CN109133448B - Circulating environment-friendly treatment process and system for viscose waste liquid - Google Patents

Circulating environment-friendly treatment process and system for viscose waste liquid Download PDF

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CN109133448B
CN109133448B CN201811310408.3A CN201811310408A CN109133448B CN 109133448 B CN109133448 B CN 109133448B CN 201811310408 A CN201811310408 A CN 201811310408A CN 109133448 B CN109133448 B CN 109133448B
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tank
acid
solution
sodium sulfate
concentration
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CN109133448A (en
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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 Haisite Fiber Co Ltd
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Yibin Grace Group 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

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  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

The invention relates to a recycling and environment-friendly treatment process and system for viscose waste liquid, and belongs to the technical field of waste recovery and environment-friendly treatment in viscose fiber production. The method comprises the steps of centrifugal separation, dissolution, pH adjustment, temperature adjustment, sodium sulfate concentration adjustment, rough filtration, fine filtration, resin chelating purification, bipolar membrane electrodialysis, post-treatment and the like, and conditions, process parameters, equipment, indexes and the like are optimized, acid, alkali and dilute salt are recycled, the problems of difficult viscose waste liquid treatment, waste material and the like are effectively solved, the purity, concentration and yield of sulfuric acid and sodium hydroxide are effectively ensured, and products in the steps are recycled in the circulating environment-friendly treatment process or viscose fiber production process, so that the purposes of low energy consumption and raw material cost saving are realized, and meanwhile, zero emission is realized, and the environmental pressure is reduced.

Description

Circulating environment-friendly treatment process and system for viscose waste liquid
Technical Field
The invention relates to a method and a system for treating viscose waste liquid, in particular to a closed environment-friendly method and a system for treating viscose waste liquid, belonging to the technical field of waste recovery and environment-friendly treatment in viscose fiber production.
Background
The viscose is a chemical fiber which is processed by using polymer materials such as wood pulp and cotton pulp containing natural cellulose through chemical and mechanical methods, is the type of chemical fiber which has the closest performance to natural fiber clothing, has the characteristics of soft hand feeling, moisture absorption and ventilation, elegant hanging, bright dyeing, static resistance, easiness in textile processing and the like, is derived from the natural source, is superior to the natural regenerated cellulose fiber, and is one of important materials of textile industry raw materials. At present, about 40 viscose fiber enterprises in China produce common viscose fibers (filaments and short fibers) and strong filaments, and high-wet-modulus type fibers and viscose fibers with special properties.
In the production process of viscose fiber, a large amount of chemical raw materials are needed, a large amount of wastewater is generated, and the wastewater contains sulfuric acid, zinc sulfate, carbon disulfide, cellulose, soluble organic matters and the like, so that the wastewater is very harmful to the environment, and is one of main pollution sources in the textile industry.
Wherein, in the viscose fiber forming process, viscose is acted with an acidic coagulating bath to neutralize alkali, and sodium cellulose sulfonate is decomposed to regenerate hydrated cellulose, and the fibers in the viscose in the process Sulfonate, free NaOH and Na generated by side reaction 2 CS 3 Side reaction products such as polysulfide and the like can react with sulfuric acid in the coagulating bath to generate sodium sulfate. The viscose fiber production comprises an acid bath process consuming sulfuric acid, and also comprises a pulp dipping process consuming sodium hydroxide, an alkali cellulose sulfonate dissolving process, an exhaust gas absorbing process, a refining press-washing process and an acid water neutralization treatment process.
The main functions of sodium sulfate in the coagulating bath are to promote the coagulation of viscose liquid flow and inhibit the dissociation of sulfuric acid, so that the regeneration speed of cellulose sulfonate is delayed, the concentration of sodium sulfate in the coagulating bath is increased, the spinning operation is easier, the yarn bundles are not easy to break, the dissociation degree of sulfuric acid can be reduced, the yarn bundles still have a certain residual esterification degree when leaving the coagulating bath, but the sodium sulfate in the coagulating bath is not too high, otherwise, the fiber is too fast to coagulate, a fine structure cannot be formed, coarse crystal particles are generated, and the inner layer and the outer layer of the fiber are also uneven.
In the spinning process, the content of sodium sulfate in the coagulating bath is continuously increased, so that the coagulating bath cannot meet the process requirement, if the total amount of the coagulating bath is increased and cannot be stored only by adding the consumed raw materials in the coagulating bath to supplement the concentration of the raw materials for recycling, the coagulating bath can only be discharged in a timed and quantitative manner, and acid, salt, metal ions and the like in the coagulating bath can cause serious environmental pollution, bring huge pressure to sewage treatment and cause huge waste of resources. And the excessive sodium sulfate in spinning is subjected to high-temperature crystallization, sodium sulfate crystals are separated, so that the content of sodium sulfate in spinning meets the process requirement, acid is not required to be discharged every day to balance spinning, acid discharge can be reduced, anhydrous sodium sulfate is produced, and environmental protection pressure is reduced by directly supplying the material to a spinning workshop after feeding, but the anhydrous sodium sulfate produced by high-temperature crystallization of sodium sulfate in a coagulating bath contains more impurities and has low added value, so that economic benefit cannot be produced, a large amount of solid salt cannot be treated, and certain pressure is still brought to environmental protection.
The national institutes of public patent document with publication number CN101343124, named "recycling tank-based viscose waste liquid environmental protection treatment device", published in 2009, 01 and 14 days: the equipment comprises an absorption tank, a collecting tank, a neutralization tank and a sedimentation tank. The utility model comprehensively considers the treatment problems of waste alkali, waste gas and zinc-containing wastewater in the viscose fiber production, not only achieves the comprehensive utilization of resources, but also reduces the waste emission, and solves the environmental protection problem that the development of the industry is restricted for a long time in the viscose fiber production process. According to the technical scheme, although the viscose waste liquid is subjected to environmental protection treatment, the waste is not subjected to treatment such as separation, purification and concentration, and is recycled, so that the recycling requirement is not met.
The national bureau of Chinese patent discloses a patent document with a publication number of CN206666261U, named as a viscose chemical fiber acid wastewater treatment device, in 2017, 11 and 24, and discloses that: a multi-medium filter, an ultrafiltration membrane, a nanofiltration membrane, a primary water producing pool, a booster pump, an RO reverse osmosis membrane and a reclaimed water storage tank; the outlet of the multi-medium filter is communicated with the inlet of the ultrafiltration membrane; the outlet of the ultrafiltration membrane is communicated with the inlet of the nanofiltration membrane; the outlet of the nanofiltration membrane is communicated with the inlet of the primary water producing pool; the outlet of the first-stage water producing pool is communicated with the inlet of the booster pump; the outlet of the booster pump is communicated with the inlet of the RO reverse osmosis membrane, and the outlet of the RO reverse osmosis membrane is communicated with the water inlet of the reclaimed water storage tank. The utility model solves the problems of high cost burden caused by treating the acid wastewater of viscose chemical fiber by adopting a neutralization sedimentation tank device at the present stage, secondary pollution caused by a large amount of lime mud which cannot be used, and the like, and the wastewater treated by the utility model can be recycled, has good purifying effect and high efficiency, reduces the waste of water resources, and is energy-saving and environment-friendly. However, the technical scheme focuses on environmental protection treatment of the viscose waste water, and recycling of the viscose waste water is not specific, cyclic, efficient and the like.
The national bureau discloses a patent document with a publication number of CN103342433A on the 10 th 09 th 2013, and the name of the patent document is a method for recycling acid and alkali from viscose sodium sulfate waste liquid by adopting a bipolar membrane electrodialysis method; the national bureau discloses a patent document with publication number of CN103388198A, named "a method for preparing acid and alkali from viscose sodium sulfate waste liquid by bipolar membrane electrodialysis method" in 2013, 11 and 13; and the national bureau discloses a patent document with publication number CN103351041a, named "electrodialysis alkali recovery process in viscose fiber production", at 10/16 of 2013. There are also the following problems: the existing viscose waste liquid treatment device can not be expanded to industrial production and is limited to an experimental stage; after the viscose waste liquid is treated, waste is discharged, which is not beneficial to environmental protection production; after the recovery of sulfuric acid, sodium hydroxide and dilute sodium sulfate, the purity and concentration of the viscose waste liquid can not meet the actual requirements, namely, the purity and concentration are more and less, and the product quality is greatly influenced after the viscose waste liquid returns to the viscose fiber production process, so that the viscose waste liquid can be used in the production process after further treatment.
Disclosure of Invention
The invention aims to solve the problems in the prior art, and provides a recycling and environment-friendly treatment process for viscose waste liquid. Through the arrangement of a centrifugal machine, a transfer tank, a blending tank, a coarse filtering device, a fine filtering device, a resin tower, a bipolar membrane device and a circulating tank, the steps of centrifugal separation, dissolution, pH adjustment, temperature adjustment, sodium sulfate concentration adjustment, coarse filtration, fine filtration, resin chelating adsorption, bipolar membrane electrodialysis, post-treatment and the like are carried out, and conditions, technological parameters, equipment, indexes and the like are optimized, so that acid, alkali and dilute salt are recovered, the problems of difficult viscose waste liquid treatment, waste of materials and the like are effectively solved, the purity, concentration and yield of sulfuric acid and sodium hydroxide are effectively ensured, and products in the steps are recycled in the circulating environment-friendly treatment process or viscose fiber production process, the purposes of low energy consumption and raw material cost saving are realized, and meanwhile, zero emission is realized, and the environmental pressure is reduced.
In order to achieve the technical purpose, the following technical scheme is provided:
a recycling and environment-friendly treatment process of viscose waste liquid,
separating the viscose waste liquid by a centrifuge to obtain powdery solid containing sodium sulfate, zinc sulfate and sulfuric acid and concentrated acid bath containing sodium sulfate, zinc sulfate and sulfuric acid, directly conveying the concentrated acid bath to an acid station acid storage tank in the viscose fiber production process through a pipeline, and placing the powdery solid containing sodium sulfate, zinc sulfate and sulfuric acid into a transfer tank;
adding desalted water into the transfer tank, and dissolving powdery solid to obtain a dissolving solution;
then, introducing the solution into a blending tank, and adjusting the temperature, pH and sodium sulfate concentration in the blending tank to obtain a suspension-containing solution;
under this condition, zinc ions in the solution combine with hydroxide ions to form a white precipitate of zinc hydroxide, and are suspended in the solution, during which about 80% of the zinc ions are precipitated;
introducing the suspension-containing solution into a coarse filtration device, and performing coarse filtration to remove large-particle zinc hydroxide precipitates to obtain filter residues I and coarse filtrate;
introducing the rough filtrate into a fine filtering device, fine filtering, and removing small-particle zinc hydroxide precipitates to obtain filter residue II and fine filtrate;
Introducing the refined filtrate into a resin tower, controlling the resin tower to be in a weak alkaline environment, and after chelating and adsorbing, combining the residual zinc ions on the resin to obtain a pure sodium sulfate solution;
introducing pure sodium sulfate solution into a circulating tank, then introducing the pure sodium sulfate solution into a bipolar membrane device, performing electrodialysis through a membrane stack mechanism and performing circulating reflux between the membrane stack mechanism and the circulating tank, obtaining acid liquor through an acid outlet of the bipolar membrane device, obtaining alkali liquor through an alkali outlet of the bipolar membrane device, and obtaining brine through a salt outlet of the bipolar membrane device;
introducing the acid liquor into a reverse osmosis device, obtaining a concentrated sulfuric acid solution and a dilute sulfuric acid solution through reverse osmosis, directly conveying the concentrated sulfuric acid solution to an acid bath process in a viscose fiber production process through a pipeline, and directly conveying the dilute sulfuric acid solution to an acid circulation tank through the pipeline;
introducing the alkali liquor into a nanofiltration device, obtaining sodium hydroxide solution and mixed solution containing sodium sulfate and sodium hydroxide through the action of nanofiltration membrane, directly conveying the sodium hydroxide solution to an impregnation or yellowing process in a viscose fiber production process through a pipeline, and directly conveying the mixed solution containing sodium sulfate and sodium hydroxide to a blending tank through the pipeline;
And (3) introducing the brine into an acid salt separation device, introducing desalted water, separating to obtain sulfuric acid solution and sodium sulfate solution, directly conveying the sulfuric acid solution to an acid bath process in the viscose fiber production process through a pipeline, and directly conveying the sodium sulfate solution to a transfer tank through the pipeline.
Further, the viscose waste liquid comprises 200-300 g/L sodium sulfate, 0.1-1 g/L zinc sulfate and 5-10 g/L sulfuric acid;
the concentration of sodium sulfate in the dissolving solution is 200-300 g/L;
the concentration of sodium sulfate in the blending tank is controlled to be 300g/L;
the acid liquor is sulfuric acid solution with the concentration of 60-80 g/L, the concentration of the concentrated sulfuric acid solution is 110-130 g/L after reverse osmosis, and the concentration of the dilute sulfuric acid solution is 10-30 g/L;
the alkali liquor comprises sodium hydroxide solution with the concentration of 45-80 g/L and sodium sulfate solution with the concentration of 0-2 g/L; after the nanofiltration membrane is used, the concentration of the sodium hydroxide solution is 45-80 g/L, the concentration of sodium sulfate in the mixed solution is 25-50 g/L, and the concentration of sodium hydroxide is 45-80 g/L;
the brine comprises sulfuric acid solution with the concentration of 20-30 g/L and sodium sulfate solution with the concentration of 100-180 g/L; after being separated by an acid salt separating device, the concentration of the sulfuric acid solution is 20-30 g/L, and the concentration of the sodium sulfate solution is 100-180 g/L.
Further, in the centrifuge, the discharge flow of sodium sulfate in the powdery solid is 2-4 t/h, the discharge flow of zinc sulfate is 0.0014-0.014 t/h, and the discharge flow of sulfuric acid is 0.07-0.14 t/h;
in the transfer tank, the feeding flow of the desalted water is 5-9.4 m/h;
in the resin tower, the feeding flow of the fine filtrate is 7-13.4 m/h;
in the circulating tank, the feeding flow of the pure sodium sulfate solution is 7-13.4 m/h;
in the bipolar membrane device, the feeding flow of the pure sodium sulfate solution is 7-13.4 m/h;
in the bipolar membrane device, the discharge flow of the acid liquor is 132-289 m/d, the discharge flow of the alkali liquor is 150-328 m/d, and the discharge flow of the salt water is 140-264 m d;
in the reverse osmosis device, the discharge flow of the concentrated sulfuric acid solution is 66-145 m for the first time, and the discharge flow of the dilute sulfuric acid solution is 66-145 m for the second time;
in the nanofiltration device, the discharge flow of the sodium hydroxide is 150-328 m/d, and the discharge flow of the mixed solution is 10-40 m/d;
in the acid salt separation device, the feeding flow of the desalted water is 140-264 m/d; the discharge flow of the sulfuric acid solution is 140-264 m/d, and the discharge flow of the sulfuric acid solution is 140-264 m/d.
Further, the rotating speed of the centrifugal machine (1) is 4000-5000 r/min;
the pH value in the blending tank is 9-11, and the temperature is 30-40 ℃;
the weak alkalinity in the resin tower means that the pH is 9-11;
in the bipolar membrane device, set is: the current is 300-400A, the voltage is 200-290V, the temperature is 30-40 ℃ and the operating pressure is 0.03-0.1 Mpa;
in the reverse osmosis device, the pressure is 6.5-8 Mpa;
in the nanofiltration device, the pressure is 2.3-2.8 Mpa;
in the acid salt separating device, a pulse feeding mode is adopted between desalted water and salt water.
Further, the filter residue I in the rough filtration and the filter residue II in the fine filtration are collected and directly conveyed to an acid bath process in the viscose fiber production process at a feed flow rate of 0.0014-0.014 kg/h.
Further, an acid salt separation device is arranged between the transfer tank and the blending tank, after the obtained solution is introduced into the acid salt separation device, desalted water is introduced into the acid salt separation device at a feeding flow of 326 m/d, concentrated sulfuric acid solution with a discharging flow of 652 m/d and a concentration of 5-15 g/L and sodium sulfate solution containing impurities are separated, the concentrated sulfuric acid solution is directly conveyed to an acid bath process in the viscose fiber production process through a pipeline, and the sodium sulfate solution containing the impurities is introduced into the blending tank for subsequent processes.
Further, the pH value in the blending tank is adjusted to 9-11, and the specific operation comprises the following steps:
if the circulating environment-friendly treatment system is used for the first time, introducing a sodium hydroxide solution with the concentration of 720g/L into a blending tank at the feeding flow of 15.27-30.61L/h;
if the circulating environment-friendly treatment system is not used for the first time, a sodium hydroxide solution with the concentration of 45-80 g/L is introduced into the blending tank at the feeding flow rate of 137.43-489.6L/h, and the sodium hydroxide solution with the concentration of 45-80 g/L is from a nanofiltration device in the circulating environment-friendly treatment system.
A circulating environment-friendly treatment system for viscose waste liquid comprises a centrifugal machine for separating the viscose waste liquid into powdery solid and concentrated acid bath liquid, a transfer tank for dissolving the powdery solid into solution, a blending tank for generating suspended matters from the solution by adjusting the temperature, the pH and the sodium sulfate concentration, a coarse filtering device for filtering solution containing suspended matters into filter residues I and coarse filtrate, a fine filtering device for filtering the coarse filtrate into filter residues II and fine filtrate, a resin tower for generating pure sodium sulfate from the fine filtrate by chelating and adsorbing, a circulating tank for circulating and refluxing fluid, and a bipolar membrane device for electrodialysis of sodium sulfate into sulfuric acid and sodium hydroxide, wherein the transfer tank is arranged at one side of a station of the centrifugal machine; the transfer tank is connected with a desalted water storage tank and is connected with the blending tank; the blending tank is connected with a temperature-adjusting heat exchanger, a pH-adjusting alkali storage tank and a sodium sulfate concentration-adjusting desalted water storage tank, and is connected with the coarse filtering device; the coarse filtering device is connected with the fine filtering device, the fine filtering device is connected with the resin tower, the resin tower is connected with the bipolar membrane device through the circulating tank, and an independent circulating passage is formed between the circulating tank and the bipolar membrane device.
Further, the coarse filter device is a bag filter with the aperture of 10-15 mu m, and the fine filter device is an ultrafilter with the aperture of 0.01-0.05 mu m.
Further, at least three resin towers are connected with each other through a pipeline, a valve and a zinc ion detector are arranged on the pipeline, and the detection range of the zinc ion detector is 0-3 ppm.
Further, the resin tower comprises a tower body, resin, an upper filter plate and a lower filter plate which are arranged in the tower body, wherein the top of the tower body is provided with a liquid inlet, and the bottom of the tower body is provided with a liquid outlet; the upper filter plate is arranged at the upper part of the tower body, the lower filter plate is arranged at the lower part of the tower body, a filter cavity is formed between the upper filter plate and the lower filter plate, and the resin is arranged in the filter cavity.
Furthermore, the upper filter plate and the lower filter plate are both filter plates with water distribution holes, and water distributors are arranged at the water distribution holes.
Further, the circulating tank comprises a tank body, a vertical partition plate, an upper transverse plate and a lower transverse plate, wherein the vertical partition plate, the upper transverse plate and the lower transverse plate are arranged in the tank body, the vertical partition plate is vertically arranged in the tank body and is fixed at the top and the side surface of the tank body, one side of the vertical partition plate and the inner wall of the tank body form a backflow cavity, the other side of the vertical partition plate and the inner wall of the tank body form a mixing cavity, and a channel is formed between the end part of the vertical partition plate and the inner wall of the bottom of the tank body; a reflux port is arranged at the top of the tank body and communicated with the reflux cavity, an overflow port is arranged at the upper part of the reflux cavity, an upper transverse plate is arranged below the overflow port, and a channel is formed between the end part of the upper transverse plate and the vertical partition plate; the top of the tank body is also provided with a feed inlet which is communicated with the mixing cavity, the lower part of the mixing cavity is provided with a discharge outlet, a lower transverse plate is arranged below the discharge outlet, and a channel is formed between the end part of the lower transverse plate and the vertical partition plate.
Further, the circulating tank comprises at least two stages of salt circulating tanks, acid circulating tanks and alkali circulating tanks, the bipolar membrane device comprises at least two stages of membrane stack mechanisms, and the salt circulating tanks, the acid circulating tanks, the alkali circulating tanks and the membrane stack mechanisms are correspondingly arranged in series;
the salt circulation tank is connected with the resin tower, the salt circulation tank discharge port is connected with the salt inlet of the membrane stack mechanism of the same level, the salt outlet of the membrane stack mechanism is connected with the salt circulation tank reflux port of the same level, an independent circulation passage is formed between the salt circulation tank and the membrane stack mechanism of the same level, the salt circulation tank is connected with the salt storage tank, and the salt circulation tank overflow port is connected with the salt circulation tank feed port of the next level; the overflow port of the salt circulation tank of the last stage is connected with an acid salt separation device, the acid outlet of the acid salt separation device is directly connected with an acid station acid storage tank in the viscose fiber production process through a pipeline, and the salt outlet of the acid salt separation device is directly connected with a transfer tank through a pipeline;
the acid circulation tank is connected with an overflow port of the next-stage acid circulation tank, a feeding port of the acid circulation tank is connected with a desalted water storage tank, a discharging port of the acid circulation tank is connected with an acid inlet of a membrane stack mechanism of the same level, an acid outlet of the membrane stack mechanism is connected with a reflux port of the same level acid circulation tank, an independent circulation passage is formed between the acid circulation tank and the membrane stack mechanism of the same level, the overflow port of the acid circulation tank is connected with a reverse osmosis device, a concentrated acid outlet of the reverse osmosis device is directly connected with an acid station acid storage tank in the viscose production process through a pipeline, and a permeate outlet of the reverse osmosis device is directly connected with the acid circulation tank through a pipeline;
The alkali circulation tank is connected with an overflow port of the next-stage alkali circulation tank, a feeding port of the alkali circulation tank is connected with a desalted water storage tank, a discharging port of the alkali circulation tank is connected with an alkali inlet of a membrane stack mechanism at the same level, an alkali outlet of the membrane stack mechanism is connected with a reflux port of the alkali circulation tank at the same level, an independent circulation passage is formed between the alkali circulation tank and the membrane stack mechanism at the same level, an overflow port of the alkali circulation tank is connected with a nanofiltration device, a filtrate port of the nanofiltration device is directly connected with a stock solution storage tank in a viscose fiber production process through a pipeline, and a concentrated solution port of the nanofiltration device is directly connected with a blending tank through a pipeline.
Further, the membrane pile mechanism comprises membrane units and membrane plates which are arranged at intervals, the membrane plates are arranged at two sides of the membrane pile mechanism, and the membrane plates at two sides are respectively connected with the pole plates; the polar plates are respectively provided with a power interface, a polar water inlet and a polar water outlet, one polar plate is connected with a power anode through the power interface, and the other polar plate is connected with a power cathode through the power interface;
the membrane units comprise a plurality of pairs of overlapped membranes and separators, each pair of membranes comprises a cathode membrane, an anode membrane and a bipolar membrane, and the membrane units are repeatedly arranged according to the arrangement of the bipolar membrane, the separators, the cathode membrane, the separators, the anode membrane and the separators; one end of the baffle is connected with a salt inlet, an acid inlet and an alkali inlet, and a salt inlet channel, an acid inlet channel and an alkali inlet channel are respectively formed in the baffle; the other end of the baffle is connected with a salt outlet, an acid outlet and an alkali outlet, and a salt outlet channel, an acid outlet channel and an alkali outlet channel are formed in the baffle.
Further, the thickness of the partition plate is 2-3 mm, a plurality of open holes are formed in two ends of the partition plate, the bipolar membrane, the negative membrane and the positive membrane, and flow passages are correspondingly formed in the open holes in the partition plate.
Further, the pair of diaphragms are correspondingly provided with a salt chamber, an acid chamber and a base chamber, and the salt chamber corresponds to a salt inlet channel and a salt outlet channel; an acid chamber corresponds to an acid inlet channel and an acid outlet channel; one alkali chamber corresponds to one alkali inlet channel and one alkali outlet channel.
When the salt, the acid and the alkali pass through the corresponding salt chamber, the acid chamber and the alkali chamber, the cross-flow filtration principle and the separation function of the membrane are applied.
A salt chamber is correspondingly arranged on the pair of diaphragms 1, a salt outlet is correspondingly arranged on the pair of diaphragms 20, and two salt outlets are correspondingly arranged on the pair of diaphragms 40.
1 pair of diaphragms are correspondingly provided with an acid chamber, 20 acid chambers are correspondingly provided with an acid outlet, 20 pairs of diaphragms are correspondingly provided with an acid outlet, and 40 pairs of diaphragms are correspondingly provided with two acid outlets.
1 pair of diaphragms are correspondingly provided with an alkali chamber, 20 alkali chambers are correspondingly provided with an alkali outlet, 20 pairs of diaphragms are correspondingly provided with an alkali outlet, and 40 pairs of diaphragms are correspondingly provided with two alkali outlets.
The bipolar membrane, the cathode membrane and the anode membrane are rectangular with 1500mm of 500mm, the total area is 0.75m, the effective area is 1200mm of 1200mm, the effective area is 0.5m, and the effective area occupies 66.67%.
The membrane voltage (10A/dm, 30 ℃) of the bipolar membrane is 1.2V; the water decomposition efficiency is more than or equal to 98 percent; the breaking strength is more than or equal to 0.4Mpa; the thickness was 0.22mm.
The type of the positive film is CSE-2, namely a strong acid positive film, and has the characteristic of high strength; the membrane impedance is 1.9 Ω cm; the breaking strength is more than 0.35 Mpa; the thickness was 0.15mm.
The model ACM of the negative film, namely the weak alkaline negative film, has the characteristic of difficult acid permeation; the membrane impedance is 2.6 Ω cm; the breaking strength is more than 0.15 Mpa; the thickness was 0.11mm.
The operating temperature of the membrane stack is 30-40 ℃, and the operating pressure of the membrane stack is 0.03-0.1 Mpa.
The nanofiltration membrane device is the prior mature technology and can be directly purchased and obtained by factories.
The acid salt separating device comprises a resin column, separates according to the difference of adsorption and desorption rates between sulfuric acid and sodium sulfate, is a mature technology in the prior art, and can be directly purchased by manufacturers. ( The manufacturer is: new Material Co.Ltd )
The reverse osmosis membrane device is the prior art and can be obtained directly through the purchase of factories.
By adopting the technical scheme, the beneficial technical effects brought are as follows:
1) The invention forms a circulating environment-friendly treatment system through the arrangement of the centrifugal machine, the transfer tank, the blending tank, the coarse filtering device, the fine filtering device, the resin tower, the circulating tank and the bipolar membrane device, and finishes the recycling of sulfuric acid, sodium hydroxide and dilute sodium sulfate solution through optimizing treatment conditions, technological parameters, equipment, indexes and the like, thereby being more suitable for industrialized production. Through the arrangement of the resin tower, the circulating tank and the bipolar membrane device, sulfuric acid, sodium hydroxide and dilute sodium sulfate solution are recovered to the maximum extent, the purity and concentration of the sulfuric acid and the sodium hydroxide are effectively ensured, secondary pollution in a treatment process is avoided, and the sulfuric acid and the sodium hydroxide can be directly recycled to a viscose production process or storage, so that zero emission is realized;
2) In the preparation tank, the pH value is limited to 9-11, the temperature is 30-40 ℃ and the concentration of sodium sulfate is 300g/L, under the setting of the pH value of 9-11, the maximum precipitation of zinc ions is ensured, meanwhile, the preparation work is carried out for the residual zinc ions to be adsorbed by resin, the optimal working environment pH value of the resin tower for adsorbing the zinc ions is 9-11, namely, the adsorption effect of the subsequent resin tower on the zinc ions under the condition is ensured, and the zinc ion impurities are prevented from being completely removed; when the pH value is less than or equal to 9, zinc ions in the solution are not completely precipitated, so that the zinc ions cannot be removed to the greatest extent; when the pH is more than or equal to 11, the precipitate is dissolved, and zinc ions can not be completely removed;
the temperature is set to be 30-40 ℃, so that the maximum solubility of sodium sulfate is ensured, and the stable proceeding of the treatment process is ensured. The temperature is lower than 30 ℃, which can lead to crystallization precipitation of sodium sulfate in the solution and block the pipeline; the temperature is higher than 40 ℃, and the chilled water consumption of downstream processes (such as bipolar membrane device electrodialysis) is increased;
the concentration of sodium sulfate is set to 300g/L, so that the electrodialysis efficiency of the bipolar membrane device is ensured, and the stable proceeding of the treatment process is ensured. Concentration lower than 300g/L, resulting in reduced equipment operating efficiency (e.g., bipolar membrane electrodialysis) and low yield; the concentration is higher than 300g/L, and sodium sulfate is easy to crystallize due to the excessive concentration, so that the risk of pipe blockage is increased, and the production control is not facilitated;
3) According to the invention, through the arrangement of the resin, the upper filter plate and the lower filter plate in the tower body of the resin tower and the limitation of the positions and the connection relation of the upper filter plate and the lower filter plate, smooth, stable and orderly falling of the refined filtrate after entering the tower body is ensured, the contact area and time between the refined filtrate and the resin are increased, zinc ions are effectively removed, and the concentration and purity of subsequent products are improved; meanwhile, the arrangement can prevent resin from overflowing, avoid blockage of a filter cavity and ensure stable performance of an environment-friendly treatment procedure of the viscose waste liquid;
4) According to the invention, through the arrangement of the vertical partition plate, the upper transverse plate, the lower transverse plate, the reflux cavity, the mixing cavity, the channel, the reflux port, the overflow port, the feed port and the discharge port in the circulating tank body and the limitation of the positions and the connection relation of the vertical partition plate, the upper transverse plate, the lower transverse plate, the reflux cavity, the mixing cavity, the channel, the reflux port, the overflow port, the feed port and the discharge port, the reflux is prevented from being immediately mixed with newly added or newly generated matters, and through the separation and the flow guiding functions, the reflux is prevented from being mixed with newly added or newly generated matters at the top of the circulating tank body, the material back mixing cost is reduced, the operation efficiency is improved, the reflux and newly added or newly generated matters are ensured to be completely mixed, the concentration of the discharge port is improved, and the electrodialysis efficiency of the bipolar membrane stack is further improved;
5) According to the invention, the arrangement of a diaphragm unit, a diaphragm plate, a polar plate, a salt inlet channel, an acid inlet channel, an alkali inlet channel, a salt outlet channel, an acid outlet channel, an alkali outlet channel and the like in the bipolar membrane device and the limitation of the positions, the compositions and the connection relation of the diaphragm unit, the diaphragm plate, the polar plate, the salt inlet channel, the acid inlet channel, the alkali outlet channel and the like ensure that sodium sulfate solution orderly, controllably and effectively enters the bipolar membrane device, promote the bipolar membrane device to stably perform cross-flow filtration and ion exchange membrane selective permeability, and perform maximum recovery on the sodium sulfate solution, thereby improving the concentration and the purity of subsequent products;
6) In the invention, the method is suitable for industrial mass production, can be directly arranged in the viscose production process, can recycle the viscose waste liquid, realizes zero emission, recycles the product to the viscose production process, saves the production cost and improves the installation integrity of equipment; the device can be independently arranged and is specially used for treating viscose waste liquid, so that the integration level of equipment is improved.
Drawings
FIG. 1 is a block diagram of the structure of the present invention;
FIG. 2 is a workflow diagram of the present invention;
FIG. 3 is a schematic diagram showing the connection of a resin column to a resin column according to the present invention;
FIG. 4 is a schematic view of the structure of the resin column of the present invention;
FIG. 5 is a schematic view of the structure of the circulation tank in the present invention;
FIG. 6 is a schematic diagram of the logical connection of embodiment 6 of the present invention;
FIG. 7 is a logic flow diagram of embodiment 6 of the present invention;
FIG. 8 is a schematic view of a bipolar membrane apparatus of the present invention;
FIG. 9 is a schematic diagram of a separator plate structure of a bipolar membrane apparatus of the present invention;
FIG. 10 is a schematic diagram of a salt compartment structure of a bipolar membrane apparatus of the present invention;
FIG. 11 is a schematic diagram of the acid chamber structure of a bipolar membrane apparatus of the present invention;
FIG. 12 is a schematic view of the base chamber structure of a bipolar membrane device of the present invention;
FIG. 13 is a schematic diagram of a bipolar membrane apparatus according to the present invention;
Wherein, in the figure: 1. centrifuge, 2, transfer tank, 3, blending tank, 4, coarse filtration device, 5, fine filtration device, 6, resin tower, 7, bipolar membrane device, 8, circulation tank, 9, brine storage tank, 10, acid storage tank, 11, alkali storage tank, 12, desalted water storage tank, 13, heat exchanger, 14, salt circulation tank, 15, acid circulation tank, 16, alkali circulation tank, 17, valve, 18, zinc ion detector, 19, acid salt separation device, 20, reverse osmosis device, 21, nanofiltration device, 22, polar water tank;
601. the tower body 602, the filter cavity 603, the upper filter plate 604, the lower filter plate 605, the liquid inlet 606, the liquid outlet 607, the water distribution hole 608 and the water distributor;
801. a tank body 802, vertical partition plates 803, an upper transverse plate 804, a lower transverse plate 805, a reflux cavity 806, a mixing cavity 807, a reflux port 808, an overflow port 809, a feed port 810 and a discharge port;
110. diaphragm unit, 120, diaphragm plate, 130, plate, 140, power interface, 150, polar water inlet, 160, polar water outlet, 111, diaphragm, 112, cathode film, 113, yang Mo, 114, bipolar film, 170, salt inlet, 180, acid inlet, 190, alkali inlet, 200, salt outlet, 210, acid outlet, 220, alkali outlet, 171, salt inlet channel, 181, acid inlet channel, 191, alkali inlet channel, 201, salt outlet channel, 211, acid outlet channel, 221, alkali outlet channel, 230, aperture, 240, flow channel, 115, salt chamber, 116, acid chamber, 117, alkali chamber, 250, pressure plate, 260, fastening bolt, 270, frame, 280, frame beam, 290, hydraulic press piston column.
Detailed Description
In the following, it is obvious that the embodiments described are only some embodiments of the present invention, but not all embodiments, by clearly and completely describing the technical solutions in the embodiments of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
A recycling and environment-friendly treatment process of viscose waste liquid,
separating the viscose waste liquid by a centrifugal machine 1 to obtain powdery solid containing sodium sulfate, zinc sulfate and sulfuric acid and concentrated acid bath containing sodium sulfate, zinc sulfate and sulfuric acid, directly conveying the concentrated acid bath to an acid standing acid storage tank in the viscose fiber production process through a pipeline, and placing the powdery solid containing sodium sulfate, zinc sulfate and sulfuric acid into a transfer tank 2;
adding desalted water into the transfer tank 2, and dissolving powdery solid to obtain a dissolving solution;
then, introducing the solution into a blending tank 3, and adjusting the temperature, pH and sodium sulfate concentration in the blending tank 3 to obtain a suspension-containing solution;
under this condition, zinc ions in the solution combine with hydroxide ions to form a white precipitate of zinc hydroxide, and are suspended in the solution, during which about 80% of the zinc ions are precipitated;
Introducing the suspension-containing solution into a coarse filtration device 4, and performing coarse filtration to remove large-particle zinc hydroxide precipitates to obtain filter residues I and coarse filtrate;
introducing the rough filtrate into a fine filtering device 5, fine filtering to remove small-particle zinc hydroxide precipitates and obtain filter residue II and fine filtrate;
introducing the refined filtrate into a resin tower 6, controlling the resin tower 6 to be in a weak alkaline environment, and after chelating and adsorbing, combining the residual zinc ions on the resin to obtain a pure sodium sulfate solution;
introducing pure sodium sulfate solution into a circulating tank 8, then introducing the pure sodium sulfate solution into a bipolar membrane device 7, performing electrodialysis through a membrane stack mechanism and circulating reflux between the membrane stack mechanism and the circulating tank 8, obtaining acid liquor through an acid outlet of the bipolar membrane device 7, obtaining alkali liquor through an alkali outlet of the bipolar membrane device 7, and obtaining salt water through a salt outlet of the bipolar membrane device 7;
introducing the acid liquor into a reverse osmosis device 20, obtaining concentrated sulfuric acid solution and dilute sulfuric acid solution through reverse osmosis, directly conveying the concentrated sulfuric acid solution to an acid bath process in a viscose fiber production process through a pipeline, and directly conveying the dilute sulfuric acid solution to a feed inlet of an acid circulation tank 15 through the pipeline;
introducing the alkali liquor into a nanofiltration device 21, obtaining sodium hydroxide solution and mixed solution containing sodium sulfate and sodium hydroxide through the action of nanofiltration membrane, directly conveying the sodium hydroxide solution to an impregnation procedure in a viscose fiber production process through a pipeline, and directly conveying the mixed solution containing sodium sulfate and sodium hydroxide to a blending tank 3 through the pipeline;
The brine is introduced into an acid salt separating device 19, desalted water is introduced, sulfuric acid solution and sodium sulfate solution are obtained through separation, the sulfuric acid solution is directly conveyed to an acid bath process in the viscose fiber production process through a pipeline, and the sodium sulfate solution is directly conveyed to a transfer tank 2 through the pipeline.
Example 2
On the basis of example 1, further,
further, the viscose waste liquid comprises sodium sulfate with the concentration of 200g/L, zinc sulfate with the concentration of 0.1g/L and sulfuric acid with the concentration of 5g/L;
the concentration of sodium sulfate in the dissolving solution is 300g/L;
the concentration of sodium sulfate in the blending tank 3 is controlled to be 300g/L;
the acid liquor is sulfuric acid solution with the concentration of 60g/L, the concentration of the concentrated sulfuric acid solution is 110g/L after reverse osmosis, and the concentration of the dilute sulfuric acid solution is 10g/L;
the alkali liquor is sodium hydroxide solution with the concentration of 45g/L; after the nanofiltration membrane is used, the concentration of the sodium hydroxide solution is 45g/L;
the brine comprises sulfuric acid solution with the concentration of 20g/L and sodium sulfate solution with the concentration of 100 g/L; after separation by the acid salt separation device 19, the concentration of the sulfuric acid solution is 20g/L, and the concentration of the sodium sulfate solution is 100g/L.
Further, in the centrifuge 1, the discharge flow rate of sodium sulfate in the powdery solid is 2t/h, the discharge flow rate of zinc sulfate is 0.0014t/h, and the discharge flow rate of sulfuric acid is 0.07t/h;
In the transfer tank 2, the feeding flow of the desalted water is 5m n/h;
in the resin tower 6, the feeding flow rate of the fine filtrate is 7 m/h;
in the circulation tank 8, the feeding flow rate of the pure sodium sulfate solution is 7m n/h;
in the bipolar membrane device 7, the feeding flow rate of the pure sodium sulfate solution is 7 m/h;
in the bipolar membrane device 7, the discharge flow rate of the acid liquor is 132 m/d, the discharge flow rate of the alkali liquor is 150 m/d, and the discharge flow rate of the salt water is 140 m/d;
in the reverse osmosis device 20, the discharging flow of the concentrated sulfuric acid solution is 66 m/d, and the discharging flow of the dilute sulfuric acid solution is 66 m/d;
in the nanofiltration device 21, the discharge flow rate of the sodium hydroxide is 150 m/d, and the discharge flow rate of the mixed solution is 10 m/d;
in the acid salt separation device 19, the feeding flow rate of the desalted water is 140 m/d; the discharge flow of the sulfuric acid solution is 140m 2/d, and the discharge flow of the sulfuric acid solution is 140m 2/d.
Further, the rotating speed of the centrifugal machine 1 is 4000r/min;
the pH value in the blending tank 3 is 9, and the temperature is 30 ℃;
the weak basicity in the resin column 6 means that the pH is 9;
in the bipolar membrane device 7, there are set: current of 360A, voltage of 255V, temperature of 35 ℃ and operating pressure of 0.06 Mpa;
In the reverse osmosis unit 20, the pressure was 6.5 Mpa;
in the nanofiltration device 21, the pressure was 2.3Mpa;
in the acid salt separating device 19, the desalted water and the acid liquid are fed in a pulse mode.
Example 3
On the basis of embodiment 2, this embodiment differs in that:
further, the viscose waste liquid comprises sodium sulfate with the concentration of 300g/L, zinc sulfate with the concentration of 1g/L and sulfuric acid with the concentration of 10 g/L;
the concentration of sodium sulfate in the dissolving solution is 300g/L;
the concentration of sodium sulfate in the blending tank 3 is controlled to be 300g/L;
the acid liquor is sulfuric acid solution with the concentration of 80g/L, the concentration of the concentrated sulfuric acid solution is 130g/L after reverse osmosis, and the concentration of the dilute sulfuric acid solution is 30g/L;
the alkali liquor comprises sodium hydroxide solution with the concentration of 80g/L and sodium sulfate solution with the concentration of 2 g/L; after the nanofiltration membrane is used, the concentration of the sodium hydroxide solution is 80g/L, the concentration of sodium sulfate in the mixed solution is 50g/L, and the concentration of sodium hydroxide is 80g/L;
the brine comprises sulfuric acid solution with the concentration of 30g/L and sodium sulfate solution with the concentration of 180 g/L; after separation by the acid salt separation device 19, the concentration of the sulfuric acid solution is 30g/L, and the concentration of the sodium sulfate solution is 180g/L.
Further, in the centrifuge 1, the discharge flow rate of sodium sulfate in the powdery solid is 2.5t/h, the discharge flow rate of zinc sulfate is 0.008t/h, and the discharge flow rate of sulfuric acid is 0.075t/h;
In the transfer tank 2, the feeding flow rate of the desalted water is 6m 3 /h；
In the resin column 6, the feed flow rate of the fine filtrate was 8.5m 3 /h；
In the recycle tank 8, the pure sodium sulfate solution was fed at a rate of 8.5m 3 /h；
In the bipolar membrane device 7, the feed rate of the pure sodium sulfate solution was 8.5m 3 /h；
In the bipolar membrane device 7, the discharge flow rate of the acid liquid is 165m 3 And/d, the discharge flow of the alkali liquor is 187.5m 3 The discharge flow rate of the brine is 168m 3 /d；
In the reverse osmosis device 20, the discharge flow rate of the concentrated sulfuric acid solution is 82.5m 3 And/d, wherein the discharge flow of the dilute sulfuric acid solution is 82.5m 3 /d；
In the nanofiltration device 21, the discharge flow rate of the sodium hydroxide was 187.5m 3 And/d, the discharge flow of the mixed solution is 13m 3 /d；
In the acid salt separation device 19, the feeding flow rate of the desalted water is 168m 3 /d; the discharge flow of the sulfuric acid solution is 168m 3 The discharge flow of the sulfuric acid solution is 168m 3 /d。
Further, the rotating speed of the centrifugal machine 1 is 4300r/min;
the pH in the blending tank 3 is 11, and the temperature is 40 ℃;
weak basicity in resin column 6 means pH 9.5;
in the bipolar membrane device 7, there are set: 400A current, 280V voltage, 33 ℃ temperature and 0.06 Mpa operating pressure;
in the reverse osmosis unit 20, the pressure is 8 Mpa;
In the nanofiltration device 21, the pressure was 2.8 Mpa;
in the acid salt separating device 19, the desalted water and the acid liquid are fed in a pulse mode.
Example 4
On the basis of examples 2-3, this example differs in that:
further, the viscose waste liquid comprises sodium sulfate with the concentration of 250g/L, zinc sulfate with the concentration of 0.6g/L and sulfuric acid with the concentration of 8 g/L;
the concentration of sodium sulfate in the dissolving solution is 300g/L;
the concentration of sodium sulfate in the blending tank 3 is controlled to be 300g/L;
the acid liquor is sulfuric acid solution with the concentration of 70g/L, the concentration of the concentrated sulfuric acid solution is 120g/L after reverse osmosis, and the concentration of the dilute sulfuric acid solution is 20g/L;
the alkali liquor comprises sodium hydroxide solution with the concentration of 64g/L and sodium sulfate solution with the concentration of 1 g/L; after the nanofiltration membrane is used, the concentration of the sodium hydroxide solution is 64g/L, the concentration of sodium sulfate in the mixed solution is 38g/L, and the concentration of sodium hydroxide is 64g/L;
the brine comprises sulfuric acid solution with the concentration of 25g/L and sodium sulfate solution with the concentration of 140 g/L; after separation by the acid salt separation means 19, the concentration of the sulfuric acid solution was 25g/L and the concentration of the sodium sulfate solution was 140g/L.
Further, in the centrifuge 1, the discharge flow rate of sodium sulfate in the powdery solid is 3t/h, the discharge flow rate of zinc sulfate is 0.008t/h, and the discharge flow rate of sulfuric acid is 0.010t/h;
In the transfer tank 2, the feeding flow of the desalted water is 7 m/h;
in the resin tower 6, the feeding flow rate of the fine filtrate is 10 m/h;
in the circulating tank 8, the feeding flow rate of the pure sodium sulfate solution is 10m n/h;
in the bipolar membrane device 7, the feeding flow rate of the pure sodium sulfate solution is 10 m/h;
in the bipolar membrane device 7, the discharge flow rate of the acid liquor is 198 m/d, the discharge flow rate of the alkali liquor is 225 m/d, and the discharge flow rate of the salt water is 196.8 m/d;
in the reverse osmosis device 20, the discharge flow rate of the concentrated sulfuric acid solution is 99 m/d, and the discharge flow rate of the dilute sulfuric acid solution is 99 m/d;
in the nanofiltration device 21, the discharge flow rate of the sodium hydroxide is 225 m/d, and the discharge flow rate of the mixed solution is 15 m/d;
in the acid salt separation device 19, the feeding flow rate of the desalted water is 196.8 m/d; the discharge flow of the sulfuric acid solution is 196.8 m/d, and the discharge flow of the sulfuric acid solution is 196.8 m/d.
Further, the rotating speed of the centrifugal machine 1 is 4500r/min;
the pH in the blending tank 3 is 10, and the temperature is 35 ℃;
weak basicity in resin column 6 means pH 10;
in the bipolar membrane device 7, there are set: 380A current, 279V voltage, 35 ℃ temperature and 0.06 Mpa operating pressure;
In the reverse osmosis unit 20, the pressure was 7.4Mpa;
in the nanofiltration device 21, the pressure was 2.6Mpa;
in the acid salt separating device 19, the desalted water and the acid liquid are fed in a pulse mode.
Example 5
On the basis of examples 2-4, this example differs in that:
further, the viscose waste liquid comprises sodium sulfate with the concentration of 230g/L, zinc sulfate with the concentration of 0.2g/L and sulfuric acid with the concentration of 6 g/L;
the concentration of sodium sulfate in the dissolving solution is 300g/L;
the concentration of sodium sulfate in the blending tank 3 is controlled to be 300g/L;
the acid liquor is sulfuric acid solution with the concentration of 65g/L, the concentration of the concentrated sulfuric acid solution is 115g/L after reverse osmosis, and the concentration of the dilute sulfuric acid solution is 15g/L;
the alkali liquor comprises sodium hydroxide solution with the concentration of 55g/L and sodium sulfate solution with the concentration of 0.9 g/L; after the nanofiltration membrane is used, the concentration of the sodium hydroxide solution is 55g/L, the concentration of sodium sulfate in the mixed solution is 30g/L, and the concentration of sodium hydroxide is 55g/L;
the brine comprises a sulfuric acid solution with the concentration of 23g/L and a sodium sulfate solution with the concentration of 120 g/L; after separation by the acid salt separation device 19, the concentration of the sulfuric acid solution is 23g/L, and the concentration of the sodium sulfate solution is 120g/L.
Further, in the centrifuge 1, the discharge flow of sodium sulfate in the powdery solid is 3.5t/h, the discharge flow of zinc sulfate is 0.010t/h, and the discharge flow of sulfuric acid is 0.011t/h;
In the transfer tank 2, the feeding flow of the desalted water is 8.2 m/h;
in the resin column 6, the feed flow rate of the fine filtrate was 11.7 m/h;
in the recycle tank 8, the feed rate of the pure sodium sulfate solution is 11.7 m/h;
in the bipolar membrane device 7, the feed rate of the pure sodium sulfate solution is 11.7 m/h;
in the bipolar membrane device 7, the discharge flow rate of the acid liquor is 231 m/d, the discharge flow rate of the alkali liquor is 262.5m 2/d, and the discharge flow rate of the salt water is 230.4 m/d;
in the reverse osmosis unit 20, the concentrated sulfuric acid solution discharge flow rate is 115.5 m/d, and the dilute sulfuric acid solution discharge flow rate is 115.5 m/d;
in the nanofiltration device 21, the discharge flow rate of the sodium hydroxide is 231.3 m/d, and the discharge flow rate of the mixed solution is 17.5 m/d;
in the acid salt separation device 19, the feeding flow rate of the desalted water is 230.4 m/d; the discharge flow of the sulfuric acid solution is 230.4m 2/d; the discharge flow of the sulfuric acid solution was 230.4m w/d.
Further, the rotating speed of the centrifugal machine 1 is 4890r/min;
the pH value in the blending tank 3 is 9.7, and the temperature is 33 ℃;
weak basicity in resin column 6 means pH 9.7;
in the bipolar membrane device 7, there are set: a current of 375A, a voltage of 265V, a temperature of 31℃and an operating pressure of 0.05 MPa;
In the reverse osmosis unit 20, the pressure was 6.8 Mpa;
in the nanofiltration device 21, the pressure was 2.6 Mpa;
in the acid salt separating device 19, the desalted water and the acid liquid are fed in a pulse mode.
Example 6
On the basis of examples 2-5, this example differs in that:
further, the viscose waste liquid comprises 280g/L sodium sulfate, 0.9g/L zinc sulfate and 8g/L sulfuric acid;
the concentration of sodium sulfate in the dissolving solution is 300g/L;
the concentration of sodium sulfate in the blending tank 3 is controlled to be 300g/L;
the acid liquor is sulfuric acid solution with the concentration of 78g/L, the concentration of the concentrated sulfuric acid solution is 125g/L after reverse osmosis, and the concentration of the dilute sulfuric acid solution is 25g/L;
the alkali liquor comprises sodium hydroxide solution with the concentration of 75g/L and sodium sulfate solution with the concentration of 1.6 g/L; after the nanofiltration membrane is used, the concentration of the sodium hydroxide solution is 73g/L, the concentration of sodium sulfate in the mixed solution is 25-75 g/L, and the concentration of sodium hydroxide is 73g/L;
the brine comprises sulfuric acid solution with the concentration of 28g/L and sodium sulfate solution with the concentration of 175 g/L; after separation by the acid salt separation means 19, the concentration of the sulfuric acid solution was 28g/L and the concentration of the sodium sulfate solution was 175g/L.
Further, in the centrifuge 1, the discharge flow rate of sodium sulfate in the powdery solid is 4t/h, the discharge flow rate of zinc sulfate is 0.014t/h, and the discharge flow rate of sulfuric acid is 0.14t/h;
in the transfer tank 2, the feeding flow of the desalted water is 9.4 m/h;
in the resin column 6, the feed flow rate of the fine filtrate was 13.4 m/h;
in the recycle tank 8, the feed rate of the pure sodium sulfate solution is 13.4m solution/h;
in the bipolar membrane device 7, the feed rate of the pure sodium sulfate solution is 13.4 m/h;
in the bipolar membrane device 7, the discharge flow of the acid liquor is 289 m/d, the discharge flow of the alkali liquor is 328 m/d, and the discharge flow of the salt water is 264 m/d;
in the reverse osmosis device 20, the discharge flow rate of the concentrated sulfuric acid solution is 144.5 m/d, and the discharge flow rate of the dilute sulfuric acid solution is 144.5 m/d;
in the nanofiltration device 21, the discharge flow rate of the sodium hydroxide is 328 m/d, and the discharge flow rate of the mixed solution is 40 m/d;
in the acid salt separation device 19, the feeding flow rate of the desalted water is 264 m/d; the discharge flow of the sulfuric acid solution is 264m 2 m W/d, and the discharge flow of the sulfuric acid solution is 264m W/d.
Further, the rotating speed of the centrifugal machine 1 is 4890r/min;
The pH in the blending tank 3 is 10.2, and the temperature is 39 ℃;
weak basicity in resin column 6 means a pH of 10.2;
in the bipolar membrane device 7, there are set: current 387A, voltage 275V, temperature 39 ℃ and operating pressure 0.08 Mpa;
in the reverse osmosis unit 20, the pressure was 7.5 Mpa;
in the nanofiltration device 21, the pressure was 2.7 Mpa;
in the acid salt separating device 19, the desalted water and the acid liquid are fed in a pulse mode.
Example 7
On the basis of examples 1-6, further,
and collecting filter residues I in the rough filtration and filter residues II in the fine filtration, and directly conveying the filter residues I and II to an acid bath process in the viscose fiber production process at a feed flow of 0.0085 kg/h.
Example 8
On the basis of example 7, further,
an acid salt separation device 19 is further arranged between the transfer tank 2 and the blending tank 3, after the obtained solution is introduced into the acid salt separation device 19, desalted water is introduced into the acid salt separation device 19 at a feed flow of 100 m/d, concentrated sulfuric acid solution with a discharge flow of 100 m/d and a concentration of 10g/L and sodium sulfate solution containing impurities are separated, the concentrated sulfuric acid solution is directly conveyed to an acid bath process in a viscose fiber production process through a pipeline, and the sodium sulfate solution containing the impurities is introduced into the blending tank 3 for subsequent processes.
Example 9
On the basis of example 8, further,
the pH in the blending tank 3 is adjusted to 10, and the specific operations comprise:
if the circulating environment-friendly treatment system is used for the first time, a sodium hydroxide solution with the concentration of 720g/L is introduced into the blending tank 3 at the feeding flow rate of 25L/h, and the sodium hydroxide solution with the concentration of 720g/L is prepared by dissolving sodium hydroxide in water;
if the circulating environment-friendly treatment system is not used for the first time, a sodium hydroxide solution with the concentration of 73g/L is introduced into the blending tank 3 at the feeding flow rate of 370L/h, and the sodium hydroxide solution with the concentration of 73g/L comes from the nanofiltration device 21 in the circulating environment-friendly treatment system.
Example 10
On the basis of examples 1-9, the following equipment was used:
as shown in fig. 1-2: a viscose waste liquid circulation environment-friendly treatment system comprises a centrifugal machine 1 for separating viscose waste liquid into powdery solid and concentrated acid bath liquid, a transfer tank 2 for dissolving the powdery solid into solution, a blending tank 3 for generating suspended matters from the solution by adjusting the temperature, the pH value and the sodium sulfate concentration, a coarse filtering device 4 for filtering solution containing suspended matters into filter residues I and coarse filtrate, a fine filtering device 5 for filtering the coarse filtrate into filter residues II and fine filtrate, a resin tower 6 for generating pure sodium sulfate from the fine filtrate by chelating adsorption, a circulation tank 8 for circulating fluid and a bipolar membrane device 7 for electrodialysis of sodium sulfate into sulfuric acid and sodium hydroxide, wherein the transfer tank 2 is arranged at one side of a station of the centrifugal machine 1; the transfer tank 2 is connected with a desalted water storage tank 12, and the transfer tank 2 is connected with the blending tank 3; the blending tank 3 is connected with a temperature-adjusting heat exchanger 13, a pH-adjusting alkali storage tank 11 and a sodium sulfate concentration-adjusting desalted water storage tank 12, and the blending tank 3 is connected with the coarse filtering device 4; the coarse filter device 4 is connected with the fine filter device 5, the fine filter device 5 is connected with the resin tower 6, the resin tower 6 is connected with the bipolar membrane device 7 through the circulating tank 8, and an independent circulating passage is formed between the circulating tank 8 and the bipolar membrane device 7.
Example 11
Further, in the embodiment 10, the coarse filtration device 4 is a bag filter having a pore size of 10 μm, and the fine filtration device 5 is an ultrafilter having a pore size of 0.01. Mu.m.
Example 12
On the basis of embodiment 11, this embodiment differs in that: the coarse filter device 4 is a bag filter with a pore diameter of 15 mu m, and the fine filter device 5 is an ultra-filter with a pore diameter of 0.05 mu m.
Example 13
On the basis of examples 11-12, this example differs in that: the coarse filter device 4 is a bag filter with a pore diameter of 13 μm, and the fine filter device 5 is an ultra-filter with a pore diameter of 0.02 μm.
Example 14
On the basis of examples 11-13, further,
as shown in fig. 3: the number of the resin towers 6 is three, the resin towers 6 and the resin towers 6 are connected through pipelines, a valve 17 and a zinc ion detector 18 are arranged on the pipelines, and the detection range of the zinc ion detector 18 is 0-3 ppm.
As shown in fig. 4: the resin tower 6 comprises a tower body 601, resin, an upper filter plate 603 and a lower filter plate 604 which are arranged in the tower body 601, wherein a liquid inlet 605 is formed in the top of the tower body 601, and a liquid outlet 606 is formed in the bottom of the tower body; the upper filter plate 603 is arranged at the upper part of the tower body 601, the lower filter plate 604 is arranged at the lower part of the tower body 601, a filter cavity 602 is formed between the upper filter plate 603 and the lower filter plate 604, and resin is arranged in the filter cavity 602.
The upper filter plate 603 and the lower filter plate 604 are both filter plates with water distribution holes 607, and water distributors 608 are arranged at the water distribution holes 607.
Example 15
Based on example 14, further,
as shown in fig. 5: the circulating tank 8 comprises a tank body 801, a vertical partition plate 802, an upper transverse plate 803 and a lower transverse plate 804, wherein the vertical partition plate 802, the upper transverse plate 803 and the lower transverse plate 804 are arranged in the tank body 801, the vertical partition plate 802 is vertically arranged in the tank body 801 and is fixed at the top and the side surface of the tank body 801, one side of the vertical partition plate 802 and the inner wall of the tank body 801 form a backflow cavity 805, the other side of the vertical partition plate 802 and the inner wall of the tank body 801 form a mixing cavity 806, and a channel is formed between the end part of the vertical partition plate 802 and the inner wall of the bottom of the tank body 801; a reflux port 807 is arranged at the top of the tank 801, the reflux port 807 is communicated with a reflux cavity 805, an overflow port 808 is arranged at the upper part of the reflux cavity 805, an upper transverse plate 803 is arranged below the overflow port 808, and a channel is formed between the end part of the upper transverse plate 803 and the vertical partition plate 802; the top of the tank 801 is also provided with a feed inlet 809, the feed inlet 809 is communicated with the mixing cavity 806, the lower part of the mixing cavity 806 is provided with a discharge outlet 810, a lower transverse plate 804 is arranged below the discharge outlet 810, and a channel is formed between the end part of the lower transverse plate 804 and the vertical partition plate 802.
The circulating tank 8 comprises a three-stage salt circulating tank 14, an acid circulating tank 15 and a base circulating tank 16, the bipolar membrane device 7 comprises a three-stage membrane stack mechanism, and the salt circulating tank 14, the acid circulating tank 15 and the base circulating tank 16 are arranged in series corresponding to the four membrane stack mechanisms;
As shown in fig. 6-7: the circulating tank 8 comprises a first-stage salt circulating tank, a first-stage acid circulating tank, a first-stage alkali circulating tank, a second-stage salt circulating tank, a second-stage acid circulating tank, a second-stage alkali circulating tank, a third-stage salt circulating tank, a third-stage acid circulating tank and a third-stage alkali circulating tank, the bipolar membrane device 7 comprises a first-stage membrane stack mechanism, a second-stage membrane stack mechanism and a third-stage membrane stack mechanism, the first-stage salt circulating tank, the first-stage acid circulating tank and the first-stage alkali circulating tank are all connected with the first-stage membrane stack mechanism, the second-stage salt circulating tank, the second-stage acid circulating tank and the second-stage alkali circulating tank are all connected with the second-stage membrane stack mechanism, and the third-stage salt circulating tank, the third-stage acid circulating tank and the third-stage alkali circulating tank are all connected with the third-stage membrane stack mechanism;
the feed inlet of the first-stage salt circulation tank is connected with the resin tower 6, the discharge outlet of the first-stage salt circulation tank is connected with the feed inlet of the first-stage membrane stack mechanism, the salt outlet of the first-stage membrane stack mechanism is connected with the reflux inlet of the first-stage salt circulation tank, an independent circulation passage is formed between the first-stage salt circulation tank and the first-stage membrane stack mechanism, and the first-stage salt circulation tank is connected with a salt storage tank;
the second-stage salt circulation tank is connected with the overflow port of the first-stage salt circulation tank, the feed port of the second-stage salt circulation tank is connected with the salt storage tank 9, the discharge port of the second-stage salt circulation tank is connected with the salt inlet of the second-stage membrane stack mechanism, the salt outlet of the second-stage membrane stack mechanism is connected with the reflux port of the second-stage salt circulation tank, and an independent circulation passage is formed between the second-stage salt circulation tank and the second-stage membrane stack mechanism;
The third-stage salt circulation tank is connected with the overflow port of the second-stage salt circulation tank, the feed port of the third-stage salt circulation tank is connected with the salt storage tank 9, the discharge port of the third-stage salt circulation tank is connected with the salt inlet of the third-stage membrane stack mechanism, the salt outlet of the third-stage membrane stack mechanism is connected with the reflux port of the third-stage salt circulation tank, and an independent circulation passage is formed between the third-stage salt circulation tank and the third-stage membrane stack mechanism. The overflow port of the third-stage salt circulating tank is connected with an acid salt separating device 19, the acid outlet of the acid salt separating device 19 is directly connected with an acid station acid storage tank in the viscose fiber production process through a pipeline, and the salt outlet of the acid salt separating device 19 is directly connected with the transfer tank 2 through a pipeline;
the feed inlet of the first-stage acid circulating tank is connected with a desalted water storage tank 12, the discharge outlet of the first-stage acid circulating tank is connected with the acid inlet of the first-stage membrane stack mechanism, the acid outlet of the first-stage membrane stack mechanism is connected with the reflux inlet of the first-stage acid circulating tank, an independent circulating passage is formed between the first-stage acid circulating tank and the first-stage membrane stack mechanism, the overflow port of the first-stage acid circulating tank is connected with a reverse osmosis device 20, the concentrated acid outlet of the reverse osmosis device 20 is directly connected with an acid station acid storage tank in the viscose production process through a pipeline, and the permeate outlet of the reverse osmosis device 20 is directly connected with the first-stage acid circulating tank through a pipeline;
The overflow port of the second-stage acid circulating tank is connected with the first-stage acid circulating tank, the feed port of the second-stage acid circulating tank is connected with the desalted water storage tank 12, the discharge port of the second-stage acid circulating tank is connected with the acid inlet of the second-stage membrane stack mechanism, the acid outlet of the second-stage membrane stack mechanism is connected with the reflux port of the second-stage acid circulating tank, and an independent circulating passage is formed between the second-stage acid circulating tank and the second-stage membrane stack mechanism;
the overflow port of the third-stage acid circulating tank is connected with the second-stage acid circulating tank, the feed port of the second-stage acid circulating tank is connected with the desalted water storage tank 12, the discharge port of the third-stage acid circulating tank is connected with the acid inlet of the third-stage membrane stack mechanism, the acid outlet of the third-stage membrane stack mechanism is connected with the reflux port of the third-stage acid circulating tank, and an independent circulating passage is formed between the third-stage acid circulating tank and the third-stage membrane stack mechanism;
the feed inlet of the first-stage alkali circulating tank is connected with a desalted water storage tank 12, the discharge outlet of the first-stage alkali circulating tank is connected with the alkali inlet of the first-stage membrane stack mechanism, the alkali outlet of the first-stage membrane stack mechanism is connected with the reflux inlet of the first-stage alkali circulating tank, an independent circulating passage is formed between the first-stage alkali circulating tank and the first-stage membrane stack mechanism, the overflow port of the first-stage alkali circulating tank is connected with a nanofiltration device 21, the filtrate port of the nanofiltration device 21 is directly connected with a stock solution storage tank in the viscose production process through a pipeline, and the concentrate port of the nanofiltration device 21 is directly connected with a blending tank 3 through a pipeline;
The overflow port of the second-stage alkali circulating tank is connected with the first-stage alkali circulating tank, the feed port of the second-stage acid circulating tank is connected with the desalted water storage tank 12, the discharge port of the second-stage alkali circulating tank is connected with the alkali inlet of the second-stage membrane stack mechanism, the alkali outlet of the second-stage membrane stack mechanism is connected with the reflux port of the second-stage alkali circulating tank, and an independent circulating passage is formed between the second-stage alkali circulating tank and the second-stage membrane stack mechanism;
the overflow port of the third-stage alkali circulating tank is connected with the second-stage alkali circulating tank, the feed port of the third-stage acid circulating tank is connected with the desalted water storage tank 12, the discharge port of the third-stage alkali circulating tank is connected with the alkali inlet of the third-stage membrane stack mechanism, the alkali outlet of the third-stage membrane stack mechanism is connected with the reflux port of the third-stage alkali circulating tank, and an independent circulating passage is formed between the third-stage alkali circulating tank and the third-stage membrane stack mechanism.
The first stage membrane stack mechanism, the second stage membrane stack mechanism and the third stage membrane stack mechanism are all connected with a polar water tank 22.
Example 16
On the basis of example 15, further,
as shown in fig. 8: the membrane pile mechanism comprises membrane units 110 and membrane plates 120 which are arranged at intervals, the membrane plates 120 are arranged at two sides of the membrane pile mechanism, and the membrane plates 120 at two sides are respectively connected with the polar plates 130; the polar plates 130 are respectively provided with a power interface 140, a polar water inlet 150 and a polar water outlet 160, one polar plate 130 is connected with the positive electrode of a power supply through the power interface 140, and the other polar plate 130 is connected with the negative electrode of the power supply through the power interface 140;
The membrane unit 110 includes a plurality of pairs of overlapping membranes and separators 111, each pair of membranes including a cathode membrane 112, a anode membrane 113, and a bipolar membrane 114, the membrane unit 110 being repeatedly arranged in an arrangement of the bipolar membrane 114, the separators 111, the cathode membrane 112, the separators 111, the anode membrane 113, the separators 111; one end of the partition 111 is connected with a salt inlet 170, an acid inlet 180 and an alkali inlet 190, and a salt inlet channel 171, an acid inlet channel 181 and an alkali inlet channel 191 are respectively formed in the partition 111; the other end of the partition 111 is connected with a salt outlet 200, an acid outlet 210 and a base outlet 220, and a salt outlet channel 201, an acid outlet channel 211 and a base outlet channel 221 are formed in the partition 111.
Example 17
On the basis of example 16, further,
as shown in fig. 9: the thickness of the separator 111 is 3mm, a plurality of openings 230 are formed at two ends of the separator 111, the bipolar membrane 114, the female membrane 112 and the male membrane 113, and the openings 230 on the separator 111 are correspondingly provided with flow passages 240.
As shown in fig. 10-12: the pair of diaphragms are correspondingly provided with a salt chamber, an acid chamber and an alkali chamber, and the salt chamber corresponds to a salt inlet channel and a salt outlet channel; an acid chamber corresponds to an acid inlet channel and an acid outlet channel; one alkali chamber corresponds to one alkali inlet channel and one alkali outlet channel.
The above salt, acid and alkali pass through the corresponding salt chamber 115, acid chamber 116 and alkali chamber 117, and the principle of cross-flow filtration and the separation effect of the membrane are applied.
A salt chamber is correspondingly arranged on the pair of diaphragms 1, a salt outlet is correspondingly arranged on the pair of diaphragms 20, and two salt outlets are correspondingly arranged on the pair of diaphragms 40.
1 pair of diaphragms are correspondingly provided with an acid chamber, 20 acid chambers are correspondingly provided with an acid outlet, 20 pairs of diaphragms are correspondingly provided with an acid outlet, and 40 pairs of diaphragms are correspondingly provided with two acid outlets.
1 pair of diaphragms are correspondingly provided with an alkali chamber, 20 alkali chambers are correspondingly provided with an alkali outlet, 20 pairs of diaphragms are correspondingly provided with an alkali outlet, and 40 pairs of diaphragms are correspondingly provided with two alkali outlets.
The bipolar membrane 114, the cathode membrane 112 and the anode membrane 113 are rectangular with 1500mm by 500mm, the total area is 0.75m, the effective area is 1200mm by 1200mm, the effective area is 0.5m, and the effective area occupies 66.67%.
The membrane voltage (10A/dm, 30 ℃ C.) of bipolar membrane 114 is 1.2V; the water decomposition efficiency is more than or equal to 98 percent; the breaking strength is more than or equal to 0.4Mpa; the thickness was 0.22mm.
The model of the positive film 113 is CSE-2, namely the strong acid positive film 113 has the characteristic of high strength; the membrane impedance is 1.9 Ω cm; the breaking strength is more than 0.35 Mpa; the thickness was 0.15mm.
The model ACM of the negative film 112, namely the weak alkaline negative film 112, has the characteristic of being difficult to penetrate acid; the membrane impedance is 2.6 Ω cm; the breaking strength is more than 0.15 Mpa; the thickness was 0.11mm.
The operating temperature of the membrane stack was 30℃and the operating pressure of the membrane stack was 0.05MPa.
Example 18
Taking viscose waste liquid with sodium sulfate content of 1T as an example, the circulating environment-friendly treatment process of the viscose waste liquid is carried out, and specifically comprises the following steps:
a, dissolving viscose waste liquid into a solution with the concentration of sodium sulfate of 250g/L, the concentration of zinc sulfate of 0.5g/L and the concentration of sulfuric acid of 5g/L by adding desalted water, wherein the total volume of the solution is 4 m;
b, introducing the solution obtained in the step A into a blending tank 3, adjusting the pH to 10, consuming 16.5kg of sodium hydroxide, and generating 1.2kg of zinc hydroxide;
c, introducing the zinc hydroxide-containing solution obtained in the step B into a bag filter, wherein about 35% of zinc hydroxide precipitate is trapped, and 0.4kg of filter residue is generated, so as to obtain crude filtrate;
d, introducing the obtained rough filtrate into an ultrafilter, and intercepting residual zinc hydroxide precipitate to generate a concentrated solution containing zinc hydroxide with the concentration of 0.13m & lt/L & gt and the concentration of 6g/L, thereby obtaining a fine filtrate, wherein the impurity content in the fine filtrate is trace;
e, introducing the obtained refined filtrate into a resin tower 6, and thoroughly removing impurities through resin adsorption to obtain a pure sodium sulfate solution with the content of 1T;
f, introducing the obtained pure sodium sulfate solution into a bipolar membrane device 7, carrying out electrodialysis through a membrane stack mechanism to generate 0.31T sulfuric acid with an electrodialysis efficiency of 60%, generating 0.34T alkali liquor, and generating dilute brine with a sodium sulfate concentration of 100g/L and a sulfuric acid concentration of 25g/L for 4 m:
1. Concentration of 0.31T sulfuric acid is 70g/L and the volume is 4.4m, after the sulfuric acid is concentrated by the reverse osmosis device 20, the concentrated sulfuric acid with the concentration of 120g/L is generated by 2.2m, and the dilute sulfuric acid with the concentration of 20g/L is generated by 2.2 m;
2. the generated 0.34T lye has economic benefit of 0.34 x 3500=1225 yuan per ton according to the lye unit price of 3500 yuan per ton;
the 0.34T alkali liquor contains sodium hydroxide solution with the concentration of 80g/L and sodium sulfate solution with the concentration of 2g/L, the total volume is 4.25m, the alkali liquor is introduced into a nanofiltration membrane system, and filtrate with the concentration of 80g/L of sodium hydroxide is produced to be 4.11 m; generating 0.14m concentrated solution with the concentration of sodium hydroxide of 80g/L and the concentration of sodium sulfate of more than 30 g/L;
3. the resulting 4m dilute brine was passed to an acid salt separation means 19 to produce a sodium sulfate solution of 4m 2 in concentration of 100g/L and sulfuric acid of 4m 2 in concentration of 25 g/L.

Claims (9)

1. A recycling and environment-friendly treatment process of viscose waste liquid is characterized by comprising the following steps of:
separating the viscose waste liquid by a centrifuge (1) to obtain powdery solid containing sodium sulfate, zinc sulfate and sulfuric acid and concentrated acid bath containing sodium sulfate, zinc sulfate and sulfuric acid, directly conveying the concentrated acid bath to an acid standing acid storage tank in the viscose fiber production process through a pipeline, and placing the powdery solid containing sodium sulfate, zinc sulfate and sulfuric acid into a transfer tank (2);
Adding desalted water into the transfer tank (2), and dissolving powdery solid to obtain a dissolving solution;
then, introducing the dissolution liquid into a blending tank (3), and adjusting the temperature, the pH value and the sodium sulfate concentration in the blending tank (3) to obtain a suspension-containing solution;
introducing the solution containing the suspended matters into a coarse filtering device (4), and performing coarse filtration to obtain filter residues I and coarse filtrate;
introducing the rough filtrate into a fine filtering device (5), and fine filtering to obtain filter residue II and fine filtrate;
introducing the refined filtrate into a resin tower (6), controlling the resin tower (6) to be in a weak alkaline environment, and chelating and adsorbing to obtain a pure sodium sulfate solution;
introducing pure sodium sulfate solution into a circulating tank (8), then introducing the pure sodium sulfate solution into a bipolar membrane device (7), obtaining acid liquor through an acid outlet of the bipolar membrane device (7) through the electro-dialysis action of a membrane stack mechanism and the circulating tank (8) and obtaining brine through an alkali outlet of the bipolar membrane device (7) through the cyclic reflux action between the membrane stack mechanism and the circulating tank (8);
introducing the acid liquor into a reverse osmosis device (20), obtaining concentrated sulfuric acid solution and dilute sulfuric acid solution through reverse osmosis, directly conveying the concentrated sulfuric acid solution to an acid bath process in a viscose fiber production process through a pipeline, and directly conveying the dilute sulfuric acid solution to an acid circulation tank (15) through the pipeline;
Introducing the alkali liquor into a nanofiltration device (21), obtaining a sodium hydroxide solution and a mixed solution containing sodium sulfate and sodium hydroxide through the action of a nanofiltration membrane, directly conveying the sodium hydroxide solution to an impregnating or yellowing process in a viscose fiber production process through a pipeline, and directly conveying the mixed solution containing sodium sulfate and sodium hydroxide to a blending tank (3) through the pipeline;
and (3) introducing the brine into an acid salt separation device (19), introducing desalted water, separating to obtain sulfuric acid solution and sodium sulfate solution, directly conveying the sulfuric acid solution to an acid bath process in the viscose fiber production process through a pipeline, and directly conveying the sodium sulfate solution to a transfer tank (2) through the pipeline.
2. The recycling and environmental-friendly treatment process of the viscose waste liquid according to claim 1, which is characterized in that:
the viscose waste liquid comprises 200-300 g/L sodium sulfate, 0.1-1 g/L zinc sulfate and 5-10 g/L sulfuric acid;
the concentration of sodium sulfate in the dissolving solution is 200-300 g/L;
the concentration of sodium sulfate in the blending tank (3) is controlled to be 300g/L;
the acid liquor is sulfuric acid solution with the concentration of 60-80 g/L, the concentration of the concentrated sulfuric acid solution is 110-130 g/L after reverse osmosis, and the concentration of the dilute sulfuric acid solution is 10-30 g/L;
The alkali liquor comprises sodium hydroxide solution with the concentration of 45-80 g/L and sodium sulfate solution with the concentration of 0-2 g/L; after the nanofiltration membrane is used, the concentration of the sodium hydroxide solution is 45-80 g/L, the concentration of sodium sulfate in the mixed solution is 25-50 g/L, and the concentration of sodium hydroxide is 45-80 g/L;
the brine comprises sulfuric acid solution with the concentration of 20-30 g/L and sodium sulfate solution with the concentration of 100-180 g/L; after being separated by an acid salt separating device (19), the concentration of the sulfuric acid solution is 20-30 g/L, and the concentration of the sodium sulfate solution is 100-180 g/L.
3. The recycling and environmental-friendly treatment process of the viscose waste liquid according to claim 1, which is characterized in that:
in the centrifugal machine (1), the discharge flow of sodium sulfate in the powdery solid is 2-4 t/h, the discharge flow of zinc sulfate is 0.0014-0.014 t/h, and the discharge flow of sulfuric acid is 0.07-0.14 t/h;
in the transfer tank (2), the feeding flow of the desalted water is 5-9.4 m/h;
in the resin tower (6), the feeding flow rate of the fine filtrate is 7-13.4 m/h;
in the circulating tank (8), the feeding flow of the pure sodium sulfate solution is 7-13.4 m/h;
in the bipolar membrane device (7), the feeding flow of the pure sodium sulfate solution is 7-13.4 m/h;
In the bipolar membrane device (7), the discharge flow of the acid liquor is 132-289 m/d, the discharge flow of the alkali liquor is 150-328 m/d, and the discharge flow of the salt water is 140-264 m m/d;
in the reverse osmosis device (20), the discharging flow of the concentrated sulfuric acid solution is 66-145 m/d, and the discharging flow of the dilute sulfuric acid solution is 66-145 m/d;
in the nanofiltration device (21), the discharge flow of the sodium hydroxide is 150-328 m/d, and the discharge flow of the mixed solution is 10-40 m/d;
in the acid salt separation device (19), the feeding flow rate of the desalted water is 140-264 m/d; the discharge flow of the sulfuric acid solution is 140-264 m/d, and the discharge flow of the sulfuric acid solution is 140-264 m/d.
4. The recycling and environmental-friendly treatment process of the viscose waste liquid according to claim 1, which is characterized in that:
the rotating speed of the centrifugal machine (1) is 4000-5000 r/min;
the pH value in the blending tank (3) is 9-11, and the temperature is 30-40 ℃;
the weak alkalinity in the resin column (6) means a pH of 9 to 11;
in a bipolar membrane device (7), setting is performed: the current is 300-400A, the voltage is 200-290V, the temperature is 30-40 ℃ and the operating pressure is 0.03-0.1 Mpa;
in the reverse osmosis device (20), the pressure is 6.5-8 Mpa;
In the nanofiltration device (21), the pressure is 2.3-2.8 Mpa;
in the acid salt separating device (19), the desalted water and the salt water are fed in a pulse mode.
5. The recycling and environmental-friendly treatment process of the viscose waste liquid according to claim 1, which is characterized in that: and collecting filter residues I in the rough filtration and filter residues II in the fine filtration, and directly conveying the filter residues I and II to an acid bath process in the viscose fiber production process at a feed flow of 0.0014-0.014 kg/h.
6. The system for recycling and environmental-friendly treatment process of viscose waste liquid according to any one of claims 1-5, wherein the system is characterized in that: the viscose waste liquid separating device comprises a centrifugal machine (1) for separating viscose waste liquid into powdery solid and concentrated acid bath liquid, a transfer tank (2) for dissolving the powdery solid into solution, a blending tank (3) for generating suspended matters from the solution by adjusting the temperature, the pH value and the sodium sulfate concentration, a coarse filtering device (4) for filtering solution containing suspended matters into filter residues I and coarse filtrate, a fine filtering device (5) for filtering the coarse filtrate into filter residues II and fine filtrate, a resin tower (6) for generating pure sodium sulfate from the fine filtrate by chelating and adsorbing, a circulating tank (8) for circulating and refluxing fluid, and a bipolar membrane device (7) for electrodialysis of sodium sulfate into sulfuric acid and sodium hydroxide, wherein the transfer tank (2) is arranged at one station side of the centrifugal machine (1); the transfer tank (2) is connected with a desalted water storage tank (12), and the transfer tank (2) is connected with the blending tank (3); the blending tank (3) is connected with a temperature-adjusting heat exchanger (13), a pH-adjusting alkali storage tank (11) and a sodium sulfate concentration-adjusting desalted water storage tank (12), and the blending tank (3) is connected with the coarse filtering device (4); the coarse filtering device (4) is connected with the fine filtering device (5), the fine filtering device (5) is connected with the resin tower (6), the resin tower (6) is connected with the bipolar membrane device (7) through the circulating tank (8), and an independent circulating passage is formed between the circulating tank (8) and the bipolar membrane device (7);
At least three resin towers (6), wherein the resin towers (6) are connected with each other through pipelines, and a valve (17) and a zinc ion detector (18) are arranged on the pipelines; the resin tower (6) comprises a tower body (601), resin arranged in the tower body (601), an upper filter plate (603) and a lower filter plate (604), wherein a liquid inlet (605) is formed in the top of the tower body (601), and a liquid outlet (606) is formed in the bottom of the tower body; the upper filter plate (603) is arranged at the upper part of the tower body (601), the lower filter plate (604) is arranged at the lower part of the tower body (601), a filter cavity (602) is formed between the upper filter plate (603) and the lower filter plate (604), and resin is arranged in the filter cavity (602);
the circulating tank (8) comprises a tank body (801) and a vertical partition plate (802), an upper transverse plate (803) and a lower transverse plate (804) which are arranged in the tank body (801), wherein the vertical partition plate (802) is vertically arranged in the tank body (801) and is fixed at the top and the side face of the tank body (801), a backflow cavity (805) is formed between one side of the vertical partition plate (802) and the inner wall of the tank body (801), a mixing cavity (806) is formed between the other side of the vertical partition plate and the inner wall of the bottom of the tank body (801), and a channel is formed between the end part of the vertical partition plate (802) and the inner wall of the bottom of the tank body (801).
7. The system for recycling and environmental treating viscose waste liquid according to claim 6, wherein: the coarse filter device (4) is a bag filter with the aperture of 10-15 mu m, and the fine filter device (5) is an ultrafilter with the aperture of 0.01-0.05 mu m.
8. The system for recycling and environmental treating viscose waste liquid according to claim 6, wherein: a reflux port (807) is arranged at the top of the tank body (801), the reflux port (807) is communicated with a reflux cavity (805), an overflow port (808) is arranged at the upper part of the reflux cavity (805), an upper transverse plate (803) is arranged below the overflow port (808), and a channel is formed between the end part of the upper transverse plate (803) and the vertical partition plate (802); the top of the tank body (801) is also provided with a feed inlet (809), the feed inlet (809) is communicated with the mixing cavity (806), the lower part of the mixing cavity (806) is provided with a discharge outlet (810), a lower transverse plate (804) is arranged below the discharge outlet (810), and a channel is formed between the end part of the lower transverse plate (804) and the vertical partition plate (802).
9. The system for recycling and environmental treating viscose waste liquid according to claim 6, wherein: the circulating tank (8) comprises at least two stages of salt circulating tanks (14), acid circulating tanks (15) and alkali circulating tanks (16), the bipolar membrane device (7) comprises at least two stages of membrane stack mechanisms, and the salt circulating tanks (14), the acid circulating tanks (15), the alkali circulating tanks (16) and the membrane stack mechanisms are arranged in series correspondingly;
The salt circulation tank (14) is connected with the resin tower (6), the discharge port of the salt circulation tank (14) is connected with the salt inlet of the membrane stack mechanism of the same level, the salt outlet of the membrane stack mechanism is connected with the reflux port of the salt circulation tank (14) of the same level, an independent circulation passage is formed between the salt circulation tank (14) and the membrane stack mechanism of the same level, the salt circulation tank (14) is connected with the salt storage tank (9), and the overflow port of the salt circulation tank (14) is connected with the feed port of the salt circulation tank (14) of the next level; the overflow port of the salt circulation tank (14) of the last stage is connected with an acid salt separation device (19), the acid outlet of the acid salt separation device (19) is directly connected with an acid station acid storage tank in the viscose fiber production process through a pipeline, and the salt outlet of the acid salt separation device (19) is directly connected with the transfer tank (2) through a pipeline;
the acid circulation tank (15) is connected with an overflow port of the next-stage acid circulation tank (15), a feed port of the acid circulation tank (15) is connected with a desalted water storage tank (12), a discharge port of the acid circulation tank (15) is connected with an acid inlet of a membrane stack mechanism of the same level, an acid outlet of the membrane stack mechanism is connected with a reflux port of the acid circulation tank (15) of the same level, an independent circulation passage is formed between the acid circulation tank (15) and the membrane stack mechanism of the same level, an overflow port of the acid circulation tank (15) is connected with a reverse osmosis device (20), a concentrated acid outlet of the reverse osmosis device (20) is directly connected with an acid storage tank of an acid station in viscose fiber production through a pipeline, and a permeate outlet of the reverse osmosis device (20) is directly connected with the acid circulation tank (15) through a pipeline;
The alkali circulation tank (16) is connected with an overflow port of the next-stage alkali circulation tank (16), a desalting water storage tank (12) is connected with a feed port of the alkali circulation tank (16), a discharge port of the alkali circulation tank (16) is connected with an alkali inlet of a membrane stack mechanism of the same level, an alkali outlet of the membrane stack mechanism is connected with a reflux port of the alkali circulation tank (16) of the same level, an independent circulation passage is formed between the alkali circulation tank (16) and the membrane stack mechanism of the same level, an overflow port of the alkali circulation tank (16) is connected with a nanofiltration device (21), a filtrate port of the nanofiltration device (21) is directly connected with a stock solution storage tank in viscose fiber production through a pipeline, and a concentrated liquid port of the nanofiltration device (21) is directly connected with a blending tank (3) through a pipeline.
CN201811310408.3A 2018-11-06 2018-11-06 Circulating environment-friendly treatment process and system for viscose waste liquid Active CN109133448B (en)

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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
CN110975405B (en) * 2019-12-20 2022-03-18 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
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
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
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

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