 100 " connects.All measuring pumps are all connected with PLC signal or circuit.
Salt-containing organic wastewater efficient oxidation contact processing system also include processing cell system 500, the first filter press 600, Second filter press 700.Handling cell system 500 includes wastewater disposal basin 510, regulating reservoir 520, purification water pool 530, sedimentation basin 540 and answers Anxious pond 550, wastewater disposal basin 510 are connected with the first filter press 600, and the first filter press 600 is connected with regulating reservoir 520, and regulating reservoir 520 divides Top not with retort 100, retort 100 ', retort 100 " is connected；Purification water pool 530 respectively with retort 100, reaction The bottom connection of tank 100 ', retort 100 "；Emergency lagoon 550 is connected with regulating reservoir 520, in addition, purification water pool 530 and retort 100th, retort 100 ', the connecting pipe of retort 100 " and emergency lagoon 550 connect；First filter press 600, the second filter press 700 are connected with sedimentation basin 540 respectively.Regulating reservoir 520, emergency lagoon 550 are connected with acidic ph modifier holding vessel 241 respectively, only Change pond 530 to be connected with alkaline pH adjusting agent holding vessel 242.
Preferably, salt-containing organic wastewater efficient oxidation processing system also includes PLC and aerator, aerator Including the air compressor machine 410 being connected respectively with retort 100, retort 100 ', the gas circuit of retort 100 ", air compressor machine 410 and PLC is controlled Device signal connection processed, air compressor machine 410 can also connect PLC by circuit or wireless signal.
Preferably, the top in retort 100 is provided with liquid level gauge 110, middle part is provided with dividing plate 120, bottom is provided with mixed bed point From device 130.Dividing plate 120, mixed bed separator 130 divide retort 100 for three warehouses.Dividing plate 120 is fixed on by support 140 In retort 100, the top of dividing plate 120 is provided with filter separator, aeration tube 150 and pH meter 160；Dividing plate 120 is provided with outlet conduit 121, outlet conduit 121 connects water-locator 122, and outlet conduit 121 is provided with valve；Aeration tube 150 is connected with air compressor machine 410, liquid Position meter 110, pH meter 160 are connected with the circuit of PLC 300 respectively；Filter separator is close to dividing plate 120；The top of retort 100 Provided with exhaust outlet 170, waterwater entrance 180, the bottom of retort 100 is provided with wastewater outlet 190, and wastewater outlet 190 is provided with valve.Cross Filter separator is sand core filter, and sand core filter aperture can use G1-G6 according to general standard（1.5μm-30μm）, mixed bed point The ion of anion bed composition from the cation bed that device 130 is hydrogen type cation exchange resin and equipped with hydrogen-oxygen type anion exchange resin is handed over Change system；Pipeline of the connection of waterwater entrance 180 with intake pump, pipeline of the connection of wastewater outlet 190 with water outlet pump, water outlet Pump, intake pump connect respectively at the circuit of PLC 300 or signal.Agitating paddle is additionally provided with retort 100.
Salt-containing organic wastewater high-efficient contact oxidization processing system workflow is as follows：
The salt-containing organic wastewater of wastewater disposal basin 510（Salt-containing organic wastewater COD is less than 1000mg/L）By the mistake of the first filter press 600 Filter enters regulating reservoir 520, and salt-containing organic wastewater respectively enters retort 100, instead through acidic ph modifier regulation in regulating reservoir 520 Tank 100 ', the processing of retort 100 " is answered to be purified water（Purified water COD is less than 60mg/L）Purification water pool 530 is flowed into again, is completed The processing of salt-containing organic wastewater.Wherein regulating reservoir 520 includes that organic wastewater is excessive or system jam, regulating reservoir 520 Interior salt-containing organic wastewater flows into emergency lagoon 550, and particularly, obtained purified water is not up to standard to be directly discharged into emergency lagoon.First press filtration Machine 600, the precipitation of the gained of the second filter press 700 are collected in the recovery of the recycling of sedimentation basin 540.
Salt-containing organic wastewater treating capacity is more than more than 600m3/d, can be in salt-containing organic wastewater high-efficient contact oxidation processes system The consistent retort 100 of the more structures of addition in parallel in system, it is also possible to reaction tank surrogate response device.
The processing cost of salt-containing organic wastewater high-efficient contact catalytic oxidation process for treating provided by the invention is low, treatment effeciency It is high.
Although having been described for the preferred embodiment of the embodiment of the present invention, those skilled in the art once know base This creative concept, then other change and modification can be made to these embodiments.So appended claims are intended to be construed to Including preferred embodiment and fall into having altered and changing for range of embodiment of the invention.

Claims (10)

1. a kind of salt-containing organic wastewater high-efficient contact catalytic oxidation process for treating, comprises the following steps：
（1）Salt-containing organic wastewater is subjected to separation of solid and liquid, the filtrate pH value of waste water after separation of solid and liquid is adjusted to 3-5；
（2）Oxygen is filled with into the filtrate waste water, and adds surface promoter so that homogenizing reaction occurs for the waste water；
（3）Homogenizing adds contact break agent, oxidant so that the salt-containing organic wastewater after completion of the reaction, to the salt-containing organic wastewater Generation contact break reaction and oxidation reaction；
（4）After oxidation reaction, the salt-containing organic wastewater pH value is adjusted to 8-9 so that salt-containing organic wastewater precipitates Reaction；
（5）After precipitation reaction, the salt-containing organic wastewater is subjected to separation of solid and liquid, water is purified, by the purified water PH is adjusted to 7-8 and obtains recycle-water；The COD contents of the purified water are less than 60mg/L, heavy metal total content is less than 1.0mg/L,
Wherein, in the homogenizing reaction, contact break reaction, the oxidation reaction and the precipitation reaction, all the time to saliferous Organic wastewater is stirred；The surface promoter contains ferrous ion and carbon or iron with microcosmic hexagonal structure unit The composite of carbon, described carbon surface or the carbon compound area load carboxyl, hydroxyl, sulfydryl.
2. salt-containing organic wastewater high-efficient contact catalytic oxidation process for treating according to claim 1, it is characterised in that to institute State recycle-water and carry out desalting processing, the desalting processing includes primary concentration processing and handled with secondary concentration.
3. salt-containing organic wastewater high-efficient contact catalytic oxidation process for treating according to claim 1, it is characterised in that described Iron and the mass ratio of carbon content are 1 in surface promoter:3-1:5.
4. salt-containing organic wastewater high-efficient contact catalytic oxidation process for treating according to claim 1, it is characterised in that institute When stating the COD of salt-containing organic wastewater and being less than or equal to 1000mg/L, the surface promoter addition be 1g/L- 5g/L, the contact break agent addition are 1mL/L-4mL/L, and the oxidant addition is 3 mL/L -8 mL/L.
5. salt-containing organic wastewater high-efficient contact catalytic oxidation process for treating according to claim 4, it is characterised in that described Contact break agent mass fraction is 10%-20%, and the oxidant mass fraction is 15%-30%.
6. salt-containing organic wastewater high-efficient contact catalytic oxidation process for treating according to claim 5, it is characterised in that described Contact break agent acidified processing before addition, the contact break agent be liquor natrii hypochloritis, postassium hypochlorite solution, sodium chlorate solution, One or more in potassium chlorate solution or perchloric acid solution；The oxidant acidified processing before addition, the oxidation Agent is the one or more in hydrogen peroxide, liquor potassic permanganate.
7. the salt-containing organic wastewater high-efficient contact catalytic oxidation process for treating according to any one of claim 1-6, it is special Sign is that the preparation method of the surface promoter comprises the following steps：
S1:One or more in ferrous nitrate, ferrous sulfate heptahydrate, bodied ferric sulfate, potassium ferrate are placed in deionized water It is middle to obtain iron-containing liquor through dissolving, the iron-containing liquor is heated and stirred, and controls the temperature of the iron-containing liquor For 413K-433K, control stir speed (S.S.) to be 60 r/min -120r/min, stirring when a length of 30-60min, stirring terminate after To the iron-based mother liquor that iron-holder is 150g/L-250g/L；
S2：One or more add in deionized water of CNT, graphene, graphene oxide, reduction graphite powder is obtained Suspension, the suspension pH value is adjusted to 1-4, the suspension is carried out to obtain after ultrasonic wave disperses 20min-40min The carbon-based dispersion liquids of 100g/L-250g/L；
S3：By the iron-based mother liquor and the carbon-based dispersion liquid with 2:1-5:1 mass ratio is mixed to get iron carbon mixed liquor, to institute State iron carbon mixed liquor to be stirred, and it is 60 r/min -120r/min to control stir speed (S.S.), to the iron carbon mixed liquor is added Enter reducing agent, the reducing agent contains the one or more in citric acid, ascorbic acid, sodium sulfite, aluminium borohydride, treats described Iron carbon mixed liquor bubble-free produces, and stops adding the reducing agent and stopping stirring obtaining surface promoter suspension, to described Surface promoter suspension carries out ultrasonic wave and disperses after 30min-60min to be filtered, washs to obtain the surface promoter.
A kind of 8. salt-containing organic wastewater high-efficient contact catalytic oxidation process for treating being used in claim 1-7 described in any one Salt-containing organic wastewater efficient oxidation processing system, it is characterised in that including retort（100）With pharmaceutical supply system（200）, The pharmaceutical supply system（200）Surface promoter charging device including being connected to the retort（210）, contact break agent Charging device（220）, oxidant charging device（230）, pH adjusting agent charging device（240）.
9. salt-containing organic wastewater efficient oxidation processing system according to claim 8, it is characterised in that the saliferous is organic Waste water high-efficiency oxidization processing system also includes PLC（300）With aerator（400）, the aerator（400）Including With the retort（100）The air compressor machine of gas circuit connection（410）, the air compressor machine（410）With the PLC（300）Letter Number connection.
10. salt-containing organic wastewater efficient oxidation processing system according to claim 9, it is characterised in that the retort （100）Interior top is provided with liquid level gauge（110）, middle part be provided with dividing plate（120）, bottom be provided with mixed bed separator（130）；It is described every Plate（120）Pass through support（140）It is fixed on the retort（100）It is interior, the dividing plate（120）Top be provided with filter separator, Aeration tube（150）And pH meter（160）；The filter separator is close to the dividing plate（120）；The dividing plate（120）Provided with water outlet Pipeline（121）, outlet conduit (121) the connection water-locator（122）, the outlet conduit（121）Provided with valve；The aeration Pipe（150）With the air compressor machine（410）It is connected, the liquid level gauge（110）, the pH meter（160）Respectively with the PLC （300）Circuit is connected；The retort（100）Top is provided with exhaust outlet（170）, waterwater entrance（180）, the retort （100）Bottom is provided with wastewater outlet（190）.
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CN108275803A (en) * 2018-02-24 2018-07-13 湖南善循环保科技有限公司 A kind of potent catalytic oxidation treatment process of high salt organic waste water
CN113488220A (en) * 2021-06-04 2021-10-08 华中科技大学 Method for treating radioactive anion exchange resin by combination of persulfuric acid compound and Fenton-like oxidation

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CN103495428A (en) * 2013-09-23 2014-01-08 同济大学 Preparation method of carbon nano-tube based Fenton-like catalyst for advanced oxidation system
CN105709755A (en) * 2016-03-22 2016-06-29 浙江清华长三角研究院 Biological carbon catalyst, iron carbon catalyst and application of biological carbon catalyst
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CN108275803A (en) * 2018-02-24 2018-07-13 湖南善循环保科技有限公司 A kind of potent catalytic oxidation treatment process of high salt organic waste water
CN113488220A (en) * 2021-06-04 2021-10-08 华中科技大学 Method for treating radioactive anion exchange resin by combination of persulfuric acid compound and Fenton-like oxidation

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