CN107417010B - 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 PDFInfo
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- CN107417010B CN107417010B CN201710736826.8A CN201710736826A CN107417010B CN 107417010 B CN107417010 B CN 107417010B CN 201710736826 A CN201710736826 A CN 201710736826A CN 107417010 B CN107417010 B CN 107417010B
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- 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
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- 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
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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
- 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
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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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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- 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
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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
- 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
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- 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
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
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- 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]
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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
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/08—Chemical Oxygen Demand [COD]; Biological Oxygen Demand [BOD]
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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
- C02F2301/00—General aspects of water treatment
- C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
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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
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical
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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
- 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 the saliferous generated in plating, hydrometallurgy, extraction processing industry technical process, high concentration organic pollutant, the invention discloses a kind of salt-containing organic wastewater high-efficient contact oxidation processing technique and systems, the following steps are included: salt-containing organic wastewater is separated by solid-liquid separation by (1), adjusting wastewater pH is 3-5(2), surface promoter is added into waste water and is filled with oxygen generation homogenizing reaction；(3) after completion of the reaction, contact break agent, oxidant is added so that oxidation contact break reaction occurs for organic coordination compound in homogenizing；(4) salt-containing organic wastewater pH value is adjusted to 8-9 by oxidation contact break end of reaction is co-precipitated the floccule body generated；(5) end of reaction is separated by solid-liquid separation, and is purified water discharge or classification reuse.The present invention is that microorganism treating high-concentration saline organic wastewater processing difficult to degrade proposes new way with recycling.
Description
Technical field
The present invention relates to organic wastewater degraded process fields, and in particular to a kind for the treatment of high-concentration saline organic wastewater catalysis oxidation
Treatment process and system.
Background technique
Plating, hydrometallurgy, the waste water that generates has that salinity is high, organic pollutant is more in extraction processing industry technical process
The characteristics of, traditional biochemical method cannot be handled.Fenton oxidation method utilizes Fe2+Catalyzing and decomposing H2O2Generate OH pollution degradation
Object, and the Fe generated3+Coagulating sedimentation occurs and removes organic matter, is capable of handling organic wastewater, but due to H2O2Stability is not strong,
Waste is big in aqueous solution, haves the defects that utilization rate is lower, treatment effeciency is low, H2O2Utilization rate is lower so that H2O2Dosage is big,
So that the processing cost of organic wastewater is high.
Summary of the invention
It is an object of the present invention to provide a kind of organic wastewater treatment process that high salinity microorganism is difficult to degrade and systems, efficiently
Contact-catalytic oxidation treatment process.
Basic principle of the technique based on hydroxyl radical free radical degradation of organic substances, comprising the following steps: (1) by saliferous organic waste
Water (salt-containing organic wastewater salt content is high and contains a large amount of heavy metal) is separated by solid-liquid separation, and 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) is adjusted to 3-5；(2) contain to described
Salt organic waste water is filled with oxygen, and surface promoter is added so that homogenizing reaction (surface promotion occurs for the salt-containing organic wastewater
Agent surface and organic matter absorption are decomposed)；(3) after completion of the reaction, contact break agent, oxidation is added in Xiang Suoshu salt-containing organic wastewater to homogenizing
So that contact break reaction and oxidation reaction occur for the salt-containing organic wastewater, (contact break reaction and oxidation reaction carry out simultaneously, contact break for agent
Reaction destroys organic coordination compound, provides condition for oxidation reaction)；The contact break agent be liquor natrii hypochloritis, postassium hypochlorite solution,
One of sodium chlorate solution, potassium chlorate solution or perchloric acid solution are a variety of；(4) after oxidation reaction, by the saliferous
Organic wastewater pH value (alkaline pH adjusting agent is adjusted, and alkaline pH adjusting agent is sodium hydroxide solution or sodium carbonate liquor) is adjusted to 8-
9 so that salt-containing organic wastewater generation precipitation reaction, can be filled with air to salt-containing organic wastewater simultaneously.(5) precipitation reaction finishes
Afterwards, salt-containing organic wastewater is separated by solid-liquid separation, is purified water and precipitating (is largely precipitated as iron hydroxide, hydroxide
Iron, aluminium hydroxide and heavy metal hydroxide), precipitating resourcebility processing recycling is used for the raw material of surface promoter；It will purification
Water pH value (acidic ph modifier is adjusted, and acidic ph modifier is dilute sulfuric acid or dust technology) is adjusted to 7-8 and obtains recycle-water, reuse
Water can be used for the recirculated water or washing slag water for the treatment of process.According to technique to the needs of recirculated water, recycle-water can be carried out further
Processing, first to recycle-water carry out desalting processing, desalting processing include primary concentration processing and secondary concentration processing, recycle-water warp
It crosses membranous system progress primary concentration to handle to obtain level-one concentrated water and softening recirculated water, level-one concentrated water is dense by membranous system progress second level
Contracting handles to obtain second level concentrated water and softening recirculated water, is distilled to obtain salinity, primary concentration processing and second level to second level concentrated water
The softening recirculated water salt content that concentration obtains is low.Wherein, anti-in homogenizing reaction, contact break reaction, the oxidation
Salt-containing organic wastewater should be stirred always in the precipitation reaction；The surface promoter is multiple for the iron carbon containing group
Condensation material, carbon or carbon compound in the surface promoter containing ferrous ion and with microcosmic hexagonal structure, institute
The carbon surface or the carbon compound area load stated carboxyl, hydroxyl, sulfydryl, ferrous ion and Zero-valent Iron.It is described equal
Changing reaction includes absorption and decomposition of the surface promoter to organic matter in salt-containing organic wastewater.Wherein, the purified water
COD content is less than 60mg/L, heavy metal total content is less than 1.0mg/L.
Preferably, iron and the mass ratio of carbon content are 1:3-1:5 in the surface promoter.
Preferably, carrying out desalting processing to the recycle-water, the desalting processing includes that primary concentration processing is dense with second level
Contracting processing, the recycle-water obtain level-one concentrated water and softening recirculated water by membranous system, this process is primary concentration processing；
The level-one concentrated water obtains second level concentrated water and softening recirculated water by membranous system, this process is secondary concentration processing.It obtains
It is low to soften recirculated water salt content.
Preferably, the surface promotes when the COD of the salt-containing organic wastewater is less than or equal to 1000mg/L
Agent additive amount is 1g/L-5g/L, the contact break agent additive amount is 1mL/L-4mL/L, the oxidant additive amount is 3mL/L-
8mL/L.That is surface promoter 1g-5g is added in every liter of salt-containing organic wastewater；Contact break agent is added in every liter of salt-containing organic wastewater
1mL-4mL；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, preceding acidified processing is added in the contact break agent, acid used in acidification is dust technology, the contact break agent
For one of liquor natrii hypochloritis, postassium hypochlorite solution, sodium chlorate solution, potassium chlorate solution or perchloric acid solution or a variety of；
Preceding acidified processing is added in the oxidant, and acid used in acidification is dilute sulfuric acid, and the oxidant is hydrogen peroxide, permanganic acid
One of potassium solution is a variety of.Contact break agent can also be 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 the following steps are included:
S1: by one of ferrous nitrate, ferrous sulfate heptahydrate, bodied ferric sulfate, potassium ferrate or it is a variety of be placed in from
Iron-containing liquor is obtained through dissolution in sub- water, the iron-containing liquor is heated and stirred, and controls the iron-containing liquor
A length of 30-60min when temperature is 413K-433K, control stirring rate is 60r/min-120r/min, stirs, after stirring
Obtain the iron-based mother liquor that iron-content is 150g/L-250g/L；Ferrous nitrate, ferrous sulfate heptahydrate, bodied ferric sulfate, potassium ferrate
It is technical grade reagent；
S2: it by carbon nanotube, graphene, graphene oxide, restores in one or more addition deionized waters of graphite powder
Suspension is obtained, the suspension pH value is adjusted to 1-4, after carrying out ultrasonic wave dispersion 20min-40min to the suspension
Obtain the carbon-based dispersion liquid of 100g/L-250g/L；
S3: being mixed to get iron carbon mixed liquor for the iron-based mother liquor and the carbon-based dispersion liquid with the mass ratio of 2:1-5:1,
The iron carbon mixed liquor is stirred, and controlling stirring rate is 60r/min-120r/min, Xiang Suoshu iron carbon mixed liquor
Be added reducing agent, the reducing agent contain citric acid, ascorbic acid, sodium sulfite, aluminium borohydride it is one or more, to described
Iron carbon mixed liquor bubble-free generates, and stops that the reducing agent is added and stops stirring to get surface promoter suspension, to described
Surface promoter suspension is filtered, washed to obtain the surface promoter after carrying out ultrasonic wave dispersion 30min-60min；Lemon
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 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 reactor tank and pharmaceutical supply system, the pharmaceutical supply system
System include be connected to the surface promoter charging device of the reactor tank, contact break agent charging device, oxidant charging device,
PH adjusting agent charging device.
Preferably, the salt-containing organic wastewater efficient oxidation processing system further includes PLC controller and aerator, it is described
Aerator includes the air compressor machine with the reactor tank air circuit connection, the air compressor machine and the PLC controller circuit connection.
Preferably, the top in the reactor tank is equipped with liquidometer, middle part is equipped with partition, lower part is equipped with mixed bed separator；
The partition is fixed by the bracket in the reactor tank, and filter separator, aeration tube and pH meter are equipped with above the partition；Institute
Filter separator is stated close to the partition；The partition is equipped with outlet conduit, and the outlet conduit connects water distributor, the water outlet
Pipeline is equipped with valve；The aeration tube is connected with the air compressor machine, and the liquidometer, the pH meter are controlled with the PLC respectively
Device signal is connected；The reactor tank top is equipped with exhaust outlet, waterwater entrance, and the reaction pot bottom is equipped with wastewater outlet.
The invention has the following advantages:
(1) Fe in surface promoter (0) Fe (II) with the carbon of hexagonal structure can generate very high potential difference,
So that the hexagonal structure edge of carbon produces OH and O2, OH and O2Organic matter can be decomposed, such reduction processing
The dosage of hydrogen peroxide improves treatment effeciency in technique, 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 the organic matter complex in salt-containing organic wastewater, contact break reaction carry out on surface promoter surface, to have
Machine object provides reacting environment, meanwhile, complex function group such as carboxyl, hydroxyl, the sulfydryl that surface promoter contains can also be inhaled
Agglomeration collection organic coordination compound, so that organic coordination compound is gathered in surface promoter to improve the rate of chemical reaction, so that
Salt-containing organic wastewater treatment effeciency is high；Surface promoter can also assemble oxidant and react with organic matter simultaneously, improve oxygen
The utilization rate of agent, 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
It manages high-efficient.
Detailed description of the invention
Fig. 1 is the preferred process flow chart of salt-containing organic wastewater high-efficient contact catalytic oxidation process for treating of the invention；
Fig. 2 is the processing system structural schematic diagram that the salt-containing organic wastewater efficient oxidation of the embodiment of the present invention 5 contacts；
Fig. 3 is the processing system structural schematic diagram that the salt-containing organic wastewater efficient oxidation of the embodiment of the present invention 7 contacts；
Fig. 4 is the partial enlarged view A of embodiment 7；
Fig. 5 is the partial enlarged view B of embodiment 7；
Fig. 6 is the partial enlarged view C of embodiment 7；
In Fig. 2:
100: reactor tank 110: liquidometer 120: partition
121: outlet conduit 122: water distributor 130: mixed bed separator
140: bracket 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 regulator charging device 300:PLC controller
400: aerator 410: air compressor machine
In Fig. 3:
100: reactor tank 100 ': 100 " reactor tank of reactor tank
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: processing cell system 510: wastewater disposal basin
520: conditioning tank 530: purification water pool
540: sedimentation basin 550: emergency lagoon
600: the first filter press, 700: the second filter press
Specific embodiment
The present invention is described in detail with reference to the accompanying drawings and examples.It should be noted that if do not conflicted, this hair
Each feature in bright embodiment and embodiment can be combined with each other, within the scope of the present invention.
Embodiment 1
The present invention provide surface promoter preparation method, comprising the following steps:
S1: ferrous nitrate (technical pure) being placed in deionized water and obtains iron-containing liquor through dissolution, is carried out to iron-containing liquor
It is a length of when the temperature for heating and stirring, and control iron-containing liquor is 433K, control stirring rate is 60r/min, stirs
60min obtains the iron-based mother liquor that iron-content is 200g/L after stirring.
S2: graphene being added in deionized water and obtains suspension, and adjusting suspension pH value is 2, is surpassed to suspension
Sound wave dispersion 30min obtains the carbon-based dispersion liquid of 200g/L.
S3: iron-based mother liquor and carbon-based dispersion liquid are mixed to get iron carbon mixed liquor with the mass ratio of 5:1, to iron carbon mixed liquor
It is stirred, and controlling stirring rate is 120r/min, is added to iron carbon mixed liquor by going back containing citric acid, ascorbic acid etc.
Former agent is generated to iron carbon mixed liquor bubble-free, is stopped that reducing agent is added and is stopped stirring to get surface promoter suspension, to table
Face promotor suspension is filtered, washed to obtain surface promoter after carrying out ultrasonic disperse 30min, is added to surface promoter
Surface promoter suspended dispersed liquid is obtained in deionized water.
Iron carbon mass ratio is 1:4 in surface promoter obtained, and surface promoter area load has ferrous ion, zeroth order
Iron, carboxyl, hydroxyl and sulfydryl.
Embodiment 2
The present invention provide surface promoter preparation method, comprising the following steps:
S1: ferrous nitrate (technical pure) being placed in deionized water and obtains iron-containing liquor through dissolution, is carried out to iron-containing liquor
It is a length of when the temperature for heating and stirring, and control iron-containing liquor is 433K, control stirring rate is 60r/min, stirs
60min obtains the iron-based mother liquor that iron-content is 150g/L after stirring.
S2: graphene being added in deionized water and obtains suspension, and adjusting suspension pH value is 2, is surpassed to suspension
Sound wave dispersion 30min obtains the carbon-based dispersion liquid of 100g/L.
S3: iron-based mother liquor and carbon-based dispersion liquid are mixed to get iron carbon mixed liquor with the mass ratio of 2:1, to iron carbon mixed liquor
It is stirred, and controlling stirring rate is 120r/min, the reducing agent contained is added to iron carbon mixed liquor, to iron carbon mixed liquor
Bubble-free, which generates, to be stopped being added reducing agent and stops stirring to get surface promoter suspension, is carried out to surface promoter suspension
It is filtered, washed to obtain surface promoter after ultrasonic disperse 30min, is added in deionized water to surface promoter and obtains surface
Promotor suspended dispersed liquid.
Iron carbon mass ratio is 1:5 in surface promoter obtained, and surface promoter area load has ferrous ion, zeroth order
Iron, carboxyl, hydroxyl and sulfydryl.
Embodiment 3
The present invention provide surface promoter preparation method, comprising the following steps:
S1: ferrous nitrate (technical pure) being placed in deionized water and obtains iron-containing liquor through dissolution, is carried out to iron-containing liquor
It is a length of when the temperature for heating and stirring, and control iron-containing liquor is 433K, control stirring rate is 60r/min, stirs
60min obtains the iron-based mother liquor that iron-content is 250g/L after stirring.
S2: graphene being added in deionized water and obtains suspension, and adjusting suspension pH value is 2, is surpassed to suspension
Sound wave dispersion 30min obtains the carbon-based dispersion liquid of 250g/L.
S3: iron-based mother liquor and carbon-based dispersion liquid are mixed to get iron carbon mixed liquor with the mass ratio of 5:1, to iron carbon mixed liquor
It is stirred, and controlling stirring rate is 120r/min, the reducing agent containing aluminium borohydride is added to iron carbon mixed liquor, to iron
Carbon mixed liquor bubble-free, which generates, to be stopped being added reducing agent and stops stirring to get surface promoter suspension, outstanding to surface promoter
Supernatant liquid is filtered, washed to obtain surface promoter after carrying out ultrasonic disperse 30min, is added in deionized water to surface promoter
Obtain surface promoter suspended dispersed liquid.
Iron carbon mass ratio is 1:3 in surface promoter obtained, and surface promoter area load has ferrous ion, zeroth order
Iron, carboxyl, hydroxyl and sulfydryl.
Embodiment 4
In conjunction with Fig. 1, salt-containing organic wastewater high-efficient contact catalytic oxidation process for treating provided by the invention is carried out detailed
Illustrate:
A kind of salt-containing organic wastewater high-efficient contact catalytic oxidation process for treating, comprising the following steps:
(1) salt-containing organic wastewater is separated by solid-liquid separation, the salt-containing organic wastewater pH value after separation of solid and liquid (is used into dilute sulfuric acid
Or dust technology adjusts pH value) it is adjusted to 4；
(2) it is filled with air to salt-containing organic wastewater, and surface promoter is added so that homogenizing occurs for salt-containing organic wastewater instead
It answers；Homogenizing reaction includes absorption and decomposition of the surface promoter to organic matter in salt-containing organic wastewater；In surface promoter
The mass ratio of ferrous ion and graphene is 1:3, and ferrous ion is carried on graphene, and the surface promoter of addition has in saliferous
Initial concentration in machine waste water is 3g/L, i.e., the initial concentration in surface promoter in salt-containing organic wastewater is 3g/L；
(3) after completion of the reaction, liquor natrii hypochloritis (contact break agent), hydrogen peroxide (oxidation is added to salt-containing organic wastewater in homogenizing
Agent) so that contact break reaction and oxidation reaction occur for salt-containing organic wastewater；The contact break agent of addition is initial in salt-containing organic wastewater
Concentration is 2mL/L, i.e. 2mL liquor natrii hypochloritis is added in every liter of salt-containing organic wastewater, and liquor natrii hypochloritis's mass fraction is
12%；Initial concentration of the oxidant of addition in salt-containing organic wastewater is 5mL/L, i.e. is added in every liter of salt-containing organic wastewater
5mL hydrogen peroxide, the mass fraction of hydrogen peroxide are 25%；The organic coordination compound destruction in salt-containing organic wastewater is decomposed in contact break agent
To organic matter, by hydroxyl radical free radical and superoxide radical, (surface promoter can generate hydroxyl radical free radical to organic matter and super oxygen is free
Ferrous ion oxygen reduction agent in base, surface promoter generates hydroxyl radical free radical) oxygenolysis is at harmless substance；
(4) after oxidation reaction, by salt-containing organic wastewater pH value (adjusting pH with the sodium hydroxide solution of 10%-30%)
8 are adjusted to so that precipitation reaction occurs for the metal ion of salt-containing organic wastewater, the coagulating absorption saliferous that iron ion occurs has
Suspended matter in machine waste water can be aerated 60min to salt-containing organic wastewater simultaneously；
(5) after precipitation reaction, salt-containing organic wastewater is separated by solid-liquid separation, water is purified and precipitating is (most of
It is precipitated as iron hydroxide and ferrous hydroxide), precipitating can be used as the raw material of surface promoter by resource utilization；By purified water pH
Value is adjusted to 7 and obtains recycle-water, and recycle-water can be used for the recirculated water for the treatment of process.It, can be right according to technique to the needs of recirculated water
Recycle-water is further processed, and first carries out desalting processing to recycle-water, and desalting processing includes primary concentration processing and second level
Concentration, recycle-water carry out primary concentration by membranous system and handle to obtain level-one concentrated water and softening recirculated water, level-one concentrated water warp
It crosses membranous system progress secondary concentration to handle to obtain second level concentrated water and softening recirculated water, second level concentrated water is distilled to obtain salinity,
Primary concentration processing is low with the softening recirculated water salt content that secondary concentration is handled.Wherein, homogenizing reaction, contact break reaction,
In oxidation reaction and precipitation reaction, salt-containing organic wastewater is stirred always.Wherein, the COD content of purified water is less than 60mg/
L, heavy metal total 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 being added；Hydrogen peroxide is sour by dilute sulfuric acid before being added
Change processing.
Embodiment 5
In conjunction with 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 reactor tank 100 and pharmaceutical supply system 200, medicament
Supply system 200 include be connected to 100 surface promoter charging devices 210 of reactor tank, contact break agent charging device 220,
Oxidant charging device 230, pH adjusting agent charging device 240.Surface promoter charging device 210 is stored including surface promoter
Tank, surface promoter holding vessel are connect by the pipeline with metering pump with reactor tank 100；Contact break agent charging device 220 includes
Contact break agent holding vessel, contact break agent holding vessel are connect by the pipeline with metering pump with reactor tank 100；Oxidant charging device
230 include oxidant holding vessel, and oxidant holding vessel is connect by the pipeline with metering pump with reactor tank 100；PH adjusting agent
Charging device 240 includes acidic ph modifier holding vessel and alkaline pH adjusting agent holding vessel, acidic ph modifier holding vessel and alkali
Property pH adjusting agent holding vessel connect respectively by the pipeline with metering pump with reactor tank 100.All metering pumps are all controlled with PLC
300 signal of device or circuit processed are connected.
Preferably, salt-containing organic wastewater efficient oxidation processing system includes PLC controller 300 and aerator 400, aeration
Device 400 includes the air compressor machine 410 with 100 air circuit connection of reactor tank, and air compressor machine 410 is connect with 300 signal of PLC controller, empty
Press 410 can also connect PLC controller 300 by circuit or wireless signal.
Preferably, the top in reactor tank 100 is equipped with liquidometer 110, middle part is equipped with partition 120, lower part is equipped with mixed bed point
From device 130.Partition 120, mixed bed separator 130 divide reactor tank 100 for three warehouses.Partition 120 is fixed on by bracket 140
In reactor tank 100, filter separator, aeration tube 150 and pH meter 160 are equipped with above partition 120；Partition 120 is equipped with outlet conduit
121, outlet conduit 121 connects water distributor 122, and outlet conduit 121 is equipped with valve, preferably, outlet pipe 121 and reactor tank 100
The treated water outlet (not shown) of side wall connects, and treated water outlet collects the purified water for not needing to carry out desalting processing；Aeration tube
150 are connected with air compressor machine 410, and liquidometer 110, pH meter 160 are connected with 300 circuit of PLC controller respectively；Filter separator is close
Partition 120；100 top of reactor tank is equipped with exhaust outlet 170, waterwater entrance 180, and 100 bottom of reactor tank is equipped with wastewater outlet 190,
Wastewater outlet 190 is equipped with valve.Filter separator is sand core filter, and sand core filter aperture can be used according to general standard
G1-G6 (1.5 μm -30 μm), mixed bed separator 130 are the cation bed of hydrogen type cation exchange resin and hand over equipped with hydrogen-oxygen type anion
Change the ion exchange system of the anion bed composition of resin；The connection of waterwater entrance 180 has the pipeline of intake pump, and wastewater outlet 190 connects
Tape splicing has the pipeline of water outlet pump, and water outlet pump, intake pump are connected respectively at 300 circuit of PLC controller or signal.In reactor tank 100
It is additionally provided with agitating paddle.
Embodiment 6
With reference to Fig. 1, Fig. 2, and combine the processing system of salt-containing organic wastewater high-efficient contact provided by the invention oxidation to containing
Salt organic waste water high-efficient contact catalytic oxidation process for treating is described in detail:
Salt-containing organic wastewater (through filter) is conveyed by intake pump and is entered in reactor tank 100 through waterwater entrance 180,
When salt-containing organic wastewater liquid level reaches predetermined position in reactor tank 100,110 feedback signal of liquidometer to PCL controller 300 with
Stop the conveying of salt-containing organic wastewater, meanwhile, PCL controller 300 issues instruction and opens to be connected with acidic ph modifier holding vessel
Metering pump to reactor tank 100 convey acidic ph modifier (dilute sulfuric acid or dust technology), when salt-containing organic wastewater in reactor tank 100
PH be 4 when, 160 feedback signal of pH meter stops the addition of acidic ph modifier, PLC controller 300 to PLC controller 300
The metering pump opening air compressor machine 410 and being connected with surface promoter holding vessel, so that every liter of salt-containing organic wastewater is added 3g's
Surface promoter, surface promoter continue to close air compressor machine after being filled with air 10min to salt-containing organic wastewater after being added
410, then PLC controller 300, which is separately turned on, stores tank connected metering pump toward reactor tank with contact break agent holding vessel, oxidant
Conveying hydrogen peroxide solution (oxidant) and liquor natrii hypochloritis's (contact break agent) in 100, so that 5mL is added in every liter of salt-containing organic wastewater
25% hydrogen peroxide so that 12% liquor natrii hypochloritis of 2mL is added in every liter of salt-containing organic wastewater；Contact break agent adds with oxidant
Alkaline pH adjusting agent (10%-30% potassium hydroxide is added to reactor tank 100 after stirring salt-containing organic wastewater 120min after entering
Solution), when the pH of salt-containing organic wastewater is 8,160 feedback signal of pH meter is to PLC controller 300 to stop alkaline pH adjusting agent
Addition, while PLC controller 300 opens air compressor machine 410 and by aeration tube 150 is filled with air, pneumatics to salt-containing organic wastewater
It is closed after closing air compressor machine 410 after the starting of machine 410 60min, then opens the valve of outlet conduit 121, salt-containing organic wastewater warp
It crosses water distributor 122 and flows through 130 desalination of mixed bed separator and be purified water, purified water has been collected through wastewater outlet 190 by water outlet pump
The processing of Cheng Yici salt-containing organic wastewater.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 is the waste water of the production of certain company, and the COD of salt-containing organic wastewater is 728mg/L, again
Total metal content is 200mg/L, (nickel content is that about 150mg/L, other content of beary metal are about 50mg/ to salt content 21g/L
L, salinity is mainly sodium sulphate), the purified water that waste water obtains after processed is through detecting, COD 56.64mg/L, nickel content
For 0.8mg/L.Processing salt-containing organic wastewater reaches outlet after national emission standard.
The saliferous that the treatment 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 being stirred always to salt-containing organic wastewater in this system treatment process, at this 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 reactor tank 100 can be increased.The intermittent addition of the reactor tank in parallel to three
Salt-containing organic wastewater, saliferous organic waste colleges and universities oxidation contact treatment system can complete 100m3/d-400m3/d saliferous organic waste
The processing of water；The successional addition salt-containing organic wastewater of the reactor tank in parallel to three, saliferous organic waste colleges and universities aoxidize contact position
Reason system can complete the processing of 400m3/d-600m3/d salt-containing organic wastewater.It is to this in conjunction with Fig. 2, Fig. 3, Fig. 4, Fig. 5, Fig. 6
System is described in detail: (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, instead
Answering device includes reactor tank 100, reactor tank 100 ', reactor tank 100 ", reactor tank 100, reactor tank 100 ', 100 " structure of reactor tank
It is identical；Pharmaceutical supply system includes be connected to reactor tank 100, reactor tank 100 ', the throwing of 100 " surface promoter of reactor tank
Expect device, contact break agent charging device, oxidant charging device, pH adjusting agent charging device；Surface promoter charging device includes
Surface promoter holding vessel 211, surface promoter holding vessel by with metering pump pipeline respectively with reactor tank 100, react
Tank 100 ', reactor tank 100 " connect；Contact break agent charging device includes contact break agent holding vessel 221, and contact break agent holding vessel 221 passes through band
There is the pipeline of metering pump to connect respectively with reactor tank 100, reactor tank 100 ', reactor tank 100 "；Oxidant charging device includes oxygen
Agent holding vessel 231, oxidant holding vessel 231 by with metering pump pipeline respectively with reactor tank 100, reactor tank 100 ',
Reactor tank 100 " connects；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 with metering pump pipeline respectively with reactor tank 100, reactor tank 100 ', react
Tank 100 " connect, alkaline pH adjusting agent holding vessel 242 by with metering pump pipeline respectively with reactor tank 100, reactor tank
100 ', reactor tank 100 " connects.All metering pumps are all connected with PLC controller signal or circuit.
Salt-containing organic wastewater efficient oxidation contact processing system further include processing cell system 500, the first filter press 600,
Second filter press 700.Processing cell system 500 includes wastewater disposal basin 510, conditioning tank 520, purification water pool 530, sedimentation basin 540 and answers
Anxious pond 550, wastewater disposal basin 510 are connect with the first filter press 600, and the first filter press 600 is connect with conditioning tank 520, and conditioning tank 520 divides
It is not connect with the top of reactor tank 100, reactor tank 100 ', reactor tank 100 "；Purification water pool 530 respectively with reactor tank 100, react
The bottom connection of tank 100 ', reactor tank 100 "；Emergency lagoon 550 is connect with conditioning tank 520, in addition, purification water pool 530 and reactor tank
100, reactor tank 100 ', the connecting pipe of reactor tank 100 " and emergency lagoon 550 connect；First filter press 600, the second filter press
700 connect with sedimentation basin 540 respectively.Conditioning tank 520, emergency lagoon 550 are connect with acidic ph modifier holding vessel 241 respectively, only
Change pond 530 to connect with alkaline pH adjusting agent holding vessel 242.
Preferably, salt-containing organic wastewater efficient oxidation processing system further includes PLC controller and aerator, aerator
Including the air compressor machine 410 respectively with reactor tank 100, reactor tank 100 ', 100 " air circuit connection of reactor tank, air compressor machine 410 and PLC are controlled
Device signal connection processed, air compressor machine 410 can also connect PLC controller by circuit or wireless signal.
Preferably, the top in reactor tank 100 is equipped with liquidometer 110, middle part is equipped with partition 120, lower part is equipped with mixed bed point
From device 130.Partition 120, mixed bed separator 130 divide reactor tank 100 for three warehouses.Partition 120 is fixed on by bracket 140
In reactor tank 100, filter separator, aeration tube 150 and pH meter 160 are equipped with above partition 120；Partition 120 is equipped with outlet conduit
121, outlet conduit 121 connects water distributor 122, and outlet conduit 121 is equipped with valve；Aeration tube 150 is connected with air compressor machine 410, liquid
Position meter 110, pH meter 160 are connected with 300 circuit of PLC controller respectively；Filter separator is close to partition 120；100 top of reactor tank
Equipped with exhaust outlet 170, waterwater entrance 180,100 bottom of reactor tank is equipped with wastewater outlet 190, and wastewater outlet 190 is equipped with valve.It crosses
Filter separator is sand core filter, and sand core filter aperture can use G1-G6 (1.5 μm -30 μm) according to general standard, 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；The connection of waterwater entrance 180 has the pipeline of intake pump, and the connection of wastewater outlet 190 has the pipeline of water outlet pump, water outlet
Pump, intake pump are connected respectively at 300 circuit of PLC controller or signal.Agitating paddle is additionally provided in reactor tank 100.
Salt-containing organic wastewater high-efficient contact oxidization processing system workflow is as follows:
The salt-containing organic wastewater (salt-containing organic wastewater COD is less than 1000mg/L) of wastewater disposal basin 510 passes through the first filter press 600
Filtering enters conditioning tank 520, in conditioning tank 520 salt-containing organic wastewater through acidic ph modifier adjusting respectively enter reactor tank 100,
Reactor tank 100 ', the processing of reactor tank 100 " are purified water (purified water COD is less than 60mg/L) and flow into purification water pool 530 again, complete
The processing of Cheng Yici salt-containing organic wastewater.Wherein conditioning tank 520 includes that organic wastewater is excessive or system jam, conditioning tank
Salt-containing organic wastewater flows into emergency lagoon 550 in 520, and particularly, obtained purified water is not up to standard to be directly discharged into emergency lagoon.First pressure
Filter 600, the resulting precipitating of the second filter press 700 are collected in 540 resource utilization of sedimentation basin.
Salt-containing organic wastewater treating capacity is greater than 600m3/d or more, can be in salt-containing organic wastewater high-efficient contact oxidation processes system
The consistent reactor tank 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 the preferred embodiment of the embodiment of the present invention has been described, once a person skilled in the art knows bases
This creative concept, then additional changes and modifications can be made to these embodiments.So the following claims are intended to be interpreted as
Including preferred embodiment and fall into all change and modification of range of embodiment of the invention.
Claims (10)
1. a kind of salt-containing organic wastewater high-efficient contact catalytic oxidation process for treating, comprising the following steps:
(1) salt-containing organic wastewater is separated by solid-liquid separation, the pH value of waste water after separation of solid and liquid is adjusted to 3-5；
(2) it is filled with oxygen in Xiang Suoshu waste water, and surface promoter is added so that homogenizing reaction occurs for the waste water；
(3) after completion of the reaction, contact break agent, oxidant is added so that the salt-containing organic wastewater in Xiang Suoshu salt-containing organic wastewater to homogenizing
Contact break reaction and oxidation reaction occurs；The contact break agent is liquor natrii hypochloritis, postassium hypochlorite solution, sodium chlorate solution, chloric acid
One of potassium solution or perchloric acid solution are a variety of；
(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 separated by solid-liquid separation, water is purified, by the purified water
PH is adjusted to 7-8 and obtains recycle-water；The COD content of the purified water is less than 60mg/L, heavy metal total content is less than 1.0mg/L,
Wherein, in homogenizing reaction, contact break reaction, the oxidation reaction and the precipitation reaction, always to saliferous
Organic wastewater is stirred；The surface promoter contains ferrous ion and carbon or iron with microcosmic hexagonal structure unit
The composite material of carbon, the 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, which is characterized in that institute
It states recycle-water and carries out desalting processing, the desalting processing includes that primary concentration processing is handled with secondary concentration.
3. salt-containing organic wastewater high-efficient contact catalytic oxidation process for treating according to claim 1, which is characterized in that described
Iron and the mass ratio of carbon content are 1:3-1:5 in surface promoter.
4. salt-containing organic wastewater high-efficient contact catalytic oxidation process for treating according to claim 1, which is characterized in that described
When the COD of salt-containing organic wastewater is less than or equal to 1000mg/L, the surface promoter additive amount is 1g/L-5g/L,
The contact break agent additive amount is 1mL/L-4mL/L, and the oxidant additive amount is 3mL/L-8mL/L.
5. salt-containing organic wastewater high-efficient contact catalytic oxidation process for treating according to claim 4, which is characterized 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, which is characterized 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 of potassium chlorate solution or perchloric acid solution are a variety of；The oxidant acidified processing before addition, the oxidation
Agent is one of hydrogen peroxide, liquor potassic permanganate or a variety of.
7. salt-containing organic wastewater high-efficient contact catalytic oxidation process for treating according to claim 1 to 6, special
Sign is, the preparation method of the surface promoter the following steps are included:
S1: by one of ferrous nitrate, ferrous sulfate heptahydrate, bodied ferric sulfate, potassium ferrate or a variety of it is placed in deionized water
It is middle to obtain iron-containing liquor through dissolution, the iron-containing liquor is heated and stirred, and controls the temperature of the iron-containing liquor
A length of 30-60min, obtains after stirring when being 60r/min-120r/min, stir for 413K-433K, control stirring rate
Iron-content is the iron-based mother liquor of 150g/L-250g/L；
S2: by carbon nanotube, graphene, graphene oxide, restore graphite powder one or more addition deionized waters in obtain
The suspension pH value is adjusted to 1-4 by suspension, is obtained after carrying out ultrasonic wave dispersion 20min-40min to the suspension
The carbon-based dispersion liquid of 100g/L-250g/L；
S3: the iron-based mother liquor and the carbon-based dispersion liquid are mixed to get iron carbon mixed liquor with the mass ratio of 2:1-5:1, to institute
It states iron carbon mixed liquor to be stirred, and controlling stirring rate is 60r/min-120r/min, Xiang Suoshu iron carbon mixed liquor is added
Reducing agent, the reducing agent contain one of citric acid, ascorbic acid, sodium sulfite, aluminium borohydride or a variety of, to the iron
Carbon mixed liquor bubble-free generates, and stops that the reducing agent is added and stops stirring to get surface promoter suspension, to the table
Face promotor suspension is filtered, washed to obtain the surface promoter after carrying out ultrasonic wave dispersion 30min-60min.
8. a kind of for salt-containing organic wastewater high-efficient contact catalytic oxidation process for treating described in any one of claim 1-7
Salt-containing organic wastewater efficient oxidation processing system, which is characterized in that including reactor tank (100) and pharmaceutical supply system (200),
The pharmaceutical supply system (200) includes the surface promoter charging device (210) for being connected to the reactor tank, 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, which is characterized in that the saliferous is organic
Waste water high-efficiency oxidization processing system further includes PLC controller (300) and aerator (400), and the aerator (400) includes
With the air compressor machine (410) of the reactor tank (100) air circuit connection, the air compressor machine (410) and the PLC controller (300) are believed
Number connection.
10. salt-containing organic wastewater efficient oxidation processing system according to claim 9, which is characterized in that the reactor tank
(100) top in is equipped with liquidometer (110), middle part is equipped with partition (120), lower part is equipped with mixed bed separator (130)；It is described every
Plate (120) is fixed in the reactor tank (100) by bracket (140), be equipped with above the partition (120) filter separator,
Aeration tube (150) and pH meter (160)；The filter separator is close to the partition (120)；The partition (120) is equipped with water outlet
Pipeline (121), the outlet conduit (121) connect water distributor (122), and the outlet conduit (121) is equipped with valve；The aeration
Pipe (150) be connected with the air compressor machine (410), the liquidometer (110), the pH meter (160) respectively with the PLC controller
(300) circuit is connected；Reactor tank (100) top is equipped with exhaust outlet (170), waterwater entrance (180), the reactor tank
(100) bottom is equipped with wastewater outlet (190).
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