CN109133448A - A kind of the environment-friendly cycle treatment process and system of viscose glue waste liquid - Google Patents

A kind of the environment-friendly cycle treatment process and system of viscose glue waste liquid Download PDF

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Publication number
CN109133448A
CN109133448A CN201811310408.3A CN201811310408A CN109133448A CN 109133448 A CN109133448 A CN 109133448A CN 201811310408 A CN201811310408 A CN 201811310408A CN 109133448 A CN109133448 A CN 109133448A
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tank
acid
circulating tank
concentration
solution
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CN109133448B (en
Inventor
邓传东
贺敏
夏长林
徐绍贤
王云
刘洪�
周勇
廖磊
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Yibin Grace Group Co Ltd
Yibin Grace Co Ltd
Yibin Haisite Fiber Co Ltd
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Yibin Grace Group Co Ltd
Yibin Grace Co Ltd
Yibin Haisite Fiber Co Ltd
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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
    • C02F1/38—Treatment of water, waste water, or sewage by centrifugal separation
    • 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
    • C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
    • 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
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
    • C02F1/4693—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis electrodialysis
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/30—Nature of the water, waste water, sewage or sludge to be treated from the textile industry
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A20/00—Water conservation; Efficient water supply; Efficient water use
    • Y02A20/124—Water desalination
    • Y02A20/131—Reverse-osmosis

Abstract

The present invention relates to a kind of environment-friendly cycle treatment process of viscose glue waste liquid and systems, belong to waste recovery and environmental protection treatment technical field in viscose rayon production.Including centrifuge, transfer tank, blend tank, coarse filter device, fine filtering apparatus, resin tower, the setting of bipolar membrane device and circulating tank, it is centrifuged, dissolution, adjust pH, temperature regulating, adjust sodium sulfate concentration, coarse filtration, essence filtering, resin chelating purification, bipolar membrane electrodialysis and post-treating and other steps, and optimal conditions, technological parameter, equipment and index etc., it will be sour, alkali and dilute salt are recycled, it is difficult effectively to solve viscose glue liquid waste processing, the problems such as data wastes, sulfuric acid has not only been effectively ensured in this, the purity of sodium hydroxide, concentration and yield, and each product in each step is back in this environment-friendly cycle treatment process or viscose rayon production process, it is low to realize energy consumption, cost of material saves purpose, simultaneously, realize zero-emission, reduce environmental pressure.

Description

A kind of the environment-friendly cycle treatment process and system of viscose glue waste liquid
Technical field
The present invention relates to the processing methods and system of a kind of viscose glue waste liquid, especially, are related to a kind of closure of viscose glue waste liquid Environment-friendly treatment method and system belong to waste recovery and environmental protection treatment technical field in viscose rayon production.
Background technique
Viscose rayon is using high molecular material wood pulp, cotton pulp containing native cellulose etc. by chemistry and mechanical means The chemical fibre being process is kind closest with natural fiber clothes performance in chemical fibre, has soft, suction It is penetrable ventilated, overhang elegant, bright, antistatic the features such as being relatively easy to textile process, be derived from day however better than it is natural again Raw cellulose fibre, is one of the important materials of textile industry raw material.There is viscose rayon enterprise about 40 in China at present, except production Outside common viscose fiber (long filament, staple fiber) and high-tenacity fibre, the viscose rayon of high wet modulus fiber and special property also has life It produces.
A large amount of industrial chemicals is needed in production process of viscose fiber, can generate a large amount of waste water, these waste water contain sulphur Acid, zinc sulfate, carbon disulfide, cellulose, dissolved organic matter etc. generate very big harm to environment, are textile industries One of primary pollution source.
Wherein, in viscose rayon forming process, viscose glue and acid coagulating bath are acted on, and are neutralized alkali, cellulose sulfonic acid Sodium is decomposed and regenerates cellulose hydrate, cellulose sulfonate, free NaOH during this in viscose glue and because of side reaction The Na of generation2CS3, the side reaction products such as polysulfide can generate sodium sulphate with the sulfuric acid reaction in coagulating bath.Viscose rayon Include the acid bath process of consumption sulfuric acid in production, further includes the sheet steeping process for consuming sodium hydroxide, alkali cellulose sulphonic acid ester Dissolution process, concise compresses and washes process and sour water neutralisation treatment operation at waste gas absorption process.
The main function of sodium sulphate is that viscose glue liquid stream is promoted to solidify and inhibit sulfuric acid dissociation in coagulating bath, makes cellulose sulfonic acid The reproduction speed of ester delays, and improves the concentration of sodium sulphate in coagulating bath, and spinning operation is easier to, and tow is not easy to break end, and can drop The degree of dissociation of low-sulfur acid, makes tow still have certain residual ester value when leaving coagulating bath, but the sodium sulphate in coagulating bath Also unsuitable excessively high, otherwise fibre solidification can be made to overrun, fine structure cannot be formed, and coarse crystalline particle is generated, fiber Ectonexine is also inhomogenous.
During the spinning process, the sodium sulphate content in coagulating bath is continuously increased so that its requirement for being unable to satisfy technique, such as Fruit only passes through the raw material being consumed in addition coagulating bath will make the total amount of coagulating bath increase to supplement its concentration recycling Add and can not store, can only at regular time and quantity discharge coagulating bath, acid therein, salt, metal ion etc. will cause serious ring Border pollution brings huge pressure to sewage treatment and causes the huge waste of resource.And by sodium sulphate extra in spinning High temperature crystallization is carried out, sodium sulfate crystal is isolated, so that the content of the sodium sulphate in spinning is met technique requirement, without arranging daily Fall acid to balance spinning, by directly continuing to use for spinning workshop after charging, acid discharge can be reduced, output anhydrous sodium sulphate reduces ring Packing pressure, but due to sodium sulphate high temperature crystallization is produced in coagulating bath anhydrous sodium sulphate it is impure it is more, added value itself is low makes Economic benefit can not be generated by obtaining it, and a large amount of solid salt can not be handled, and still bring certain pressure to environmental protection.
State knows that office disclosed a kind of Publication No. CN101343124 on 01 14th, 2009, entitled " based on circulating tank The patent document of viscose glue waste liquid environment-friendly processing unit ", open: equipment includes absorbing filling, collecting tank, neutralization pond, sedimentation basin.The hair The bright governing problem for comprehensively considering salkali waste, exhaust gas and zinc-containing water in viscose rayon production, had not only reached the comprehensive utilization of resource, but also Waste discharge is reduced, solves the environmental issue for restricting industry development in viscose glue production process for a long time.The technical solution is although right Viscose glue waste liquid carries out environmental protection treatment, but the processing such as is not separated, purified, be concentrated to waste, and be recycled, discontented Sufficient cycling and reutilization requirement.
State knows that office discloses a kind of Publication No. CN206666261U, a kind of entitled " viscose glue on November 24th, 2017 The patent document of fine acid waste water processing unit ", open: multimedium filter, ultrafiltration membrane, nanofiltration membrane, level-one produce pond, pressurization Pump, RO reverse osmosis membrane and recycling water storage tank；The outlet of multimedium filter and the inlet communication of ultrafiltration membrane；The outlet of ultrafiltration membrane with receive The inlet communication of filter membrane；The outlet of nanofiltration membrane and level-one produce the inlet communication in pond；Level-one produces outlet and the booster pump in pond Inlet communication；Outlet and the inlet communication of RO reverse osmosis membrane of booster pump, the outlet of RO reverse osmosis membrane and recycling water storage tank into Mouth of a river connection.The utility model solves the neutralization precipitation pool device processing viscose fiber acid waste water used at this stage and brings High cost burden, secondary pollution problems caused by the lime slag that is not available largely, and handle through the utility model useless Water can recycle, good purification, high-efficient, reduce water resource waste, energy conservation and environmental protection.But the technical solution stresses pair Viscose Waste Water carries out environmental protection treatment, and not specific, circulation and being recycled to Viscose Waste Water efficiently etc..
State knows that office discloses a kind of Publication No. CN103342433A on October 09th, 2013, and entitled " a kind of viscose glue is fine The patent document of the method that dimension sodium sulfate waste liquid recycles soda acid using bipolar membrane electrodialysis method "；State knows office November 13 in 2013 Disclose a kind of Publication No. CN103388198A day, entitled " a kind of bipolar membrane electrodialysis method is useless from viscose sodium sulfate The patent document of the method that liquid produces soda acid "；And state knows that office discloses a kind of Publication No. on October 16th, 2013 CN103351041A, the patent document of entitled " the electrodialysis alkali recovery process in a kind of production of viscose rayon ".There is also with Lower problem: existing viscose glue liquid waste treating apparatus can not be expanded to industrialized production, be only limitted to the experimental stage；Viscose glue waste liquid carries out After processing, there is also wastes discharge, is unfavorable for environmentally friendly production；Sulfuric acid, sodium hydroxide, dilute sulfuric acid sodium is carried out to viscose glue waste liquid to return After receipts, purity and concentration are not able to satisfy actual demand, i.e., impurity is more, concentration is small, are back to after cellulose viscose manufacturing technique to production Quality influences greatly, therefore could be used in production technology after need to being further processed.
Summary of the invention
Present invention seek to address that prior art problem, and propose a kind of environment-friendly cycle treatment process of viscose glue waste liquid.It is logical It crosses and centrifuge, transfer tank, blend tank, coarse filter device, fine filtering apparatus, resin tower, bipolar membrane device and circulating tank is set It sets, is centrifuged, dissolves, adjust pH, temperature regulating, adjust sodium sulfate concentration, coarse filtration, essence filtering, the absorption of resin chelating, Bipolar Membrane Electrodialysis and post-treating and other steps and optimal conditions, technological parameter, equipment and index etc., acid, alkali and dilute salt are returned The problems such as receiving, effectively solving viscose glue liquid waste processing difficult, data waste, this be not only effectively ensured sulfuric acid, sodium hydroxide it is pure Degree, concentration and yield, and each product in each step is back to this environment-friendly cycle treatment process or viscose rayon production work In sequence, realizes the low, cost of material that consumes energy and save purpose, meanwhile, it realizes zero-emission, reduces environmental pressure.
In order to achieve the above technical purposes, the following technical solution is proposed:
A kind of environment-friendly cycle treatment process of viscose glue waste liquid,
Viscose glue waste liquid obtains the powdery solid containing sodium sulphate, zinc sulfate and sulfuric acid and contains sodium sulphate, sulphur after centrifuge separates Gelled acid bath foam is directly delivered to the acid in cellulose viscose manufacturing technique by pipeline and stood by the gelled acid bath foam of sour zinc and sulfuric acid Powdery solid containing sodium sulphate, zinc sulfate and sulfuric acid is placed in transfer tank by acid storage tank；
By adding demineralized water into transfer tank, powdery solid dissolution obtains lysate；
Then, lysate is passed through into blend tank, adjusts temperature, pH and sodium sulfate concentration in blend tank, obtains molten containing suspended matter Liquid；
Under this condition, the zinc ion in lysate generates zinc hydroxide white precipitate in conjunction with hydroxide ion, and is suspended in In solution, there is about 80% zinc ion to be deposited during this；
Suspended matter solution will be contained to be passed through in coarse filter device, coarse filtration, and remove bulky grain zinc hydroxide precipitation, and obtain filter residue I and thick Filtrate；
Coarse filtration liquid is passed through into fine filtering apparatus, essence filtering removes little particle zinc hydroxide precipitation, obtains filter residue II and refined filtration Liquid；
Refined filtration liquid is passed through into resin tower, is weakly alkaline environment in control resin tower, after chelating absorption, remaining zinc ion It is incorporated on resin, obtains pure metabisulfite solution；
Pure metabisulfite solution is passed through into circulating tank, is then passed through again into bipolar membrane device, through the electrodialysis of membrane stack mechanism Effect and the circulating reflux effect between membrane stack mechanism and circulating tank, obtain acid solution through bipolar membrane device acid mouth, through Bipolar Membrane Device alkali outlet obtains lye, obtains salt water through bipolar membrane device salt outlet；
The acid solution is passed through into reverse osmosis unit, through counter osmosis, concentrated vitriol solution and dilution heat of sulfuric acid is obtained, passes through Concentrated vitriol solution is directly delivered to the acid bath process in cellulose viscose manufacturing technique by pipeline, by pipeline directly by dilute sulfuric acid Solution is delivered to sour circulating tank；
The lye is passed through into nanofiltration device, is acted on through nanofiltration membrane, sodium hydroxide solution and sulfur acid sodium, sodium hydroxide are obtained Mixed liquor, sodium hydroxide solution is directly delivered to by dipping or yellow process in cellulose viscose manufacturing technique by pipeline, And the mixed solution of sulfur acid sodium, sodium hydroxide is directly delivered to by blend tank by pipeline；
The salt water is passed through into hydrochlorate separator, demineralized water is passed through, is separated, obtains sulfuric acid solution and metabisulfite solution, Sulfuric acid solution is directly delivered to the acid bath process in cellulose viscose manufacturing technique by pipeline, and by pipeline directly by sulfuric acid Sodium solution is delivered to transfer tank.
Further, the viscose glue waste liquid include concentration be 200~300g/L sodium sulphate, concentration be 0.1~1g/L's The sulfuric acid that zinc sulfate and concentration are 5~10g/L；
Sodium sulfate concentration is 200~300g/L in the lysate；
Sodium sulfate concentration control is 300g/L in the blend tank；
The acid solution is the sulfuric acid solution of 60~80g/L of concentration, and after counter osmosis, the concentrated vitriol solution concentration is 110~130g/L, the dilution heat of sulfuric acid concentration are 10~30g/L；
The metabisulfite solution that the lye includes the sodium hydroxide solution that concentration is 45~80g/L and concentration is 0~2g/L；Through receiving After filter membrane effect, the concentration of sodium hydroxide solution is 45~80g/L, and sodium sulfate concentration is 25~50g/L, hydrogen-oxygen in mixed liquor Change na concn is 45~80g/L；
The metabisulfite solution that the salt water includes the sulfuric acid solution that concentration is 20~30g/L and concentration is 100~180g/L；Through acid After the separation of salt separator, the sulfuric acid solution concentration is 20~30g/L, and metabisulfite solution concentration is 100~180g/L.
Further, in centrifuge, the discharging flow of sodium sulphate is 2~4t/h in the powdery solid, zinc sulfate Discharging flow is 0.0014~0.014t/h, and the discharging flow of sulfuric acid is 0.07~0.14t/h；
In transfer tank, the feed rate of the demineralized water is 5~9.4m3/h；
In resin tower, the feed rate of the refined filtration liquid is 7~13.4m3/h；
In circulating tank, the feed rate of the pure metabisulfite solution is 7~13.4m3/h；
In bipolar membrane device, the feed rate of the pure metabisulfite solution is 7~13.4m3/h；
In bipolar membrane device, the discharging flow of the acid solution is 132~289m3/d, and the discharging flow of lye is 150~328m 3/d, the discharging flow of salt water are 140~264 m3/d；
In reverse osmosis unit, the concentrated vitriol solution discharging flow is 66~145m3/d, the dilution heat of sulfuric acid reactor effluent stream Amount is 66~145m3/d；
In nanofiltration device, the discharging flow of the sodium hydroxide is 150~328m3/d, and the discharging flow of the mixed liquor is 10~40m3/d；
In hydrochlorate separator, the feed rate of the demineralized water is 140~264m3/d；The reactor effluent stream of the sulfuric acid solution Amount is 140~264m3/d, and the discharging flow of sulfuric acid solution is 140~264m3/d.
Further, centrifuge (1) revolving speed is 4000~5000r/min；
PH is 9~11 in blend tank, and temperature is 30~40 DEG C；
Alkalescent in resin tower refers to that pH is 9~11；
In bipolar membrane device, set: electric current as 300~400A, voltage be 200~290V, temperature be 30~40 DEG C and fortune Row pressure is 0.03~0.1 Mpa；
In reverse osmosis unit, pressure is 6.5~8 Mpa；
In nanofiltration device, pressure is 2.3~2.8 Mpa；
It is pulsed feeds mode between demineralized water and salt water in hydrochlorate separator.
Further, the filter residue II in the filter residue I and essence filtering in coarse filtration is collected, and directly by the two with feed rate The acid bath process being delivered to for 0.0014-0.014kg/h in cellulose viscose manufacturing technique.
Further, it is additionally provided with hydrochlorate separator between the transfer tank and blend tank, resulting lysate is passed through After into hydrochlorate separator, demineralized water is passed through for 326m3/d with feed rate into hydrochlorate separator, separates, must discharge The concentrated sulfuric acid solution and impure metabisulfite solution that flow is 652m3/d, concentration is 5~15g/L, directly will be dense by pipeline Sulfuric acid solution is delivered to the acid bath process in cellulose viscose manufacturing technique, and impure metabisulfite solution is passed through to blend tank In, carry out subsequent handling.
Further, adjusting pH in blend tank is 9~11, and concrete operations include:
If this environment-friendly cycle processing system uses for the first time, with feed rate for 15.27~30.61L/h, it is passed through into blend tank Concentration is the sodium hydroxide solution of 720g/L；
If this environment-friendly cycle processing system is not to use for the first time, with feed rate for 137.43~489.6 L/h, to blend tank It is inside passed through the sodium hydroxide solution that concentration is 45~80g/L, concentration is that 45~80g/L sodium hydroxide solution comes from this environment-friendly cycle Nanofiltration device in processing system.
A kind of environment-friendly cycle processing system of viscose glue waste liquid, including viscose glue waste liquid is separated into powdery solid and concentration acid bath Lysate by adjusting temperature and is adjusted pH and tune sulfuric acid by the centrifuge of liquid, the transfer tank that powdery solid is dissolved as to lysate Na concn and there is suspended matter to generate blend tank, solution containing suspended matter is filtered into filter residue I and coarse filtration liquid coarse filter device, will Coarse filtration liquid is filtered into the fine filtering apparatus of filter residue II and refined filtration liquid, has pure sodium sulphate to generate by chelating absorption refined filtration liquid Resin tower, fluid circulation reflux circulating tank and by sodium sulphate electrodialysis be sulfuric acid and sodium hydroxide bipolar membrane device, in Turn trough is arranged in centrifuge station side；Transfer tank is connected with desalination water storage tank, and transfer tank is connect with blend tank；Blend tank is connected with The heat exchanger of temperature regulating, the storage alkali tank for adjusting pH and the desalination water storage tank for adjusting sodium sulfate concentration, and blend tank and coarse filter device connect It connects；Coarse filter device is connect with fine filtering apparatus, and fine filtering apparatus is connect with resin tower, and resin tower by circulating tank with it is bipolar Film device connection, forms the access of an independent loops between circulating tank and bipolar membrane device.
Further, the coarse filter device is the bag filter in 10~15 μm of aperture, and fine filtering apparatus is aperture 0.01~0.05 μm of ultrafilter.
Further, the resin tower at least three, is connected between resin tower and resin tower by pipeline, and pipeline is equipped with Valve and zinc ion detector, 0~3ppm of zinc ion detector test range.
Further, the resin tower includes tower body and is arranged on the intracorporal resin of tower, upper filter plate and lower filter plate, tower body top Portion is provided with inlet, and bottom is provided with liquid outlet；On tower body top, lower filter plate is arranged in tower body lower part for upper filter plate setting, on Filter chamber is formed between filter plate and lower filter plate, resin is arranged in filter chamber.
Further, the upper filter plate, lower filter plate are the filter plate with water distributing pore, are equipped with water distributor at water distributing pore.
Further, the circulating tank includes tank body and setting in the intracorporal vertical clapboard of tank, upper cross plate and lower cross plate, erect every Plate is vertically provided in tank body, and is fixed on top of the tank and side, and vertical clapboard side and inner tank wall form back cavity, another Side and inner tank wall form mixing chamber, form channel between vertical clapboard end and tank base inner wall；Top of the tank is equipped with reflux Mouthful, refluxing opening be connected to back cavity, and back cavity top is equipped with overflow port, equipped with upper cross plate below overflow port, upper cross plate end and Channel is formed between vertical clapboard；Top of the tank is additionally provided with feed inlet, and feed inlet is connected to mixing chamber, and mixing chamber lower part is equipped with discharging Mouthful, it is equipped with lower cross plate below discharge port, forms channel between lower cross plate end and vertical clapboard.
Further, the circulating tank includes the salt circulating tank, sour circulating tank and alkali circulating tank of at least two-stage, Bipolar Membrane dress It sets including at least two-stage membrane stack mechanism, salt circulating tank, sour circulating tank, alkali circulating tank and membrane stack mechanism series are correspondingly arranged；
Salt circulating tank feed inlet is connect with resin tower, and salt circulating tank discharge port is connect with membrane stack mechanism at the same level into salt mouth, membrane stack Mechanism salt outlet is connect with salt circulating tank refluxing opening at the same level, and an independence is formed between salt circulating tank and the membrane stack mechanism of peer The access of circulation, and salt circulating tank is connected with storage brine tank, salt circulating tank overflow port is connect with next stage salt circulating tank feed inlet；Most The salt circulating tank overflow port of rear stage is connected with hydrochlorate separator, hydrochlorate separator acid mouth by pipeline directly and viscose glue Acid station acid storage tank connection in fibre manufacturing technique, hydrochlorate separator salt outlet are directly connect with transfer tank by pipeline；
Sour circulating tank is connect with next stage acid circulating tank overflow port, and sour circulating tank feed inlet is connected with desalination water storage tank, acid circulation Tank discharge port is connect with membrane stack mechanism acid inlet at the same level, and membrane stack mechanism acid mouth is connect with sour circulating tank refluxing opening at the same level, The access of an independent loops is formed between sour circulating tank and the membrane stack mechanism of peer, sour circulating tank overflow port is connected with reverse osmosis dress It sets, the outlet of reverse osmosis unit concentrated acid is directly connect with the acid station acid storage tank in viscose glue production process by pipeline, reverse osmosis unit Penetrating fluid outlet is directly connect with sour circulating tank by pipeline；
Alkali circulating tank is connect with next stage alkali circulating tank overflow port, and alkali circulating tank feed inlet is connected with desalination water storage tank, alkali circulation Tank discharge port is connect with membrane stack mechanism alkali inlet at the same level, and membrane stack mechanism alkali outlet is connect with alkali circulating tank refluxing opening at the same level, The access of an independent loops is formed between alkali circulating tank and the membrane stack mechanism of peer, alkali circulating tank overflow port is connected with nanofiltration dress It sets, nanofiltration device filtrate port is directly connect with the stoste storage tank in cellulose viscose manufacturing technique by pipeline, nanofiltration device concentration Liquid mouth is directly connect with blend tank by pipeline.
Further, the membrane stack mechanism includes spaced diaphragm block and diaphragm plate, and membrane stack mechanism two sides are film The diaphragm plate of plate, two sides is connect with pole plate respectively；Power interface, pole water inlet and pole water out, a pole plate are equipped on pole plate Positive pole is connected by power interface, another pole plate connects power cathode by power interface；
The diaphragm block includes the multipair diaphragm and partition overlapped, and each pair of diaphragm includes cavity block, anode membrane and Bipolar Membrane, film Blade unit repeats to be arranged according to the arrangement of Bipolar Membrane, partition, cavity block, partition, anode membrane, partition；Partition one end be connected with into Yan Kou, Acid inlet and alkali inlet are respectively formed in diaphragm internal into the channel Yan Kou, acid inlet channel and alkali inlet channel；The partition other end It is connected with salt outlet, acid mouth and alkali outlet, forms salt outlet channel, acid mouth channel and alkali outlet channel in diaphragm internal.
Further, the block board thickness is 2~3mm, partition, Bipolar Membrane, cavity block and anode membrane both ends be provided with it is more A aperture, the aperture on partition are correspondingly arranged on runner.
Further, the pair of diaphragm is correspondingly arranged on a salt room, an acid compartment and an alkaline chamber, a salt room pair Answer one into the channel Yan Kou and a salt outlet channel；One corresponding acid inlet channel of acid compartment and an acid mouth channel； One corresponding alkali inlet channel of alkaline chamber and an alkali outlet channel.
When the above salt, bronsted lowry acids and bases bronsted lowry are by corresponding salt room, acid compartment and alkaline chamber, the separation of cross-flow filtration principle and film has been used Effect.
1 pair of diaphragm is correspondingly arranged on a salt room, the corresponding salt outlets in 20 salt rooms, 20 pairs of films, one salt outlet, and 40 Diaphragm is correspondingly arranged there are two salt outlet.
1 pair of diaphragm is correspondingly arranged on an acid compartment, the corresponding acid mouths of 20 acid compartments, 20 pairs of films, one acid mouth, and 40 Diaphragm is correspondingly arranged there are two acid mouth.
1 pair of diaphragm is correspondingly arranged on an alkaline chamber, the corresponding alkali outlets of 20 alkaline chambers, 20 pairs of films, one alkali outlet, and 40 Diaphragm is correspondingly arranged there are two alkali outlet.
The rectangle of the Bipolar Membrane, cavity block and anode membrane for 1500mm*500mm, gross area 0.75m2, effective coverage are long 1200mm*420mm, effective area 0.5m2, effective area accounting 66.67%.
The membrane voltage (10A/dm2,30 DEG C) of Bipolar Membrane is 1.2V；Water decomposition efficiency >=98%；Rupture strength >=0.4Mpa； With a thickness of 0.22mm.
Anode membrane model CSE-2, i.e. highly acid anode membrane have high-intensitive characteristic；Membrane impedance is 1.9 Ω cm2；Rupture is strong Degree is greater than 0.35 Mpa；With a thickness of 0.15mm.
Cavity block model ACM, i.e. alkalescent cavity block have the characteristic for being not easy acid；Membrane impedance is 2.6 Ω cm2；Rupture strength Greater than 0.15 Mpa；With a thickness of 0.11mm.
The running temperature of membrane stack is 30~40 DEG C, and the operating pressure of membrane stack is 0.03~0.1Mpa.
Nano filter membrance device is existing mature technology, can directly be bought and be obtained by producer.
Hydrochlorate separator includes resin column, it is different from the Adsorption and desorption rate of sodium sulphate between the two according to sulfuric acid and Separation, the device are existing mature technology, can directly be bought and be obtained by producer.(producer are as follows: Xi'an indigo plant knows scientific and technological new material stock Part Co., Ltd)
Reverse osmosis membrane apparatus is existing mature technology, can directly be bought and be obtained by producer.
Using the technical program, bring advantageous effects are as follows:
1) present invention by centrifuge, transfer tank, blend tank, coarse filter device, fine filtering apparatus, resin tower, circulating tank and The setting of bipolar membrane device forms environment-friendly cycle processing system, and by optimization for the treatment of conditions, technological parameter, equipment and refers to Mark etc., recycling of the completion to sulfuric acid, sodium hydroxide, dilute sulfuric acid sodium solution, and more applicable craft mass production.And by pair The setting of resin tower, circulating tank and bipolar membrane device, maximum recycling sulfuric acid, sodium hydroxide, dilute sulfuric acid sodium solution, and be effectively ensured The purity and concentration of sulfuric acid, sodium hydroxide, and the secondary pollution in non-treated process, can direct reuse in viscose glue production process or Zero-emission is realized in storage；
2) in blend tank of the invention, limit that pH is 30~40 DEG C as 9~11, temperature and sodium sulfate concentration is 300g/L, Under the setting that the pH is 9~11, guarantee that zinc ion utmostly precipitates, while being prepared work for remaining zinc ion by resin adsorption Make, the best effort environmental pH that resin tower adsorbs zinc ion is 9~11, that is, guarantees postorder resin tower under this condition to zinc The adsorption effect of ion avoids zinc ion impurity that from cannot completely removing；When pH≤9, zinc ion does not precipitate completely in solution, causes Zinc ion can not be removed utmostly；When pH >=11, precipitating dissolution, also resulting in zinc ion can not be completely removed；
Temperature setting is 30~40 DEG C, guarantees the maxima solubility of sodium sulphate, guarantees that stablizing for treatment process carries out.Temperature is lower than 30 DEG C, it will lead to sulfate crystal in solution and be precipitated, block pipeline；Temperature is higher than 40 DEG C, increases downstream process (such as: Bipolar Membrane Device electrodialysis) freezing water consumption；
Sodium sulfate concentration is set as 300g/L, guarantees the electrodialysis efficiency of bipolar membrane device, guarantees that stablizing for treatment process carries out. Concentration is lower than 300g/L, and equipment operating efficiency is caused to decline (such as: bipolar membrane device electrodialysis), low output；Concentration is higher than 300g/ L, excessive concentration causes sodium sulphate to be easy to appear crystallization, and then plugging risk increases, and is unfavorable for producing control；
3) in the present invention, by the setting of the intracorporal resin of resin tower tower, upper filter plate and lower filter plate, and limit its position and Connection relationship, guarantee refined filtration liquid enter after tower body smoothly, stablize, orderly fall, and increase the contact area of refined filtration liquid and resin And the time, zinc ion is effectively removed, the concentration and purity of subsequent products are improved；Meanwhile the setting can prevent resin from overflowing, and keep away Exempt from filter chamber blocking, guarantees that viscose glue waste liquid environmental protection treatment process is stablized and carry out；
4) in the present invention, by recycling the vertical clapboard in tank, upper cross plate, lower cross plate, back cavity, mixing chamber, channel, returning The setting of head piece, overflow port, feed inlet and discharge port, and its position and connection relationship are limited, avoid reflux and new addition Or newly-generated object mixes immediately, and by separation and guide functions, avoid reflux and new addition or newly-generated object in circulating tank Top mixes, and reduces material back-mixing cost, improves operational efficiency, guarantees that reflux mixes completely with new addition or newly-generated object, And the concentration of discharge port is improved, and then improve Bipolar Membrane membrane stack " electrodialysis " efficiency；
5) in the present invention, by diaphragm block in bipolar membrane device, diaphragm plate, pole plate, into the channel Yan Kou, acid inlet channel, into The setting in alkali mouth channel, salt outlet channel, acid mouth channel and alkali outlet channel etc., and limit its position, composition and connection Relationship guarantees that metabisulfite solution is orderly, controllable and effectively enter bipolar membrane device, promotes bipolar membrane device to stablize and carry out Cross-flow filtration and selective permeability of ionexchange membrane, and maximum recycling is carried out to metabisulfite solution, improve the dense of subsequent products Degree and purity；
6) in the present invention, the present invention is suitable for industrialized production, can not only be directly arranged in viscose glue production process, to viscous Glue waste liquid is recycled, and realizes zero-emission, and by product reuse to viscose glue production process, saves production cost, and improve The globality of equipment installation；And the present apparatus can also be separately provided, and be exclusively used in the processing of viscose glue waste liquid, improve device integration.
Detailed description of the invention
Fig. 1 is structural block diagram of the invention；
Fig. 2 is work flow diagram of the invention；
Fig. 3 is the connection schematic diagram of resin tower and resin tower in the present invention；
Fig. 4 is the structural schematic diagram of resin tower in the present invention；
Fig. 5 is the structural schematic diagram of circulating tank in the present invention；
Fig. 6 is the logical connection schematic diagram of embodiment 6 in the present invention；
Fig. 7 is that embodiment 6 patrols work flow diagram in the present invention；
Fig. 8 is the schematic diagram of bipolar membrane device in the present invention；
Fig. 9 is the diaphragm structure schematic diagram of bipolar membrane device in the present invention；
Figure 10 is the salt cell structure schematic diagram of bipolar membrane device in the present invention；
Figure 11 is the acid compartment structural schematic diagram of bipolar membrane device in the present invention；
Figure 12 is the alkaline chamber structural schematic diagram of bipolar membrane device in the present invention；
Figure 13 is the schematic illustration of bipolar membrane device in the present invention；
Wherein, in figure: 1, centrifuge, 2, transfer tank, 3, blend tank, 4, coarse filter device, 5, fine filtering apparatus, 6, resin tower, 7, bipolar membrane device, 8, circulating tank, 9, storage brine tank, 10, acid storage tank, 11, storage alkali tank, 12, desalination water storage tank, 13, heat exchanger, 14, salt circulating tank, 15, sour circulating tank, 16, alkali circulating tank, 17, valve, 18, zinc ion detector, 19, hydrochlorate separator, 20, reverse osmosis unit, 21, nanofiltration device, 22, pole water pot；
601, tower body, 602, filter chamber, 603, upper filter plate, 604, lower filter plate, 605, inlet, 606, liquid outlet, 607, water distributing pore, 608, water distributor；
801, tank body, 802, vertical clapboard, 803, upper cross plate, 804, lower cross plate, 805, back cavity, 806, mixing chamber, 807, reflux Mouthful, 808, overflow port, 809, feed inlet, 810, discharge port；
110, diaphragm block, 120, diaphragm plate, 130, pole plate, 140, power interface, 150, pole water inlet, 160, pole water out, 111, partition, 112, cavity block, 113, anode membrane, 114, Bipolar Membrane, 170, into Yan Kou, 180, acid inlet, 190, alkali inlet, 200, go out Salt mouth, 210, acid mouth, 220, alkali outlet, 171, into the channel Yan Kou, 181, acid inlet channel, 191, alkali inlet channel, 201, Salt outlet channel, 211, acid mouth channel, 221, alkali outlet channel, 230, aperture, 240, runner, 115, salt room, 116, acid compartment, 117, alkaline chamber, 250, pressure plate, 260, fastening bolt, 270, rack, 280, rack beam, 290, hydraulic press piston boit.
Specific embodiment
Below by technical scheme in the embodiment of the invention is clearly and completely described, it is clear that described reality Applying example is only a part of the embodiments of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this field is general Logical technical staff all other embodiment obtained without making creative work belongs to what the present invention protected Range.
Embodiment 1
A kind of environment-friendly cycle treatment process of viscose glue waste liquid,
Viscose glue waste liquid through centrifuge 1 separation after, obtain the powdery solid containing sodium sulphate, zinc sulfate and sulfuric acid and containing sodium sulphate, The gelled acid bath foam of zinc sulfate and sulfuric acid, the acid being directly delivered to gelled acid bath foam by pipeline in cellulose viscose manufacturing technique It stands acid storage tank, the powdery solid containing sodium sulphate, zinc sulfate and sulfuric acid is placed in transfer tank 2；
By adding demineralized water into transfer tank 2, powdery solid dissolution obtains lysate；
Then, lysate is passed through into blend tank 3, adjusts temperature, pH and sodium sulfate concentration in blend tank 3, obtains containing suspended matter Solution；
Under this condition, the zinc ion in lysate generates zinc hydroxide white precipitate in conjunction with hydroxide ion, and is suspended in In solution, there is about 80% zinc ion to be deposited during this；
Suspended matter solution will be contained to be passed through in coarse filter device 4, coarse filtration, and remove bulky grain zinc hydroxide precipitation, and obtain filter residue I and thick Filtrate；
Coarse filtration liquid is passed through into fine filtering apparatus 5, essence filtering removes little particle zinc hydroxide precipitation, obtains filter residue II and refined filtration Liquid；
Refined filtration liquid is passed through into resin tower 6, control resin tower 6 in be weakly alkaline environment, through chelating absorption after, remaining zinc from Son combines on resin, obtains pure metabisulfite solution；
Pure metabisulfite solution is passed through into circulating tank 8, is then passed through again into bipolar membrane device 7, through membrane stack mechanism electric osmose Analysis effect and the circulating reflux effect between membrane stack mechanism and circulating tank 8, obtain acid solution through 7 acid mouth of bipolar membrane device, through double Film device 7 alkali outlet in pole obtains lye, obtains salt water through 7 salt outlet of bipolar membrane device；
The acid solution is passed through into reverse osmosis unit 20, through counter osmosis, obtains concentrated vitriol solution and dilution heat of sulfuric acid, is led to Concentrated vitriol solution is directly delivered to the acid bath process in cellulose viscose manufacturing technique by piping, by pipeline directly by dilute sulphur Acid solution is delivered to sour 15 feed inlet of circulating tank；
The lye is passed through into nanofiltration device 21, is acted on through nanofiltration membrane, sodium hydroxide solution and sulfur acid sodium, hydroxide are obtained Sodium hydroxide solution is directly delivered to the dipping process in cellulose viscose manufacturing technique by pipeline, and led to by the mixed liquor of sodium The mixed solution of sulfur acid sodium, sodium hydroxide is directly delivered to blend tank 3 by piping；
The salt water is passed through into hydrochlorate separator 19, demineralized water is passed through, is separated, sulfuric acid solution is obtained and sodium sulphate is molten Sulfuric acid solution is directly delivered to the acid bath process in cellulose viscose manufacturing technique by pipeline, and passes through pipeline and directly will by liquid Metabisulfite solution is delivered to transfer tank 2.
Embodiment 2
On the basis of embodiment 1, further,
Further, the viscose glue waste liquid include concentration be 200g/L sodium sulphate, concentration be 0.1g/L zinc sulfate and concentration For the sulfuric acid of 5g/L；
Sodium sulfate concentration is 300g/L in the lysate；
Sodium sulfate concentration control is 300g/L in the blend tank 3；
The acid solution is the sulfuric acid solution of concentration 60g/L, and after counter osmosis, the concentrated vitriol solution concentration is 110g/ L, the dilution heat of sulfuric acid concentration are 10g/L；
The lye is the sodium hydroxide solution that concentration is 45g/L；After nanofiltration membrane acts on, the concentration of sodium hydroxide solution is 45g/L；
The metabisulfite solution that the salt water includes the sulfuric acid solution that concentration is 20g/L and concentration is 100g/L；It separates and fills through hydrochlorate After setting 19 separation, the sulfuric acid solution concentration is 20g/L, and metabisulfite solution concentration is 100g/L.
Further, in centrifuge 1, the discharging flow of sodium sulphate is 2t/h in the powdery solid, and zinc sulfate goes out Stream amount is 0.0014t/h, and the discharging flow of sulfuric acid is 0.07t/h；
In transfer tank 2, the feed rate of the demineralized water is 5m3/h；
In resin tower 6, the feed rate of the refined filtration liquid is 7m3/h；
In circulating tank 8, the feed rate of the pure metabisulfite solution is 7m3/h；
In bipolar membrane device 7, the feed rate of the pure metabisulfite solution is 7m3/h；
In bipolar membrane device 7, the discharging flow of the acid solution is 132m3/d, and the discharging flow of lye is 150m3/d, salt water Discharging flow be 140m3/d；
In reverse osmosis unit 20, the concentrated vitriol solution discharging flow is 66m3/d, the dilution heat of sulfuric acid discharging flow For 66m3/d；
In nanofiltration device 21, the discharging flow of the sodium hydroxide is 150m3/d, and the discharging flow of the mixed liquor is 10m ³/d；
In hydrochlorate separator 19, the feed rate of the demineralized water is 140m3/d；The discharging flow of the sulfuric acid solution is 140m3/d, the discharging flow of sulfuric acid solution are 140m3/d.
Further, 1 revolving speed of centrifuge is 4000r/min；
PH is 9 in blend tank 3, and temperature is 30 DEG C；
Alkalescent in resin tower 6 refers to that pH is 9；
In bipolar membrane device 7, set: electric current 360A, voltage 255V, temperature are 35 DEG C and operating pressure is 0.06 Mpa；
In reverse osmosis unit 20, pressure is 6.5 Mpa；
In nanofiltration device 21, pressure 2.3Mpa；
It is pulsed feeds mode between demineralized water and acid solution in hydrochlorate separator 19.
Embodiment 3
On the basis of embodiment 2, the present embodiment difference is:
Further, the viscose glue waste liquid include concentration be 300g/L sodium sulphate, concentration be 1g/L zinc sulfate and concentration be The sulfuric acid of 10g/L；
Sodium sulfate concentration is 300g/L in the lysate；
Sodium sulfate concentration control is 300g/L in the blend tank 3；
The acid solution is the sulfuric acid solution of concentration 80g/L, and after counter osmosis, the concentrated vitriol solution concentration is 130g/ L, the dilution heat of sulfuric acid concentration are 30g/L；
The metabisulfite solution that the lye includes the sodium hydroxide solution that concentration is 80g/L and concentration is 2g/L；Make through nanofiltration membrane With rear, the concentration of sodium hydroxide solution is 80g/L, in mixed liquor sodium sulfate concentration be 50g/L, naoh concentration 80g/ L；
The metabisulfite solution that the salt water includes the sulfuric acid solution that concentration is 30g/L and concentration is 180g/L；It separates and fills through hydrochlorate After setting 19 separation, the sulfuric acid solution concentration is 30g/L, and metabisulfite solution concentration is 180g/L.
Further, in centrifuge 1, the discharging flow of sodium sulphate is 2.5t/h in the powdery solid, zinc sulfate Discharging flow is 0.008t/h, and the discharging flow of sulfuric acid is 0.075t/h；
In transfer tank 2, the feed rate of the demineralized water is 6m3/h；
In resin tower 6, the feed rate of the refined filtration liquid is 8.5m3/h；
In circulating tank 8, the feed rate of the pure metabisulfite solution is 8.5m3/h；
In bipolar membrane device 7, the feed rate of the pure metabisulfite solution is 8.5m3/h；
In bipolar membrane device 7, the discharging flow of the acid solution is 165m3/ d, the discharging flow of lye are 187.5m3/ d, salt The discharging flow of water is 168m3/d；
In reverse osmosis unit 20, the concentrated vitriol solution discharging flow is 82.5m3/ d, the dilution heat of sulfuric acid reactor effluent stream Amount is 82.5m3/d；
In nanofiltration device 21, the discharging flow of the sodium hydroxide is 187.5m3The discharging flow of/d, the mixed liquor is 13m3/d；
In hydrochlorate separator 19, the feed rate of the demineralized water is 168m3/d；The discharging flow of the sulfuric acid solution is 168m3/ d, the discharging flow of sulfuric acid solution are 168m3/d。
Further, 1 revolving speed of centrifuge is 4300r/min；
PH is 11 in blend tank 3, and temperature is 40 DEG C；
Alkalescent in resin tower 6 refers to that pH is 9.5；
In bipolar membrane device 7, set: electric current 400A, voltage 280V, temperature are 33 DEG C and operating pressure is 0.06 Mpa；
In reverse osmosis unit 20, pressure is 8 Mpa；
In nanofiltration device 21, pressure is 2.8 Mpa；
It is pulsed feeds mode between demineralized water and acid solution in hydrochlorate separator 19.
Embodiment 4
On the basis of embodiment 2-3, the present embodiment difference is:
Further, the viscose glue waste liquid include concentration be 250g/L sodium sulphate, concentration be 0.6g/L zinc sulfate and concentration For the sulfuric acid of 8g/L；
Sodium sulfate concentration is 300g/L in the lysate；
Sodium sulfate concentration control is 300g/L in the blend tank 3；
The acid solution is the sulfuric acid solution of concentration 70g/L, and after counter osmosis, the concentrated vitriol solution concentration is 120g/ L, the dilution heat of sulfuric acid concentration are 20g/L；
The metabisulfite solution that the lye includes the sodium hydroxide solution that concentration is 64g/L and concentration is 1g/L；Make through nanofiltration membrane With rear, the concentration of sodium hydroxide solution is 64g/L, in mixed liquor sodium sulfate concentration be 38g/L, naoh concentration 64g/ L；
The metabisulfite solution that the salt water includes the sulfuric acid solution that concentration is 25g/L and concentration is 140g/L；It separates and fills through hydrochlorate After setting 19 separation, the sulfuric acid solution concentration is 25g/L, and metabisulfite solution concentration is 140g/L.
Further, in centrifuge 1, the discharging flow of sodium sulphate is 3t/h in the powdery solid, and zinc sulfate goes out Stream amount is 0.008t/h, and the discharging flow of sulfuric acid is 0.010t/h；
In transfer tank 2, the feed rate of the demineralized water is 7m3/h；
In resin tower 6, the feed rate of the refined filtration liquid is 10m3/h；
In circulating tank 8, the feed rate of the pure metabisulfite solution is 10m3/h；
In bipolar membrane device 7, the feed rate of the pure metabisulfite solution is 10m3/h；
In bipolar membrane device 7, the discharging flow of the acid solution is 198m3/d, and the discharging flow of lye is 225m3/d, salt water Discharging flow be 196.8m3/d；
In reverse osmosis unit 20, the concentrated vitriol solution discharging flow is 99m3/d, the dilution heat of sulfuric acid discharging flow For 99m3/d；
In nanofiltration device 21, the discharging flow of the sodium hydroxide is 225m3/d, and the discharging flow of the mixed liquor is 15m ³/d；
In hydrochlorate separator 19, the feed rate of the demineralized water is 196.8m3/d；The discharging flow of the sulfuric acid solution For 196.8m3/d, the discharging flow of sulfuric acid solution is 196.8m3/d.
Further, 1 revolving speed of centrifuge is 4500r/min；
PH is 10 in blend tank 3, and temperature is 35 DEG C；
Alkalescent in resin tower 6 refers to that pH is 10；
In bipolar membrane device 7, set: electric current 380A, voltage 279V, temperature are 35 DEG C and operating pressure is 0.06 Mpa；
In reverse osmosis unit 20, pressure 7.4Mpa；
In nanofiltration device 21, pressure 2.6Mpa；
It is pulsed feeds mode between demineralized water and acid solution in hydrochlorate separator 19.
Embodiment 5
On the basis of embodiment 2-4, the present embodiment difference is:
Further, the viscose glue waste liquid include concentration be 230g/L sodium sulphate, concentration be 0.2g/L zinc sulfate and concentration For the sulfuric acid of 6g/L；
Sodium sulfate concentration is 300g/L in the lysate；
Sodium sulfate concentration control is 300g/L in the blend tank 3；
The acid solution is the sulfuric acid solution of concentration 65g/L, and after counter osmosis, the concentrated vitriol solution concentration is 115g/ L, the dilution heat of sulfuric acid concentration are 15g/L；
The metabisulfite solution that the lye includes the sodium hydroxide solution that concentration is 55g/L and concentration is 0.9g/L；Through nanofiltration membrane After effect, the concentration of sodium hydroxide solution is 55g/L, and sodium sulfate concentration is 30g/L in mixed liquor, naoh concentration is 55g/L；
The metabisulfite solution that the salt water includes the sulfuric acid solution that concentration is 23g/L and concentration is 120g/L；It separates and fills through hydrochlorate After setting 19 separation, the sulfuric acid solution concentration is 23g/L, and metabisulfite solution concentration is 120g/L.
Further, in centrifuge 1, the discharging flow of sodium sulphate is 3.5t/h in the powdery solid, zinc sulfate Discharging flow is 0.010t/h, and the discharging flow of sulfuric acid is 0.011t/h；
In transfer tank 2, the feed rate of the demineralized water is 8.2m3/h；
In resin tower 6, the feed rate of the refined filtration liquid is 11.7m3/h；
In circulating tank 8, the feed rate of the pure metabisulfite solution is 11.7m3/h；
In bipolar membrane device 7, the feed rate of the pure metabisulfite solution is 11.7m3/h；
In bipolar membrane device 7, the discharging flow of the acid solution is 231m3/d, and the discharging flow of lye is 262.5m3/d, salt The discharging flow of water is 230.4m3/d；
In reverse osmosis unit 20, the concentrated vitriol solution discharging flow is 115.5m3/d, the dilution heat of sulfuric acid reactor effluent stream Amount is 115.5m3/d；
In nanofiltration device 21, the discharging flow of the sodium hydroxide is 231.3m3/d, and the discharging flow of the mixed liquor is 17.5m³/d；
In hydrochlorate separator 19, the feed rate of the demineralized water is 230.4m3/d；The discharging flow of the sulfuric acid solution For 230.4m3/d；The discharging flow of sulfuric acid solution is 230.4m3/d.
Further, 1 revolving speed of centrifuge is 4890r/min；
PH is 9.7 in blend tank 3, and temperature is 33 DEG C；
Alkalescent in resin tower 6 refers to that pH is 9.7；
In bipolar membrane device 7, set: electric current 375A, voltage 265V, temperature are 31 DEG C and operating pressure is 0.05 Mpa；
In reverse osmosis unit 20, pressure is 6.8 Mpa；
In nanofiltration device 21, pressure is 2.6 Mpa；
It is pulsed feeds mode between demineralized water and acid solution in hydrochlorate separator 19.
Embodiment 6
On the basis of embodiment 2-5, the present embodiment difference is:
Further, the viscose glue waste liquid include concentration be 280g/L sodium sulphate, concentration be 0.9g/L zinc sulfate and concentration For the sulfuric acid of 8g/L；
Sodium sulfate concentration is 300g/L in the lysate；
Sodium sulfate concentration control is 300g/L in the blend tank 3；
The acid solution is the sulfuric acid solution of concentration 78g/L, and after counter osmosis, the concentrated vitriol solution concentration is 125g/ L, the dilution heat of sulfuric acid concentration is 25g/L；
The metabisulfite solution that the lye includes the sodium hydroxide solution that concentration is 75g/L and concentration is 1.6g/L；Through nanofiltration membrane After effect, the concentration of sodium hydroxide solution is 73g/L, and sodium sulfate concentration is 25~75g/L, naoh concentration in mixed liquor For 73g/L；
The metabisulfite solution that the salt water includes the sulfuric acid solution that concentration is 28g/L and concentration is 175g/L；It separates and fills through hydrochlorate After setting 19 separation, the sulfuric acid solution concentration is 28g/L, and metabisulfite solution concentration is 175g/L.
Further, in centrifuge 1, the discharging flow of sodium sulphate is 4t/h in the powdery solid, and zinc sulfate goes out Stream amount is 0.014t/h, and the discharging flow of sulfuric acid is 0.14t/h；
In transfer tank 2, the feed rate of the demineralized water is 9.4m3/h；
In resin tower 6, the feed rate of the refined filtration liquid is 13.4m3/h；
In circulating tank 8, the feed rate of the pure metabisulfite solution is 13.4m3/h；
In bipolar membrane device 7, the feed rate of the pure metabisulfite solution is 13.4m3/h；
In bipolar membrane device 7, the discharging flow of the acid solution is 289m3/d, and the discharging flow of lye is 328m3/d, salt water Discharging flow be 264m3/d；
In reverse osmosis unit 20, the concentrated vitriol solution discharging flow is 144.5m3/d, the dilution heat of sulfuric acid reactor effluent stream Amount is 144.5m3/d；
In nanofiltration device 21, the discharging flow of the sodium hydroxide is 328m3/d, and the discharging flow of the mixed liquor is 40m ³/d；
In hydrochlorate separator 19, the feed rate of the demineralized water is 264m3/d；The discharging flow of the sulfuric acid solution is 264m3/d, the discharging flow of sulfuric acid solution are 264m3/d.
Further, 1 revolving speed of centrifuge is 4890r/min；
PH is 10.2 in blend tank 3, and temperature is 39 DEG C；
Alkalescent in resin tower 6 refers to that pH is 10.2；
In bipolar membrane device 7, set: electric current 387A, voltage 275V, temperature are 39 DEG C and operating pressure is 0.08 Mpa；
In reverse osmosis unit 20, pressure is 7.5 Mpa；
In nanofiltration device 21, pressure is 2.7 Mpa；
It is pulsed feeds mode between demineralized water and acid solution in hydrochlorate separator 19.
Embodiment 7
On the basis of embodiment 1-6, further,
The filter residue II in the filter residue I and essence filtering in coarse filtration is collected, and with feed rate is directly 0.0085kg/h by the two The acid bath process being delivered in cellulose viscose manufacturing technique.
Embodiment 8
On the basis of embodiment 7, further,
It is additionally provided with hydrochlorate separator 19 between the transfer tank 2 and blend tank 3, resulting lysate is passed through to hydrochlorate and is separated After in device 19, demineralized water is passed through for 100m3/d with feed rate into hydrochlorate separator 19, is separated, obtaining discharging flow is 100m3/d, the concentrated sulfuric acid solution and impure metabisulfite solution that concentration is 10g/L, by pipeline directly by concentrated sulfuric acid solution The acid bath process being delivered in cellulose viscose manufacturing technique, impure metabisulfite solution is passed through into blend tank 3, after progress Continuous process.
Embodiment 9
On the basis of embodiment 8, further,
Adjusting pH in blend tank 3 is 10, and concrete operations include:
It is 25L/h with feed rate if this environment-friendly cycle processing system uses for the first time, being passed through concentration into blend tank 3 is The sodium hydroxide solution of 720g/L, concentration be 720g/L sodium hydroxide solution by sodium hydroxide be dissolved in water preparation obtained by；
If this environment-friendly cycle processing system is not to use for the first time, with feed rate for 370 L/h, it is passed through into blend tank 3 dense Degree is the sodium hydroxide solution of 73g/L, and concentration is nanofiltration of the 73g/L sodium hydroxide solution in this environment-friendly cycle processing system Device 21.
Embodiment 10
On the basis of embodiment 1-9, following equipment is utilized:
It is as shown in Figs. 1-2: a kind of environment-friendly cycle processing system of viscose glue waste liquid, including by viscose glue waste liquid be separated into powdery solid with Lysate is passed through adjusting temperature and tune by the centrifuge 1 of gelled acid bath foam, the transfer tank 2 that powdery solid is dissolved as to lysate PH and adjust sodium sulfate concentration and there is suspended matter to generate blend tank 3, solution containing suspended matter is filtered into the thick of filter residue I and coarse filtration liquid Filter device 4, the fine filtering apparatus 5 that coarse filtration liquid is filtered into filter residue II and refined filtration liquid have refined filtration liquid by chelating absorption The circulating tank 8 and be sulfuric acid and sodium hydroxide by sodium sulphate electrodialysis that the resin tower 6 of pure sodium sulphate generation, fluid circulation flow back Bipolar membrane device 7, transfer tank 2 be arranged in 1 station side of centrifuge；Transfer tank 2 is connected with desalination water storage tank 12, and transfer tank 2 It is connect with blend tank 3；Blend tank 3 is connected with the heat exchanger 13 of temperature regulating, adjusts the storage alkali tank 11 of pH and adjusts the desalination of sodium sulfate concentration Water storage tank 12, and blend tank 3 is connect with coarse filter device 4；Coarse filter device 4 is connect with fine filtering apparatus 5, fine filtering apparatus 5 It is connect with resin tower 6, and resin tower 6 is connect by circulating tank 8 with bipolar membrane device 7, between circulating tank 8 and bipolar membrane device 7 Form the access of an independent loops.
Embodiment 11
On the basis of embodiment 10, further, the coarse filter device 4 is the bag filter in 10 μm of aperture, smart mistake Filter the ultrafilter that device 5 is 0.01 μm of aperture.
Embodiment 12
On the basis of embodiment 11, the present embodiment difference is: the coarse filter device 4 is the bag type filtering in 15 μm of aperture Device, fine filtering apparatus 5 are the ultrafilter in 0.05 μm of aperture.
Embodiment 13
On the basis of embodiment 11-12, the present embodiment difference is: the coarse filter device 4 is the pocket type mistake in 13 μm of aperture Filter, fine filtering apparatus 5 are the ultrafilter in 0.02 μm of aperture.
Embodiment 14
On the basis of embodiment 11-13, further,
As shown in Figure 3: the resin tower 6 is three, is connected between resin tower 6 and resin tower 6 by pipeline, and pipeline is equipped with valve Door 17 and zinc ion detector 18,18 0~3ppm of detection range of zinc ion detector.
It is as shown in Figure 4: the resin tower 6 include tower body 601 and be arranged in tower body 601 resin, upper filter plate 603 and under Filter plate 604 is provided with inlet 605 at the top of tower body 601, and bottom is provided with liquid outlet 606；Upper filter plate 603 is arranged in tower body 601 Top, lower filter plate 604, which is arranged between 601 lower part of tower body, upper filter plate 603 and lower filter plate 604, forms filter chamber 602, resin setting In filter chamber 602.
The upper filter plate 603, lower filter plate 604 are the filter plate with water distributing pore 607, are equipped with water distribution at water distributing pore 607 Device 608.
Embodiment 15
On the basis of embodiment 14, further,
It is as shown in Figure 5: vertical clapboard 802,803 and of upper cross plate that the circulating tank 8 includes tank body 801 and is arranged in tank body 801 Lower cross plate 804, vertical clapboard 802 are vertically provided in tank body 801, and are fixed on 801 top of tank body and side, vertical clapboard 802 1 Side and 801 inner wall of tank body form back cavity 805, and the other side and 801 inner wall of tank body form mixing chamber 806,802 end of vertical clapboard with Channel is formed between 801 bottom interior wall of tank body；Refluxing opening 807 is equipped at the top of tank body 801, refluxing opening 807 and back cavity 805 connect Logical, 805 top of back cavity is equipped with overflow port 808, is equipped with upper cross plate 803 below overflow port 808,803 end of upper cross plate and it is perpendicular every Channel is formed between plate 802；Feed inlet 809 is additionally provided at the top of tank body 801, feed inlet 809 is connected to mixing chamber 806, mixing chamber 806 lower parts are equipped with discharge port 810, lower cross plate 804 are equipped with below discharge port 810, between 804 end of lower cross plate and vertical clapboard 802 Form channel.
The circulating tank 8 includes that the salt circulating tank 14, sour circulating tank 15 and alkali circulating tank 16, bipolar membrane device 7 of three-level wrap Include three-level membrane stack mechanism, salt circulating tank 14, sour circulating tank 15, alkali circulating tank 16 and membrane stack mechanism series are correspondingly arranged；
As shown in fig. 6-7: the circulating tank 8 include first order salt circulating tank, first order acid circulating tank, first order alkali circulating tank, Second level salt circulating tank, second level acid circulating tank, second level alkali circulating tank, third level salt circulating tank, third level acid circulating tank and Third level alkali circulating tank, bipolar membrane device 7 include first order membrane stack mechanism, second level membrane stack mechanism and third level membrane stack mechanism, First order salt circulating tank, first order acid circulating tank, first order alkali circulating tank are connect with first order membrane stack mechanism, and second level salt follows Ring tank, second level acid circulating tank, second level alkali circulating tank are connect with second level membrane stack mechanism, third level salt circulation, the third level Sour circulating tank and third level alkali circulating tank are connect with third level membrane stack mechanism；
First order salt circulating tank feed inlet is connect with resin tower 6, first order salt circulating tank discharge port and first order membrane stack mechanism into The connection of salt mouth, first order membrane stack mechanism salt outlet are connect with first order salt circulating tank refluxing opening, first order salt circulating tank and first The access of an independent loops is formed between grade membrane stack mechanism, first order salt circulating tank is connected with storage brine tank；
Second level salt circulating tank is connect with first order salt circulating tank overflow port, second level salt circulating tank feed inlet and storage brine tank 9 Connection, and second level salt circulating tank discharge port is connect with second level membrane stack mechanism into salt mouth, second level membrane stack mechanism salt outlet and The connection of second level salt circulating tank refluxing opening, forms an independent loops between second level salt circulating tank and second level membrane stack mechanism Access；
Third level salt circulating tank is connect with second level salt circulating tank overflow port, third level salt circulating tank feed inlet and storage brine tank 9 Connection, and third level salt circulating tank discharge port is connect with third level membrane stack mechanism into salt mouth, third level membrane stack mechanism salt outlet and The connection of third level salt circulating tank refluxing opening, forms an independent loops between third level salt circulating tank and third level membrane stack mechanism Access.Third level salt circulating tank overflow port is connected with hydrochlorate separator 19, and 19 acid mouth of hydrochlorate separator is straight by pipeline It connects and connect with the acid station acid storage tank in viscose rayon production process, 19 salt outlet of hydrochlorate separator passes through pipeline directly and transfer Slot 2 connects；
First order acid circulating tank feed inlet is connected with desalination water storage tank 12, first order acid circulating tank discharge port and first order membrane stack mechanism Acid inlet connection, first order membrane stack mechanism acid mouth connect with first order acid circulating tank refluxing opening, first order acid circulating tank and the The access of an independent loops is formed between level-one membrane stack mechanism, first order acid circulating tank overflow port is connected with reverse osmosis unit 20, The outlet of 20 concentrated acid of reverse osmosis unit is directly connect with the acid station acid storage tank in viscose glue production process by pipeline, reverse osmosis unit 20 Penetrating fluid outlet is directly connect with first order acid circulating tank by pipeline；
Second level acid circulating tank overflow port is connect with first order acid circulating tank, second level acid circulating tank feed inlet and desalination water storage tank 12 connections, second level acid circulating tank discharge port connect with second level membrane stack mechanism acid inlet, second level membrane stack mechanism acid mouth and The connection of second level acid circulating tank refluxing opening, forms an independent loops between second level acid circulating tank and second level membrane stack mechanism Access；
Third level acid circulating tank overflow port is connect with second level acid circulating tank, second level acid circulating tank feed inlet and desalination water storage tank 12 connections, third level acid circulating tank discharge port connect with third level membrane stack mechanism acid inlet, third level membrane stack mechanism acid mouth and The connection of third level acid circulating tank refluxing opening, forms an independent loops between third level acid circulating tank and third level membrane stack mechanism Access；
First order alkali circulating tank feed inlet is connected with desalination water storage tank 12, first order alkali circulating tank discharge port and first order membrane stack mechanism Alkali inlet connection, first order membrane stack mechanism alkali outlet connect with first order alkali circulating tank refluxing opening, first order alkali circulating tank and the The access of an independent loops is formed between level-one membrane stack mechanism, first order alkali circulating tank overflow port is connected with nanofiltration device 21, receives Filter 21 filtrate port of device is directly connect with the stoste storage tank in viscose glue production process by pipeline, and 21 concentrate mouth of nanofiltration device is logical Piping is directly connect with blend tank 3；
Second level alkali circulating tank overflow port is connect with first order alkali circulating tank, second level acid circulating tank feed inlet and desalination water storage tank 12 connections, second level alkali circulating tank discharge port connect with second level membrane stack mechanism alkali inlet, second level membrane stack mechanism alkali outlet and The connection of second level alkali circulating tank refluxing opening, forms an independent loops between second level alkali circulating tank and second level membrane stack mechanism Access；
Third level alkali circulating tank overflow port is connect with second level alkali circulating tank, third level acid circulating tank feed inlet and desalination water storage tank 12 connections, third level alkali circulating tank discharge port connect with third level membrane stack mechanism alkali inlet, third level membrane stack mechanism alkali outlet and The connection of third level alkali circulating tank refluxing opening, forms an independent loops between third level alkali circulating tank and third level membrane stack mechanism Access.
First order membrane stack mechanism, second level membrane stack mechanism and third level membrane stack mechanism are connected with pole water pot 22.
Embodiment 16
On the basis of embodiment 15, further,
As shown in Figure 8: the membrane stack mechanism includes spaced diaphragm block 110 and diaphragm plate 120, and membrane stack mechanism two sides are The diaphragm plate 120 of diaphragm plate 120, two sides is connect with pole plate 130 respectively；Power interface 140, pole water inlet 150 are equipped on pole plate 130 With pole water out 160, a pole plate 130 connects positive pole by power interface 140, another pole plate 130 is connect by power supply Mouth 140 connects power cathodes；
The diaphragm block 110 includes the multipair diaphragm overlapped and partition 111, and each pair of diaphragm includes cavity block 112, anode membrane 113 and Bipolar Membrane 114, diaphragm block 110 is according to Bipolar Membrane 114, partition 111, cavity block 112, partition 111, anode membrane 113, partition 111 arrangement repeats to be arranged；111 one end of partition is connected with into salt mouth 170, acid inlet 180 and alkali inlet 190, in partition 111 Portion is respectively formed into the channel Yan Kou 171, acid inlet channel 181 and alkali inlet channel 191；111 other end of partition is connected with out salt Mouthfuls 200, acid mouth 210 and alkali outlet 220 form salt outlet channel 201, acid mouth channel 211 and alkali out inside partition 111 Mouth channel 221.
Embodiment 17
On the basis of embodiment 16, further,
As shown in Figure 9: for the partition 111 with a thickness of 3mm, partition 111, Bipolar Membrane 114, the both ends of cavity block 112 and anode membrane 113 are equal Multiple apertures 230 are provided with, the aperture 230 on partition 111 is correspondingly arranged on runner 240.
As shown in figs. 10-12: the pair of diaphragm is correspondingly arranged on a salt room, an acid compartment and an alkaline chamber, and one Salt room corresponds to one into the channel Yan Kou and a salt outlet channel；One corresponding acid inlet channel of acid compartment and an acid mouth Channel；One corresponding alkali inlet channel of alkaline chamber and an alkali outlet channel.
When the above salt, bronsted lowry acids and bases bronsted lowry are by corresponding salt room 115, acid compartment 116 and alkaline chamber 117, cross-flow filtration principle has been used With the centrifugation of film.
1 pair of diaphragm is correspondingly arranged on a salt room, the corresponding salt outlets in 20 salt rooms, 20 pairs of films, one salt outlet, and 40 Diaphragm is correspondingly arranged there are two salt outlet.
1 pair of diaphragm is correspondingly arranged on an acid compartment, the corresponding acid mouths of 20 acid compartments, 20 pairs of films, one acid mouth, and 40 Diaphragm is correspondingly arranged there are two acid mouth.
1 pair of diaphragm is correspondingly arranged on an alkaline chamber, the corresponding alkali outlets of 20 alkaline chambers, 20 pairs of films, one alkali outlet, and 40 Diaphragm is correspondingly arranged there are two alkali outlet.
The Bipolar Membrane 114, cavity block 112 and anode membrane 113 are the rectangle of 1500mm*500mm, and gross area 0.75m2 has Imitate the long 1200mm*420mm in region, effective area 0.5m2, effective area accounting 66.67%.
The membrane voltage (10A/dm2,30 DEG C) of Bipolar Membrane 114 is 1.2V；Water decomposition efficiency >=98%；Rupture strength >= 0.4Mpa；With a thickness of 0.22mm.
113 model CSE-2 of anode membrane, i.e. highly acid anode membrane 113 have high-intensitive characteristic；Membrane impedance is 1.9 Ω cm2； Rupture strength is greater than 0.35 Mpa；With a thickness of 0.15mm.
112 model ACM of cavity block, i.e. alkalescent cavity block 112 have the characteristic for being not easy acid；Membrane impedance is 2.6 Ω cm2；It is broken Resistance to spalling is greater than 0.15 Mpa；With a thickness of 0.11mm.
The running temperature of membrane stack is 30 DEG C, and the operating pressure of membrane stack is 0.05Mpa.
Embodiment 18
By taking sodium sulphate content is the viscose glue waste liquid of 1T as an example, the environment-friendly cycle treatment process of viscose glue waste liquid is carried out, specific as follows:
It is dense to be dissolved as sodium sulfate concentration 250g/L, sulfuric acid zinc concentration 0.5g/L and sulfuric acid by addition demineralized water by A for viscose glue waste liquid Spend the solution of 5g/L, overall solution volume 4m3；
B will be passed through through the resulting solution of step A into blend tank 3, and adjusting pH is 10, consumes sodium hydroxide 16.5kg, generate hydrogen-oxygen Change zinc 1.2kg；
C will be passed through through the resulting hydrogeneous burnett's solution of step B into bag filter, and about 35% zinc hydroxide precipitation is cut It stays, generates filter residue 0.4kg, obtain coarse filtration liquid；
Resulting coarse filtration liquid is passed through into ultrafilter by D, and remaining zinc hydroxide precipitation is trapped, and generates the concentration containing zinc hydroxide Liquid 0.13m3 and its concentration 6g/L, and refined filtration liquid is obtained, and impurity content is micro in refined filtration liquid；
Resulting refined filtration liquid is passed through into resin tower 6 by E, through resin adsorption, completely removes impurity, and obtaining content is the pure of 1T Metabisulfite solution；
Resulting pure metabisulfite solution is passed through into bipolar membrane device 7 by F, through the electrodialysis of membrane stack mechanism, with electrodialysis efficiency For 60% meter, 0.31T sulfuric acid, generation 0.34T lye, and generation sodium sulfate concentration 100g/L, sulfuric acid concentration 25g/L are generated Weak brine 4m3:
One, the concentration of 0.31T sulfuric acid is 70g/L, volume 4.4m3, after reverse osmosis unit 20 is by sulphuric acid concentration, is generated The concentrated sulfuric acid 2.2m3 of 120g/L, and generate the dilute sulfuric acid 2.2m3 of 20g/L；
Two, produced to obtain 0.34T lye, it is based on 3500 yuan/ton by lye unit price, generation economic benefit is 0.34*3500=1225 Member；
Metabisulfite solution containing sodium hydroxide solution and concentration 2g/L that concentration is 80g/L in 0.34T lye, total volume are Lye is passed through into nanofiltration membrane system by 4.25m3, generates the filtrate 4.11m3 that naoh concentration is 80g/L；And it generates Naoh concentration is the concentrate 0.14m3 that 80g/L and sodium sulfate concentration are greater than 30g/L；
Three, resulting 4m3 weak brine is passed through into hydrochlorate separator 19, generates the metabisulfite solution 4m that concentration is 100g/L 3 and concentration be 25g/L sulfuric acid 4m3.

Claims (10)

1. a kind of environment-friendly cycle treatment process of viscose glue waste liquid, it is characterised in that:
Viscose glue waste liquid obtains the powdery solid containing sodium sulphate, zinc sulfate and sulfuric acid and contains sulfuric acid after centrifuge (1) separates Gelled acid bath foam is directly delivered in cellulose viscose manufacturing technique by the gelled acid bath foam of sodium, zinc sulfate and sulfuric acid by pipeline Acid station acid storage tank, the powdery solid containing sodium sulphate, zinc sulfate and sulfuric acid is placed in transfer tank (2)；
By adding demineralized water into transfer tank (2), powdery solid dissolution obtains lysate；
Then, lysate is passed through into blend tank (3), adjusts blend tank (3) interior temperature, pH and sodium sulfate concentration, obtains containing outstanding Floating object solution；
Suspended matter solution will be contained to be passed through in coarse filter device (4), coarse filtration obtains filter residue I and coarse filtration liquid；
Coarse filtration liquid is passed through into fine filtering apparatus (5), essence filtering obtains filter residue II and refined filtration liquid；
Refined filtration liquid is passed through into resin tower (6), is weakly alkaline environment in control resin tower (6), after chelating absorption, is obtained pure Metabisulfite solution；
Pure metabisulfite solution is passed through into circulating tank (8), is then passed through again into bipolar membrane device (7), through membrane stack electromechanics Circulating reflux effect between dialyzing and membrane stack mechanism and circulating tank (8), obtains sour through bipolar membrane device (7) acid mouth Liquid, obtains lye through bipolar membrane device (7) alkali outlet, obtains salt water through bipolar membrane device (7) salt outlet；
The acid solution is passed through into reverse osmosis unit (20), through counter osmosis, obtains concentrated vitriol solution and dilution heat of sulfuric acid, Concentrated vitriol solution is directly delivered to the acid bath process in cellulose viscose manufacturing technique by pipeline, it directly will be dilute by pipeline Sulfuric acid solution is delivered to sour circulating tank (15)；
The lye is passed through into nanofiltration device (21), is acted on through nanofiltration membrane, sodium hydroxide solution and sulfur acid sodium, hydrogen-oxygen are obtained Change the mixed liquor of sodium, the dipping or yellow work directly sodium hydroxide solution being delivered to by pipeline in cellulose viscose manufacturing technique Sequence, and the mixed solution of sulfur acid sodium, sodium hydroxide is directly delivered to by blend tank (3) by pipeline；
The salt water is passed through into hydrochlorate separator (19), and is passed through demineralized water, is separated, obtains sulfuric acid solution and sodium sulphate Sulfuric acid solution is directly delivered to the acid bath process in cellulose viscose manufacturing technique by pipeline by solution, and direct by pipeline Metabisulfite solution is delivered to transfer tank (2).
2. the environment-friendly cycle treatment process of viscose glue waste liquid according to claim 1, it is characterised in that:
The viscose glue waste liquid include concentration be 200~300g/L sodium sulphate, concentration be 0.1~1g/L zinc sulfate and concentration be The sulfuric acid of 5~10g/L；
Sodium sulfate concentration is 200~300g/L in the lysate；
The interior sodium sulfate concentration control of blend tank (3) is 300g/L；
The acid solution is the sulfuric acid solution of 60~80g/L of concentration, and after counter osmosis, the concentrated vitriol solution concentration is 110~130g/L, the dilution heat of sulfuric acid concentration are 10~30g/L；
The metabisulfite solution that the lye includes the sodium hydroxide solution that concentration is 45~80g/L and concentration is 0~2g/L；Through receiving After filter membrane effect, the concentration of sodium hydroxide solution is 45~80g/L, and sodium sulfate concentration is 25~50g/L, hydrogen-oxygen in mixed liquor Change na concn is 45~80g/L；
The metabisulfite solution that the salt water includes the sulfuric acid solution that concentration is 20~30g/L and concentration is 100~180g/L；Through acid After salt separator (19) separation, the sulfuric acid solution concentration is 20~30g/L, and metabisulfite solution concentration is 100~180g/L.
3. the environment-friendly cycle treatment process of viscose glue waste liquid according to claim 1, it is characterised in that:
In centrifuge (1), the discharging flow of sodium sulphate is 2~4t/h in the powdery solid, and the discharging flow of zinc sulfate is 0.0014~0.014t/h, the discharging flow of sulfuric acid are 0.07~0.14t/h；
In transfer tank (2), the feed rate of the demineralized water is 5~9.4m3/h；
In resin tower (6), the feed rate of the refined filtration liquid is 7~13.4m3/h；
In circulating tank (8), the feed rate of the pure metabisulfite solution is 7~13.4m3/h；
In bipolar membrane device (7), the feed rate of the pure metabisulfite solution is 7~13.4m3/h；
In bipolar membrane device (7), the discharging flow of the acid solution is 132~289m3/d, the discharging flow of lye is 150~ 328m3/d, the discharging flow of salt water are 140~264 m3/d；
In reverse osmosis unit (20), the concentrated vitriol solution discharging flow is 66~145m3/d, and the dilution heat of sulfuric acid goes out Stream amount is 66~145m3/d；
In nanofiltration device (21), the discharging flow of the sodium hydroxide is 150~328m3/d, the reactor effluent stream of the mixed liquor Amount is 10~40m3/d；
In hydrochlorate separator (19), the feed rate of the demineralized water is 140~264m3/d；The sulfuric acid solution goes out Stream amount is 140~264m3/d, and the discharging flow of sulfuric acid solution is 140~264m3/d.
4. the environment-friendly cycle treatment process of viscose glue waste liquid according to claim 1, it is characterised in that:
Centrifuge (1) revolving speed is 4000~5000r/min；
Blend tank (3) interior pH is 9~11, and temperature is 30~40 DEG C；
Alkalescent in resin tower (6) refers to that pH is 9~11；
In bipolar membrane device (7), set: electric current as 300~400A, voltage be 200~290V, temperature be 30~40 DEG C and Operating pressure is 0.03~0.1 Mpa；
In reverse osmosis unit (20), pressure is 6.5~8 Mpa；
In nanofiltration device (21), pressure is 2.3~2.8 Mpa；
It is pulsed feeds mode between demineralized water and salt water in hydrochlorate separator (19).
5. the environment-friendly cycle treatment process of viscose glue waste liquid according to claim 1, it is characterised in that: collect in coarse filtration Filter residue II in filter residue I and essence filtering, and the two is directly delivered to viscose glue fibre with feed rate for 0.0014-0.014kg/h Acid bath process in terylene short fiber production technology.
6. the environment-friendly cycle processing system of viscose glue waste liquid described in any one of -5 according to claim 1, it is characterised in that: packet It includes and viscose glue waste liquid is separated into the centrifuge (1) of powdery solid and gelled acid bath foam, powdery solid is dissolved as in lysate Turn trough (2), by lysate by adjust temperature and adjust pH and adjust sodium sulfate concentration have suspended matter generate blend tank (3), will Solution containing suspended matter is filtered into the coarse filter device (4) of filter residue I and coarse filtration liquid, coarse filtration liquid is filtered into filter residue II and refined filtration liquid Fine filtering apparatus (5) flows back refined filtration liquid by chelating resin tower (6), fluid circulation that absorption has pure sodium sulphate to generate Circulating tank (8) and by sodium sulphate electrodialysis be sulfuric acid and sodium hydroxide bipolar membrane device (7), transfer tank (2) setting from Scheming (1) station side；Transfer tank (2) is connected with desalination water storage tank (12), and transfer tank (2) is connect with blend tank (3)；Blend tank (3) it is connected with the heat exchanger (13) of temperature regulating, the storage alkali tank (11) of pH is adjusted and adjusts the desalination water storage tank (12) of sodium sulfate concentration, and is adjusted Distribution tank (3) is connect with coarse filter device (4)；Coarse filter device (4) is connect with fine filtering apparatus (5), fine filtering apparatus (5) and tree Rouge tower (6) connection, and resin tower (6) is connect by circulating tank (8) with bipolar membrane device (7), circulating tank (8) and bipolar membrane device (7) access of an independent loops is formed between.
7. the environment-friendly cycle processing system of viscose glue waste liquid according to claim 6, it is characterised in that: the coarse filter device It (4) is the bag filter in 10~15 μm of aperture, fine filtering apparatus (5) is the ultrafilter in 0.01~0.05 μm of aperture.
8. the environment-friendly cycle processing system of viscose glue waste liquid according to claim 6, it is characterised in that: the resin tower (6) At least three, it is connect between resin tower (6) and resin tower (6) by pipeline, pipeline is equipped with valve (17) and zinc ion detects Instrument (18)；The resin tower (6) includes resin, upper filter plate (603) and the lower filter of tower body (601) and setting in tower body (601) Plate (604), tower body (601) top are provided with inlet (605), and bottom is provided with liquid outlet (606)；Upper filter plate (603) setting On tower body (601) top, shape is arranged between tower body (601) lower part, upper filter plate (603) and lower filter plate (604) in lower filter plate (604) At filter chamber (602), resin setting is in filter chamber (602).
9. the environment-friendly cycle processing system of viscose glue waste liquid according to claim 6, it is characterised in that: the circulating tank (8) Including tank body (801) and the vertical clapboard (802), upper cross plate (803) and the lower cross plate (804) that are arranged in tank body (801), vertical clapboard (802) it is vertically provided in tank body (801), and is fixed on tank body (801) top and side, vertical clapboard (802) side and tank body (801) inner wall forms back cavity (805), and the other side and tank body (801) inner wall form mixing chamber (806), vertical clapboard (802) end Channel is formed between tank body (801) bottom interior wall；Refluxing opening (807) are equipped at the top of tank body (801), refluxing opening (807) with return Chamber (805) connection is flowed, back cavity (805) top is equipped with overflow port (808), upper cross plate (803) are equipped with below overflow port (808), Channel is formed between upper cross plate (803) end and vertical clapboard (802)；It is additionally provided with feed inlet (809), feeds at the top of tank body (801) Mouth (809) is connected to mixing chamber (806), and mixing chamber (806) lower part is equipped with discharge port (810), is equipped with down below discharge port (810) Transverse slat (804) forms channel between lower cross plate (804) end and vertical clapboard (802).
10. the environment-friendly cycle processing system of viscose glue waste liquid according to claim 6, it is characterised in that: the circulating tank (8) Salt circulating tank (14), sour circulating tank (15) and alkali circulating tank (16), bipolar membrane device (7) including at least two-stage include at least two Grade membrane stack mechanism, salt circulating tank (14), sour circulating tank (15), alkali circulating tank (16) and membrane stack mechanism series are correspondingly arranged；
Salt circulating tank (14) feed inlet is connect with resin tower (6), and salt circulating tank (14) discharge port and membrane stack mechanism at the same level are into salt Mouth connection, membrane stack mechanism salt outlet are connect with salt circulating tank (14) refluxing opening at the same level, salt circulating tank (14) and membrane stack at the same level The access of an independent loops is formed between mechanism, and salt circulating tank (14) is connected with storage brine tank (9), salt circulating tank (14) overflow Mouth is connect with next stage salt circulating tank (14) feed inlet；Salt circulating tank (14) overflow port of afterbody is connected with hydrochlorate separation dress It sets (19), hydrochlorate separator (19) acid mouth is directly connected with the acid station acid storage tank in cellulose viscose manufacturing technique by pipeline It connects, hydrochlorate separator (19) salt outlet is directly connect with transfer tank (2) by pipeline；
Sour circulating tank (15) connect with next stage acid circulating tank (15) overflow port, and sour circulating tank (15) feed inlet is connected with demineralized water Storage tank (12), sour circulating tank (15) discharge port are connect with membrane stack mechanism acid inlet at the same level, membrane stack mechanism acid mouth and peer Sour circulating tank (15) refluxing opening connection, forms the logical of an independent loops between sour circulating tank (15) and the membrane stack mechanism of peer Road, sour circulating tank (15) overflow port are connected with reverse osmosis unit (20), reverse osmosis unit (20) concentrated acid outlet by pipeline directly with Viscose rayon production in acid station acid storage tank connection, reverse osmosis unit (20) penetrating fluid outlet by pipeline directly with sour circulating tank (15) it connects；
Alkali circulating tank (16) is connect with next stage alkali circulating tank (16) overflow port, and alkali circulating tank (16) feed inlet is connected with demineralized water Storage tank (12), alkali circulating tank (16) discharge port are connect with membrane stack mechanism alkali inlet at the same level, membrane stack mechanism alkali outlet and peer The connection of alkali circulating tank (16) refluxing opening forms the logical of an independent loops between alkali circulating tank (16) and the membrane stack mechanism of peer Road, alkali circulating tank (16) overflow port are connected with nanofiltration device (21), and nanofiltration device (21) filtrate port is directly fine with viscose glue by pipeline Stoste storage tank connection in dimension production, nanofiltration device (21) concentrate mouth are directly connect with blend tank (3) by pipeline.
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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110904465A (en) * 2019-10-22 2020-03-24 新疆中泰创新技术研究院有限责任公司 Device and method for treating byproduct mirabilite of viscose factory
CN110975405A (en) * 2019-12-20 2020-04-10 宜宾海丝特纤维有限责任公司 Alkali liquor desalting process
CN111470560A (en) * 2019-01-24 2020-07-31 山东雅美科技有限公司 Method for recycling acid wastewater in viscose fiber production
CN111484569A (en) * 2020-05-29 2020-08-04 新疆中泰纺织集团有限公司 Zero-emission treatment method of viscose squeezed alkali liquor
CN112725942A (en) * 2020-12-28 2021-04-30 宜宾丝丽雅股份有限公司 Viscose sodium sulfate waste liquid regeneration and recycling process
CN112758957A (en) * 2020-12-28 2021-05-07 宜宾丝丽雅股份有限公司 Process for purifying sodium hydroxide concentration by electrodialysis
CN112853550A (en) * 2020-12-28 2021-05-28 宜宾丝丽雅股份有限公司 Treatment method for recycling alkali liquor
CN113800608A (en) * 2021-09-10 2021-12-17 宜宾丝丽雅股份有限公司 Control method and system for treating viscose waste liquid by using bipolar membrane applicable to spinning system

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103343402A (en) * 2013-07-24 2013-10-09 宜宾海翔化工有限责任公司 Novel viscose sodium sulfate waste liquor acid and alkali recycling technology through utilizing bipolar membrane electrodialysis method
CN105800885A (en) * 2016-05-23 2016-07-27 北京今大禹环境技术股份有限公司 Resource recycling and treatment system of high-concentration degradation-resistant salt-containing organic waste water
CN206051730U (en) * 2016-08-30 2017-03-29 杭州上拓环境科技股份有限公司 A kind of system using various membrane technology recycling treatment kelp processing waste water
CN209322625U (en) * 2018-11-06 2019-08-30 宜宾海丝特纤维有限责任公司 A kind of environment-friendly cycle processing system of viscose glue waste liquid

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103343402A (en) * 2013-07-24 2013-10-09 宜宾海翔化工有限责任公司 Novel viscose sodium sulfate waste liquor acid and alkali recycling technology through utilizing bipolar membrane electrodialysis method
CN105800885A (en) * 2016-05-23 2016-07-27 北京今大禹环境技术股份有限公司 Resource recycling and treatment system of high-concentration degradation-resistant salt-containing organic waste water
CN206051730U (en) * 2016-08-30 2017-03-29 杭州上拓环境科技股份有限公司 A kind of system using various membrane technology recycling treatment kelp processing waste water
CN209322625U (en) * 2018-11-06 2019-08-30 宜宾海丝特纤维有限责任公司 A kind of environment-friendly cycle processing system of viscose glue waste liquid

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111470560A (en) * 2019-01-24 2020-07-31 山东雅美科技有限公司 Method for recycling acid wastewater in viscose fiber production
CN110904465A (en) * 2019-10-22 2020-03-24 新疆中泰创新技术研究院有限责任公司 Device and method for treating byproduct mirabilite of viscose factory
CN110975405A (en) * 2019-12-20 2020-04-10 宜宾海丝特纤维有限责任公司 Alkali liquor desalting process
CN111484569A (en) * 2020-05-29 2020-08-04 新疆中泰纺织集团有限公司 Zero-emission treatment method of viscose squeezed alkali liquor
CN112725942A (en) * 2020-12-28 2021-04-30 宜宾丝丽雅股份有限公司 Viscose sodium sulfate waste liquid regeneration and recycling process
CN112758957A (en) * 2020-12-28 2021-05-07 宜宾丝丽雅股份有限公司 Process for purifying sodium hydroxide concentration by electrodialysis
CN112853550A (en) * 2020-12-28 2021-05-28 宜宾丝丽雅股份有限公司 Treatment method for recycling alkali liquor
CN113800608A (en) * 2021-09-10 2021-12-17 宜宾丝丽雅股份有限公司 Control method and system for treating viscose waste liquid by using bipolar membrane applicable to spinning system
CN113800608B (en) * 2021-09-10 2022-07-05 宜宾丝丽雅股份有限公司 Control method and system for treating viscose waste liquid by using bipolar membrane applicable to spinning system
WO2023035288A1 (en) * 2021-09-10 2023-03-16 宜宾丝丽雅股份有限公司 Control method and system suitable for treating viscose waste liquid by means of bipolar membrane in spinning system

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