CN108358375A - A kind of industrial sewage process method - Google Patents

A kind of industrial sewage process method Download PDF

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CN108358375A
CN108358375A CN201810402269.0A CN201810402269A CN108358375A CN 108358375 A CN108358375 A CN 108358375A CN 201810402269 A CN201810402269 A CN 201810402269A CN 108358375 A CN108358375 A CN 108358375A
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water
water outlet
sewage
heavy metal
industrial sewage
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CN108358375B (en
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许欠欠
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Industrial University environment Co.,Ltd.
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许欠欠
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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
    • C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/24—Treatment of water, waste water, or sewage by flotation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/30—Treatment of water, waste water, or sewage by irradiation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/34—Treatment of water, waste water, or sewage with mechanical oscillations
    • C02F1/36—Treatment of water, waste water, or sewage with mechanical oscillations ultrasonic vibrations
    • 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
    • C02F1/40—Devices for separating or removing fatty or oily substances or similar floating material
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by 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
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/442—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/48—Treatment of water, waste water, or sewage with magnetic or electric fields
    • C02F1/488—Treatment of water, waste water, or sewage with magnetic or electric fields for separation of magnetic materials, e.g. magnetic flocculation
    • 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
    • C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
    • C02F1/56—Macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/70—Treatment of water, waste water, or sewage by reduction
    • 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
    • C02F2303/00—Specific treatment goals
    • C02F2303/04—Disinfection
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2303/00—Specific treatment goals
    • C02F2303/06—Sludge reduction, e.g. by lysis
    • 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
    • C02F2305/10—Photocatalysts
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
    • C02F5/02—Softening water by precipitation of the hardness

Abstract

The present invention provides a kind of industrial sewage process methods, and steps are as follows：（One）Mechanical treatment；（Two）Sofening treatment；（Three）Enhanced coagulation；（Four）Pulsed discharge plasma photocatalysis Synergistic degradation organic matter；（Five）The processing of supersonic synergic nano Zero-valent Iron；（Six）Wire mesh cage fibrous skeleton element aeroge adsorbs；（Seven）The reverse osmosis integrated membrane process processing of ultrafiltration/nanofiltration.Industrial sewage process method provided by the invention is simple for process, the cycle of operation is short, the pollutants such as contained suspended matter, organic matter, salt in trade effluent can thoroughly be removed, there is preferable removal effect to a plurality of types of persistence organic pollutants and heavy metal, and there is versatility to the removal of pollutant, heavy metal recovery rate is high, it is good in economic efficiency, technological flexibility is high, capacity of resisting impact load is strong, the sewage rate of recovery is high, is suitable for the multiple fields sewage disposals such as electric power, photovoltaic, photoelectricity, semiconductor, electronics, pharmacy, metallurgy, petrochemical industry.

Description

A kind of industrial sewage process method
Technical field
The present invention relates to technical field of sewage, and in particular to a kind of industrial sewage process method.
Background technology
Trade effluent complicated component is directly discharged to if these pollutant components are not pocessed in environment, to soil Very big harm can be caused with pollution of waterhead.Persistence organic pollutant (POPs) refer to by various surrounding mediums (big gas and water, Organism etc.) can long-distance migration and long-term existence in environment, have extended residual, bioconcentration, half volatile and High toxicity has the natural or artificial synthesized organic pollution materials seriously endangered to human health and environment.For persistence Organic pollution has the characteristics that high toxicity, persistence, characteristic of concentration, mobility are big, and research is thoroughly thorough by its in sewage disposal Bottom degradation becomes the hot spot of Recent study without generating new pollutant.
Water quality of industrial sewage complicated component usually has suspended matter and turbidity high, and salt content is high, and COD is high, weight Feature more than metal species.Currently, Industrial Waste Water Treatments are mainly comprehensive to use the technical sides such as Physical, chemical method and bioanalysis Method；Physical includes multiple-effect evaporation, ionization, reverse osmosis, ultrafiltration, nanofiltration etc., needs a large amount of electric power resource, operating cost high It is expensive；Oxidation polymer agent and chemical floc is typically added in chemical method in water, and that there are dosages is big, time of repose is long, production The shortcomings that raw secondary pollution；Biochemical process have the advantages that in sanitary sewage disposal stablize, it is at low cost, but can not handle a huge sum of money Belong to high content, organic concentration height and trade effluent with high salt.Therefore, for trade effluent the characteristics of, research one kind can be comprehensive The place of multiple pollutant in conjunction removal sewage, persistence organic pollutant of thoroughly degrading, high efficiente callback heavy metal and water resource Reason method has a very important significance.
Invention content
The object of the present invention is to provide a kind of easy to operate, techniques flexibly, persistence organic pollutant good degrading effect, weight Metal recovery rate is high, it is of low cost, do not generate the high industrial sewage process method of secondary pollution, the sewage rate of recovery.
The purpose of the present invention is achieved through the following technical solutions：
A kind of industrial sewage process method, its step are as follows：
(1) mechanical treatment：Trade effluent to be filtered by mechanical grille, filtered water outlet enters oil water separator, with Remove sundries, oil slick and suspended matter；
(2) sofening treatment：The water outlet of oil water separator is passed through in chemical reactor, and soda ash is added, is stirred, makes pH Value ranging from 8~11, goes the hardness ions such as removing calcium and magnesium that water body is made to soften, and simultaneous reactions generate suspension floc particle；
(3) enhanced coagulation：Water outlet after sofening treatment is passed through coagulation air-float machine, and sun is added by 0.1~0.3kg of water per ton Ionic flocculant drives away the suspension floc particle that grease, colloid, suspended solid and step (2) generate, and reduces the BOD in sewage With COD contents；
(4) pulsed discharge plasma-photocatalysis Synergistic degradation organic matter：The water outlet of coagulation air-float machine is passed directly into pulse Discharge plasma-photo catalysis reactor reacts 20~40min；
(5) supersonic synergic nano Zero-valent Iron is handled：Under ultrasonication, nano zero valence iron and pulsed discharge plasma-light Reduction, absorption, co-precipitation synergistic effect occur for the heavy metal in catalytic reactor water outlet, to reach removal effect, and heavy Shallow lake area is separated by solid-liquid separation；
(6) wire mesh cage fibrous skeleton element aeroge adsorbs：Water outlet after separation is passed through adsorption tank, and wire mesh cage skeleton is added Cellulose aerogels detach after 20~40s of processing with water body under magnetic fields, and desorption recycles heavy metal ion；
(7) the reverse osmosis integrated membrane process processing of ultrafiltration/nanofiltration-：Adsorption tank is discharged through the reverse osmosis integrated membrane process of ultrafiltration/nanofiltration- After processing, water outlet COD is less than 15mg/L, and conductivity is less than 20 μ S/cm, reaches I class water environment quality standard (GB- of country 3838-2002)。
Specifically, cationic flocculant used is logical with acrylamide and dimethyl diallyl ammonium chloride in step (3) Irradiation progress Raolical polymerizable is crossed to obtain.
Specifically, pulsed discharge plasma-photo catalysis reactor is column in step (4), and wall material is quartzy glass Glass, what placement length was different between discharge anode and aluminium net cathode is modified with TiO2-Bi2WO4The quartz glass plate of film is as blocking Medium.
Specifically, the preparation method of wire mesh cage fibrous skeleton element aeroge is in step (6)：
(1) PVA is mixed with DMSO, and water is added to form mixed liquor, then this mixed liquor and cellulose nano microcrystalline are suspended Liquid is mixed to form final suspension；
(2) 4h is stirred at room temperature in final suspension, be transferred in glass container；
(3) suspension in glass container is injected into iron cage skeleton die, liquid nitrogen orientation freezes 10min, after freezing immediately It is put into freeze dryer, distillation removes ice crystal, obtains wire mesh cage fibrous skeleton element aeroge, average diameter 10mm.
Specifically, ultrafiltration membrane used is Triafol T ultrafiltration membrane in step (7), and NF membrane used is that PVC bases are hollow Fiber composite NF membrane, reverse osmosis membrane used are that double guanidinated polyvinylamines are modified reverse osmosis membrane.
The present invention increases sofening treatment step after mechanical treatment, can remove removing calcium and magnesium hardness ions, and reaction, which generates, to suspend Floc particle can accelerate rate of settling when enhanced coagulation, can greatly improve coagulation efficiency, reduce making for cationic flocculant Dosage；Furthermore, it is possible to mitigate the pollution level of film when follow-up integrated membrane process is handled, backwash cycle is extended, the fortune of technique is improved Row stability；
Pulsed discharge plasma-photo catalysis reactor used in the present invention, pulsed discharge plasma set high energy electricity Sub- bombardment, hydroxyl radical free radical oxidation, ultraviolet degradation, ozone oxidation effect are in one, by persistence organic pollutant dyestuff point Son, phenol, bioxin, bisphenol-A, Polychlorinated biphenyls and chloroform, acetic acid, acetaldehyde etc. are degraded to CO2、H2O and inorganic salts, light Catalytic reaction catalyst uses TiO2-Bi2WO4Composite catalyst, TiO2The ultraviolet light of process of pulse discharge generation can be absorbed, Since wall of reactor selects quartz material, Bi2WO4Natural light can be directly utilized as visible light catalyst, electric energy can be reduced Consumption, composite catalyst can significantly improve organic matter degradation rate；The granularity of photochemical catalyst is smaller, and performance is higher, but is more difficult to To recycle and recycle, the photochemical catalyst used in the prior art is TiO2Powder, and TiO2Powder is water-treated in photocatalysis There is easily aggregation, easy in inactivation in journey, it is more difficult to which the shortcomings of recycling and being difficult to recycle, the present invention is by TiO2-Bi2WO4It is compound to urge Agent is film modified to arrive quartz glass plate surface, plays the role of dielectric impedance, and contacted with water body convenient for catalyst, in sewage The quantity and area of quartz glass plate can be adjusted in processing procedure according to organic concentration size, it is ensured that organic matter degradation is complete, Quartz glass plate is convenient to remove, is conducive to the separation and recovery of catalyst.
Wire mesh cage fibrous skeleton element aeroge due to being added a small amount of DMSO as mixed solvent, gas in water used in the present invention Homogeneous structural is presented in gel, has porous structure and high porosity, using wire mesh cage as the skeleton of cellulose aerogels, on the one hand The shape and size of aeroge can be controlled in preparation process；On the other hand make cellulose airsetting using the ferromagnetism of wire mesh cage Glue displacement under magnetic fields is fully acted on water body, the heavy metal ion of trace in adsorbed water body, the structure of aeroge Size is bigger, and its compression performance is better, and wire mesh cage fibrous skeleton element aeroge used is compared with common nano adsorber, absorption Performance is more preferable, and size is larger, not easily runs off, and recycling and desorption are convenient, and reuse ratio is high.
The present invention has the advantages that compared with prior art：
1. method treated the trade effluent of the present invention, water outlet no suspended substance detection, COD are less than 15mg/L, heavy metal Removal rate is more than 99%, and total hardness is less than 20mg/L, and conductivity is less than 20 μ S/cm, and the water resource rate of recovery is more than 90%；
2. in enhanced coagulation step of the present invention, the cationic flocculant used is with acrylamide and dimethyl diallyl Ammonium chloride copolymer has the advantages that positive charge density is high, cation mono meta structure is stable, good water solubility, using irradiation method one Step synthesis, non-secondary pollution have unique multi-level tight quarters space network, and flocculating effect is better than common flocculation Agent；
3. the present invention handles trade effluent using supersonic synergic nano Zero-valent Iron, the shock wave that ultrasound generates makes nano zero-valence Iron particle dispersion is suspended in reaction system, increases reactivity site, while making molecule quick oscillation, in homogenization system Reaction condition can also enhance the mass transfer effect of two-phase interface, accelerate falling off for nano zero valence iron surface oxide layer, accelerate reaction Rate, and be integrated equipment, floor space is small, and conveniently, treatment effeciency is high, and sludge quantity is few, and can for simple for process, operational management The valuable metals such as the gold, silver in sludge are recycled, it is good in economic efficiency；
4. the reverse osmosis integrated membrane process of ultrafiltration/nanofiltration-that the present invention uses by that can remove the bacterium in water body, have completely Machine object macromolecular, heavy metal ion, this method is easy to operate, low energy consumption, non-secondary pollution, and salt rejection rate is high, and producing water water quality is stablized, Water outlet can direct reuse in production.
Description of the drawings
Fig. 1 is pulsed discharge plasma-photo catalysis reactor schematic diagram, wherein 1- air compression systems, 2- gas streams Gauge, the 3- pulse powers, the discharge of 4- tail gas clean-ups, 5- discharge anodes, 6- are modified with TiO2-Bi2WO4The quartz glass plate of film, 7- aluminium net cathodes.
Specific implementation mode
Further to illustrate the present invention technological means and its effect taken, below in conjunction with the excellent of attached drawing and the present invention Embodiment is selected to be described in detail.
There is the sewage generated in certain chemical workshop production process source complexity, wastewater flow rate and waste water quality to fluctuate big Feature, major pollutants content are shown in Table 1, and persistence organic pollutant content is shown in Table 2, and content of beary metal is shown in Table 3.
Pollutant load in the sewage generated in certain the chemical workshop production process of table 1
Persistence organic pollutant content in the sewage generated in certain the chemical workshop production process of table 2
Content of beary metal in the sewage generated in certain the chemical workshop production process of table 3
Embodiment 1
A kind of industrial sewage process method, its step are as follows：
(1) mechanical treatment：Trade effluent to be filtered by mechanical grille, filtered water outlet enters oil water separator, with Remove sundries, oil slick and suspended matter；
(2) sofening treatment：The water outlet of oil water separator is passed through in chemical reactor, and soda ash is added, is stirred, makes pH Value is 8, goes the hardness ions such as removing calcium and magnesium that water body is made to soften, and simultaneous reactions generate suspension floc particle；
(3) enhanced coagulation：Water outlet after sofening treatment is passed through coagulation air-float machine, and cationic wadding is added by water 0.1kg per ton The suspension floc particle that grease, colloid, suspended solid and step (2) generate is driven away in solidifying agent, reduces BOD and COD in sewage Content；
(4) pulsed discharge plasma-photocatalysis Synergistic degradation organic matter：The water outlet of coagulation air-float machine is passed directly into pulse Discharge plasma-photo catalysis reactor (shown in Fig. 1) reacts 20min；
(5) supersonic synergic nano Zero-valent Iron is handled：Under ultrasonication, nano zero valence iron and pulsed discharge plasma-light Reduction, absorption, co-precipitation synergistic effect occur for the heavy metal in catalytic reactor water outlet, to reach removal effect, and heavy Shallow lake area is separated by solid-liquid separation；
(6) wire mesh cage fibrous skeleton element aeroge adsorbs：Water outlet after separation is passed through adsorption tank, and wire mesh cage skeleton is added Cellulose aerogels detach after processing 20s with water body under magnetic fields, and desorption recycles heavy metal ion；
(7) the reverse osmosis integrated membrane process processing of ultrafiltration/nanofiltration-：Adsorption tank is discharged through the reverse osmosis integrated membrane process of ultrafiltration/nanofiltration- After processing, water outlet COD is 14mg/L, and conductivity is 17 μ S/cm, reaches I class water environment quality standard (GB-3838- of country 2002)。
Specifically, cationic flocculant used is logical with acrylamide and dimethyl diallyl ammonium chloride in step (3) Irradiation progress Raolical polymerizable is crossed to obtain.
Specifically, pulsed discharge plasma-photo catalysis reactor (shown in Fig. 1) is column, wall material in step (4) Matter is quartz glass, places that length is different is modified between discharge anode (in Fig. 1 shown in 3) and aluminium net cathode (in Fig. 1 shown in 7) TiO2-Bi2WO4The quartz glass plate (in Fig. 1 shown in 6) of film is used as block media.
Specifically, the preparation method of wire mesh cage fibrous skeleton element aeroge is in step (6)：
(1) PVA is mixed with DMSO, and water is added to form mixed liquor, then this mixed liquor and cellulose nano microcrystalline are suspended Liquid is mixed to form final suspension；
(2) 4h is stirred at room temperature in final suspension, be transferred in glass container；
(3) suspension in glass container is injected into iron cage skeleton die, liquid nitrogen orientation freezes 10min, after freezing immediately It is put into freeze dryer, distillation removes ice crystal, obtains wire mesh cage fibrous skeleton element aeroge, average diameter 10mm.
Specifically, ultrafiltration membrane used is Triafol T ultrafiltration membrane in step (7), and NF membrane used is that PVC bases are hollow Fiber composite NF membrane, reverse osmosis membrane used are that double guanidinated polyvinylamines are modified reverse osmosis membrane.
Embodiment 2
A kind of industrial sewage process method, its step are as follows：
(1) mechanical treatment：Trade effluent to be filtered by mechanical grille, filtered water outlet enters oil water separator, with Remove sundries, oil slick and suspended matter；
(2) sofening treatment：The water outlet of oil water separator is passed through in chemical reactor, and soda ash is added, is stirred, makes pH Value is 9, goes the hardness ions such as removing calcium and magnesium that water body is made to soften, and simultaneous reactions generate suspension floc particle；
(3) enhanced coagulation：Water outlet after sofening treatment is passed through coagulation air-float machine, and cationic wadding is added by water 0.2kg per ton The suspension floc particle that grease, colloid, suspended solid and step (2) generate is driven away in solidifying agent, reduces BOD and COD in sewage Content；
(4) pulsed discharge plasma-photocatalysis Synergistic degradation organic matter：The water outlet of coagulation air-float machine is passed directly into pulse Discharge plasma-photo catalysis reactor (shown in Fig. 1) reacts 30min；
(5) supersonic synergic nano Zero-valent Iron is handled：Under ultrasonication, nano zero valence iron and pulsed discharge plasma-light Reduction, absorption, co-precipitation synergistic effect occur for the heavy metal in catalytic reactor water outlet, to reach removal effect, and heavy Shallow lake area is separated by solid-liquid separation；
(6) wire mesh cage fibrous skeleton element aeroge adsorbs：Water outlet after separation is passed through adsorption tank, and wire mesh cage skeleton is added Cellulose aerogels detach after processing 30s with water body under magnetic fields, and desorption recycles heavy metal ion；
(7) the reverse osmosis integrated membrane process processing of ultrafiltration/nanofiltration-：Adsorption tank is discharged through the reverse osmosis integrated membrane process of ultrafiltration/nanofiltration- After processing, water outlet COD is 13mg/L, and conductivity is 16 μ S/cm, reaches I class water environment quality standard (GB-3838- of country 2002)。
Specifically, cationic flocculant used is logical with acrylamide and dimethyl diallyl ammonium chloride in step (3) Irradiation progress Raolical polymerizable is crossed to obtain.
Specifically, pulsed discharge plasma-photo catalysis reactor (shown in Fig. 1) is column, wall material in step (4) Matter is quartz glass, places that length is different is modified between discharge anode (in Fig. 1 shown in 3) and aluminium net cathode (in Fig. 1 shown in 7) TiO2-Bi2WO4The quartz glass plate (in Fig. 1 shown in 6) of film is used as block media.
Specifically, the preparation method of wire mesh cage fibrous skeleton element aeroge is in step (6)：
(1) PVA is mixed with DMSO, and water is added to form mixed liquor, then this mixed liquor and cellulose nano microcrystalline are suspended Liquid is mixed to form final suspension；
(2) 4h is stirred at room temperature in final suspension, be transferred in glass container；
(3) suspension in glass container is injected into iron cage skeleton die, liquid nitrogen orientation freezes 10min, after freezing immediately It is put into freeze dryer, distillation removes ice crystal, obtains wire mesh cage fibrous skeleton element aeroge, average diameter 10mm.
Specifically, ultrafiltration membrane used is Triafol T ultrafiltration membrane in step (7), and NF membrane used is that PVC bases are hollow Fiber composite NF membrane, reverse osmosis membrane used are that double guanidinated polyvinylamines are modified reverse osmosis membrane.
Embodiment 3
A kind of industrial sewage process method, its step are as follows：
(1) mechanical treatment：Trade effluent to be filtered by mechanical grille, filtered water outlet enters oil water separator, with Remove sundries, oil slick and suspended matter；
(2) sofening treatment：The water outlet of oil water separator is passed through in chemical reactor, and soda ash is added, is stirred, makes pH Value ranging from 11, goes the hardness ions such as removing calcium and magnesium that water body is made to soften, and simultaneous reactions generate suspension floc particle；
(3) enhanced coagulation：Water outlet after sofening treatment is passed through coagulation air-float machine, and cationic wadding is added by water 0.3kg per ton The suspension floc particle that grease, colloid, suspended solid and step (2) generate is driven away in solidifying agent, reduces BOD and COD in sewage Content；
(4) pulsed discharge plasma-photocatalysis Synergistic degradation organic matter：The water outlet of coagulation air-float machine is passed directly into pulse Discharge plasma-photo catalysis reactor (shown in Fig. 1) reacts 40min；
(5) supersonic synergic nano Zero-valent Iron is handled：Under ultrasonication, nano zero valence iron and pulsed discharge plasma-light Reduction, absorption, co-precipitation synergistic effect occur for the heavy metal in catalytic reactor water outlet, to reach removal effect, and heavy Shallow lake area is separated by solid-liquid separation；
(6) wire mesh cage fibrous skeleton element aeroge adsorbs：Water outlet after separation is passed through adsorption tank, and wire mesh cage skeleton is added Cellulose aerogels detach after processing 40s with water body under magnetic fields, and desorption recycles heavy metal ion；
(7) the reverse osmosis integrated membrane process processing of ultrafiltration/nanofiltration-：Adsorption tank is discharged through the reverse osmosis integrated membrane process of ultrafiltration/nanofiltration- After processing, water outlet COD is 11mg/L, and conductivity is 10 μ S/cm, reaches I class water environment quality standard (GB-3838- of country 2002)。
Specifically, cationic flocculant used is logical with acrylamide and dimethyl diallyl ammonium chloride in step (3) Irradiation progress Raolical polymerizable is crossed to obtain.
Specifically, pulsed discharge plasma-photo catalysis reactor (shown in Fig. 1) is column, wall material in step (4) Matter is quartz glass, places that length is different is modified between discharge anode (in Fig. 1 shown in 3) and aluminium net cathode (in Fig. 1 shown in 7) TiO2-Bi2WO4The quartz glass plate (in Fig. 1 shown in 6) of film is used as block media.
Specifically, the preparation method of wire mesh cage fibrous skeleton element aeroge is in step (6)：
(1) PVA is mixed with DMSO, and water is added to form mixed liquor, then this mixed liquor and cellulose nano microcrystalline are suspended Liquid is mixed to form final suspension；
(2) 4h is stirred at room temperature in final suspension, be transferred in glass container；
(3) suspension in glass container is injected into iron cage skeleton die, liquid nitrogen orientation freezes 10min, after freezing immediately It is put into freeze dryer, distillation removes ice crystal, obtains wire mesh cage fibrous skeleton element aeroge, average diameter 10mm.
Specifically, ultrafiltration membrane used is Triafol T ultrafiltration membrane in step (7), and NF membrane used is that PVC bases are hollow Fiber composite NF membrane, reverse osmosis membrane used are that double guanidinated polyvinylamines are modified reverse osmosis membrane.
Water analysis method
The coloration of water body is measured using extension rate method；Suspended matter uses gravimetric detemination；COD is surveyed using potassium dichromate method It is fixed；BOD is measured using dilution and inocalation method；The measurement of total hardness uses disodium ethylene diamine tetraacetate titration measuring；Conductivity It is measured according to standard method of test with pH；Persistence organic pollutant uses Solid Phase Extraction column extracting, mass spectrum or gas phase in sewage Chromatographic determination；Heavy metal Cu in sewage, Cd, Pb, Ni, Zn concentration use Flame Atomic Absorption Spectrometry Determination, Hg and As's Concentration uses AFS DETERMINATION.
Treatment effect
The sewage generated in above-mentioned chemical workshop production process is discharged water after industrial sewage process method of the present invention processing Matter is shown in Table 4.
4 trade effluent of table is through Examples 1 to 3 treated effluent quality
Embodiment Embodiment 1 Embodiment 2 Embodiment 3
Coloration 1 1 0
SS(mg/L) 0 0 0
COD(mg/L) 14 13 11
BOD(mg/L) 5.6 5.3 4.1
Total hardness (mg/L) 19 12 17
Conductivity (us/cm) 17 16 10
Bioxin 0.05 0.06 0.01
Bisphenol-A 0.02 0.01 0.02
Phenol 0 0 0
Polychlorinated biphenyls 0.03 0.09 0.04
Toluene 0 0.01 0
Dibutyl phthalate 0 0 0
pH 7.1 6.9 7.4
Copper (mg/L) 0.16 0.10 0.08
Cadmium (mg/L) 0.008 0.007 0.006
Lead (mg/L) 0.006 0.006 0.005
Nickel (mg/L) 0.01 0.01 0.01
Zinc (mg/L) 0.02 0.03 0.01
Manganese (mg/L) 0.04 0.05 0.03
Mercury (mg/L) 0.001 0.001 0.001
Arsenic (mg/L) 0.009 0.007 0.006
As shown in Table 4, trade effluent handles the coloration that can significantly reduce sewage through the embodiment of the present invention 1~3, goes completely Except the suspended matter in sewage, organic matter removal is thorough, and COD is less than 20mg/L, BOD in 10mg/L hereinafter, salt rejection rate is high, total hardness Less than 20mg/L, conductivity is less than 20us/cm, has removal effect well to a variety of persistence organic pollutants and heavy metal Fruit, effluent quality reach national I class water environment quality standard (GB-3838-2002), can direct reuse in production, sewage The rate of recovery is up to 90% or more.
Valuable metal recovery utilizes
This method wet mud yield is 0.4~1.1kg/t sewage, and wet mud moisture content is 40%~50%.In sludge Platinum content is 3~40g/t；Palladium content is 5~80g/t；Gold content is 20~155g/t, and silver content is 35~450g/t, and copper contains Amount is 275~3600g/t, and platinum, palladium, gold, silver, copper recovery value are higher, produce larger economic benefit.
Economic analysis
Cost of sewage disposal includes the electricity charge, medicament expense, labour cost etc..Wherein the electricity charge are 1.2 yuan/t, medicament expense 12.0 Member/t, labour cost are 0.25 yuan/t.
Industrial sewage process method provided by the invention removes big sundries, oil slick and suspension by mechanical treatment first Object；Then water body is softened by the way that soda ash is added, and reacts and generates cotton-shaped particle；It is removed later by enhanced coagulation big absolutely Partial suspended thing, colloid and larger molecular organics；It is organic by step 4 pulsed discharge plasma-photocatalysis Synergistic degradation again Object, it is water, carbon dioxide and inorganic salts that can would become hard to biodegradable persistence organic pollutant exhaustive oxidation, ensures Water COD is less than 15mg/L, and the degradation of organic matter is also beneficial to the release of complexation heavy metal ion, convenient for follow-up heavy metal ion It removes；Using the heavy metal in removal polluted-water at supersonic synergic nano Zero-valent Iron in step 5, nano zero valence iron grain size is small, Large specific surface area, reactivity is high, and there is very strong reproducibility, the shock wave that ultrasound generates to keep the dispersion of nano zero-valence iron particle outstanding Float in reaction system, increases reactivity site, while making molecule quick oscillation, the reaction condition in homogenization system, also The mass transfer effect of two-phase interface can be enhanced, accelerate falling off for nano zero valence iron surface oxide layer, sludge settling performance is good, sludge In valuable metal can realize recycling；The heavy metal ion that denier is not removed by nano zero valence iron can be by magnetic fields The wire mesh cage fibrous skeleton element aeroge of lower movement adsorbs, to be detached with water body so that all kinds of heavy metals in sewage after processing Content can meet drinking water standard；The last reverse osmosis integrated membrane process processing of ultrafiltration/nanofiltration-, can remove most of inorganic Salt goes out total hardness of water and is less than 20mg/L after processing, conductivity is in 20us/cm or less.
To sum up, industrial sewage process method provided by the invention is simple for process, and the cycle of operation is short, can thoroughly remove industry The pollutants such as contained suspended matter, organic matter, salt in sewage, there is a plurality of types of persistence organic pollutants and heavy metal Preferable removal effect, and there is versatility to the removal of pollutant, heavy metal recovery rate is high, and good in economic efficiency, technique is flexible Property it is high, capacity of resisting impact load is strong, and the sewage rate of recovery is high, is suitable for electric power, photovoltaic, photoelectricity, semiconductor, electronics, pharmacy, smelting The multiple fields sewage disposal such as gold, petrochemical industry.
The above description is merely a specific embodiment, but scope of protection of the present invention is not limited thereto, ability Other modifications or equivalent replacement that domain those of ordinary skill makes technical scheme of the present invention, without departing from skill of the present invention The spirit and scope of art scheme, are intended to be within the scope of the claims of the invention.

Claims (5)

1. a kind of industrial sewage process method, which is characterized in that steps are as follows：
（One）Mechanical treatment：Heavy metal containing sewage is filtered by mechanical grille, filtered water outlet enters oil water separator, to remove Remove sundries, oil slick and suspended matter；
（Two）Sofening treatment：The water outlet of oil water separator is passed through in chemical reactor, and soda ash is added, is stirred, makes pH value model It is 8 ~ 11 to enclose, and goes the hardness ions such as removing calcium and magnesium that water body is made to soften, and simultaneous reactions generate suspension floc particle；
（Three）Enhanced coagulation：Water outlet after sofening treatment is passed through coagulation air-float machine, and cation is added by 0.1 ~ 0.3 kg of water per ton Flocculant drives away grease, colloid, suspended solid and step（Two）The suspension floc particle of generation, reduce sewage in BOD and COD contents；
（Four）Pulsed discharge plasma-photocatalysis Synergistic degradation organic matter：The water outlet of coagulation air-float machine is passed directly into pulsed discharge Plasma-photo catalysis reactor reacts 20 ~ 40 min；
（Five）The processing of supersonic synergic nano Zero-valent Iron：Under ultrasonication, nano zero valence iron and pulsed discharge plasma-photocatalysis Reduction, absorption, co-precipitation synergistic effect occur for the heavy metal in reactor water outlet, to reach removal effect, and in settling zone It is separated by solid-liquid separation；
（Six）Wire mesh cage fibrous skeleton element aeroge adsorbs：Water outlet after separation is passed through adsorption tank, and wire mesh cage fibrous skeleton is added Plain aeroge detaches after 20 ~ 40 s of processing with water body under magnetic fields, and desorption recycles heavy metal ion；
（Seven）The reverse osmosis integrated membrane process processing of ultrafiltration/nanofiltration-：Adsorption tank water outlet is handled through the reverse osmosis integrated membrane process of ultrafiltration/nanofiltration- Afterwards, water outlet COD is less than 15 mg/L, and conductivity is less than 20 μ S/cm, reaches national I class water environment quality standard（GB- 3838-2002）.
2. a kind of industrial sewage process method according to claim 1, which is characterized in that step（Three）In cation used Flocculant is to carry out Raolical polymerizable by irradiation with acrylamide and dimethyl diallyl ammonium chloride to obtain.
3. a kind of industrial sewage process method according to claim 1, which is characterized in that step（Four）Middle pulsed discharge etc. Gas ions-photo catalysis reactor is column, and wall material is quartz glass, and it is different that length is placed between discharge anode and aluminium net cathode Be modified with TiO2-Bi2WO4The quartz glass plate of film is as block media.
4. a kind of industrial sewage process method according to claim 1, which is characterized in that step（Six）Middle wire mesh cage skeleton The preparation method of cellulose aerogels is：
（1）PVA is mixed with DMSO, and water is added to form mixed liquor, then this mixed liquor and cellulose nano microcrystalline suspension are mixed Conjunction forms final suspension；
（2）4 h are stirred at room temperature in final suspension, are transferred in glass container；
（3）Suspension in glass container is injected into iron cage skeleton die, liquid nitrogen orientation 10 min of freezing are immediately placed in after freezing Freeze dryer, distillation remove ice crystal, obtain wire mesh cage fibrous skeleton element aeroge, 10 mm of average diameter.
5. a kind of industrial sewage process method according to claim 1, which is characterized in that step（Seven）In ultrafiltration membrane used For Triafol T ultrafiltration membrane, NF membrane used is PVC base hollow fiber compound nanofiltration membranes, and reverse osmosis membrane used is biguanides base Change polyvinylamine and is modified reverse osmosis membrane.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109437459A (en) * 2018-12-07 2019-03-08 绔ュ勾 A kind of mixed industrial waste water administering method
CN112321067A (en) * 2020-10-14 2021-02-05 开平汇顺科技有限公司 Sewage treatment method

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN2832800Y (en) * 2004-06-23 2006-11-01 大连理工大学 Device for photo-catalytic treatment of organic wastewater induced by needle-board type pulse discharge plasma
CN102030437A (en) * 2010-11-04 2011-04-27 河北省首钢迁安钢铁有限责任公司 Method for comprehensive wastewater desalination and zero release in steel production
CN106219834A (en) * 2016-08-31 2016-12-14 四川中物环保科技有限公司 A kind of mercurous gas water processing method
CN106396314A (en) * 2016-11-30 2017-02-15 河海大学 Method using ultrasonic to assist nanoscale zero-valence iron to remedy soil or sludge polluted by heavy metals

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN2832800Y (en) * 2004-06-23 2006-11-01 大连理工大学 Device for photo-catalytic treatment of organic wastewater induced by needle-board type pulse discharge plasma
CN102030437A (en) * 2010-11-04 2011-04-27 河北省首钢迁安钢铁有限责任公司 Method for comprehensive wastewater desalination and zero release in steel production
CN106219834A (en) * 2016-08-31 2016-12-14 四川中物环保科技有限公司 A kind of mercurous gas water processing method
CN106396314A (en) * 2016-11-30 2017-02-15 河海大学 Method using ultrasonic to assist nanoscale zero-valence iron to remedy soil or sludge polluted by heavy metals

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109437459A (en) * 2018-12-07 2019-03-08 绔ュ勾 A kind of mixed industrial waste water administering method
CN109437459B (en) * 2018-12-07 2021-06-22 童年 Mixed industrial sewage treatment method
CN112321067A (en) * 2020-10-14 2021-02-05 开平汇顺科技有限公司 Sewage treatment method

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