CN103341320A - Novel process for recycling acid and base from viscose sodium sulfate waste liquid by using a bipolar membrane electrodialysis method - Google Patents
Novel process for recycling acid and base from viscose sodium sulfate waste liquid by using a bipolar membrane electrodialysis method Download PDFInfo
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Abstract
The invention discloses a novel process for recycling acid and base from viscose sodium sulfate waste liquid by using a bipolar membrane electrodialysis method. The novel process is characterized by sequentially comprising the following steps of crystallizing, regulating pH, carrying out primary prefiltration, oxidizing reducing substances by utilizing O3, carrying out secondary prefiltration, removing organic matters by utilizing activated carbon, removing zinc ions by utilizing ion exchange resin, carrying out filtering and refined filtration by utilizing pp (polypropylene) micropores, and preparing and concentrating the acid and the base. According to the novel process, the recycling rates of the acid and the base in the viscose waste liquid are improved, the damage of a bipolar membrane caused by impurities of the waste liquid is reduced, the service life of the bipolar membrane is prolonged, and the smooth operation of bipolar membrane electrodialysis and subsequent processes can be guaranteed.
Description
Technical field
The present invention relates to the method that material is handled in a kind of Chemical Manufacture, more particularly, the present invention relates to viscose rayon sodium sulphate waste liquid through the new technology of bipolar membrane electrodialysis method recovery soda acid, belong to the viscose rayon production technical field.
Background technology
Viscose glue and acid coagulating bath effect are neutralized alkali in the viscose rayon forming process in chemical fibre industry, and sodium cellulose xanghate is decomposed and the regeneration cellulose hydrate, the cellulose sulfonate in this process in the viscose glue, free NaOH and the Na that generates because of side reaction
2CS
3, side reaction product such as polysulfide all can with coagulating bath in sulfuric acid reaction generate sodium sulphate.Comprise the acid bath operation that consumes sulfuric acid in the viscose rayon production, comprise that also the sheet steeping operation, alkali cellulose sulphonic acid ester dissolution process, the waste gas that consume NaOH absorb operation, concise operation and the sour water neutralisation treatment operation of compressing and washing.
In the coagulating bath the main effect of sodium sulphate be impel viscose stream to solidify and suppress sulfolysis from, the reproduction speed of cellulose sulfonate is delayed, improve the concentration of sodium sulphate in the coagulating bath, spinning operation is easier to, tow is difficult for broken end, and can reduce the degree of dissociation of sulfuric acid, make tow when leaving coagulating bath, still have certain residue esterification degree, but the sodium sulphate in the coagulating bath is also unsuitable too high, otherwise fiber is solidified overruns, can not form fine structure, and generate thick crystalline particle, the ectonexine of fiber is heterogeneity also.
In spinning process, sodium sulphate content in the coagulating bath constantly increases makes it can't satisfy the requirement of technology, if only by adding the raw material that is consumed in the coagulating bath to replenish its concentration recycling and will make the total amount of coagulating bath increase and can't store, can only be at regular time and quantity with the coagulating bath discharging, acid wherein, salt, metal ion etc. will cause that serious environmental pollutes, brings huge pressure and cause the huge waste of resource to sewage disposal.And sodium sulphate unnecessary in the acid bath is carried out high temperature crystallization, isolate sodium sulfate crystal, make the content of the sodium sulphate in the acid bath meet technological requirement, the acid that do not need to drain every day comes the balance acid bath, directly continue to use for spinning workshop by reinforced back, can reduce acid discharge, the output glauber salt, reduce environmental protection pressure, but make it can not produce economic benefit because impure many, the own added values of glauber salt that the sodium sulphate high temperature crystallization is produced in the coagulating bath are low, a large amount of solid salts can't be handled, and has still brought certain pressure to environmental protection.
Bipolar Membrane is a kind of novel ion-exchange composite membranes, and it is composited by cation exchange layer (N type film), interface hydrophilic layer (Catalytic Layer) and anion exchange layer (P type film) usually, is reaction film truly.Under the DC electric field effect, Bipolar Membrane can obtain hydrogen ion and hydroxide ion respectively in the film both sides with hydrolytic dissociation.Utilize this characteristics, the bipolar membrane electrodialysis system with Bipolar Membrane and other anion and cation exchange membranes are combined into can be converted into corresponding bronsted lowry acids and bases bronsted lowry with the salt in the aqueous solution under the situation of not introducing new component, and this technology is called the bipolar membrane electrodialysis technology.Compare outstanding technical advantage such as that the bipolar membrane electrodialysis technology has is energy-efficient, environmental friendliness, simple operation with traditional handicraft.In recent years, bipolar membrane electrodialysis technology technology has all obtained fast development in research and aspect using two, membrane preparation technology and operation parameter optimization are constantly obtained new progress, range of application from the albumen of the desalination of chemical field and soda acid preparation, biological field and amino acid purify the purifying that is extended to industrial wastewater the environmental protection field, concentrate, field such as high purity water preparation, renovating, developing in cleaner production and the recycling economy process and playing the part of the role who becomes more and more important in traditional chemical separating technology.
The research report of relevant Bipolar Membrane just occurred from 50 mid-nineties 90s of 20th century, its evolution can be divided into three phases: 50 initial stages age mid-nineties 90 to 80 of 20th century of phase I, this is that Bipolar Membrane develops period very slowly, Bipolar Membrane only is directly to be suppressed by two anion and cation exchange membranes, poor performance, the theoretical pressure drop of water decomposition voltage ratio is high tens times, and application study also is in the laboratory stage based on water decomposition; Second stage is from the 80's of 20th century first arrivals beginning of the nineties, because the monolithic type Bipolar Membrane has successfully been developed in the improvement of Bipolar Membrane technology of preparing, its performance improves greatly, obtained successful Application in relieving haperacidity alkali and desulfur technology, the commodity Bipolar Membrane has appearred in this stage.At the beginning of the 90's of 20th century so far, it is the period that Bipolar Membrane develops rapidly, along with the further investigation to Bipolar Membrane course of work mechanism, carried out significant improvement from membrane structure, membrane material and preparation process, the performance of Bipolar Membrane is greatly improved, it wherein mainly is the improvement to cavity block and anode membrane contact interface, " monolithic type " structure that begins to occur at the beginning of from initial simple " pressure stratotype " or " coating type " structure to the 80's of 20th century, the labyrinth of " Catalytic Layer " greatly reduces membrane voltage in the middle of occurring again subsequently having.
At present, the bipolar membrane electrodialysis technology has been brought into play original effect in optimizing traditional industry process and new industrial process.Its appearance has changed traditional industry and has separated and preparation process, for the technical barrier that solves in the fields such as environment, chemical industry, biology, marine chemical industry is brought new vigor and vitality into, provide effective means for solving problems such as environment that the mankind face, resource, the energy simultaneously.
It is CN102167293A that State Intellectual Property Office discloses a publication number in 2011.3.10, name is called the patent of invention of " a kind of method of using the bipolar membrane electrodialysis device to produce sulfuric acid and NaOH ", a kind of method of using the bipolar membrane electrodialysis device to produce sulfuric acid and NaOH is disclosed, this method is that metabisulfite solution is injected in the compartment of anion selective membrane and cation selective membrane formation, water is injected into Bipolar Membrane and anion selective membrane, in the compartment that cation selective membrane forms, under the effect of DC electric field power, in the compartment that compartment that cation selective membrane and Bipolar Membrane form towards the anion selection face of anode and/or cation selective membrane and negative electrode form, obtain NaOH, in the compartment of the compartment of the cation selective face formation of negative electrode and/or anion selective membrane and anode formation, obtain sulfuric acid in anion selective membrane and Bipolar Membrane.The method that the present invention adopts can re-use the sodium sulphate waste liquid, produces the sulfuric acid and the NaOH that can secondary utilize, and it is turned waste into wealth, and has remarkable economic efficiency and environmental benefit.
Though above-mentioned patent can accomplish to dispose waste liquid; make acid-alkali regeneration; environment has been played the certain protection effect; but still exist the soda acid rate of recovery not high; energy consumption is big, can't online recovery and recycling, and because the pre-treatment step before entering film device not; can cause runner obstruction, film resistance increase, regenerated acid alkali ability in the film device to reduce, and service life of equipment is short.
It is CN102107972A that State Intellectual Property Office discloses a publication number in 2010.12.1, name is called the patent of invention of " a kind of Bipolar Membrane is to hyperfiltration desalinization preprocess method ", disclose a kind of chemical treatment method, specifically referred to a kind of to the preceding preprocess method in the desalting process.The present invention puts into the Bipolar Membrane device to seawater, and Bipolar Membrane wherein is a divalence diffusion barrier; Utmost point liquid is sodium chloride or the metabisulfite solution of mass concentration 1-10%; Then the alkali lye in the Bipolar Membrane device alkali chamber is mixed with water inlet, the micro-filtrate membrane filtration of the water inlet after the above-mentioned alkalization with the 0.1-0.5 micron, and then regulate pH with the acid solution of bipolar acid chamber, and regulate the pH value to 8.2-8.8, namely can be used as desalinization and handle and use.Advantage of the present invention is that less investment, operating cost boron content low, easy to operate, that produce water meets drinking water standard, can carry out Bipolar Membrane desalinization product water hardening and tempering method and technology that heavy construction is used, solves the technical bottleneck of desalinization development.The present invention can be widely used in the desalinization occasion.The content of this patent disclosure is not suitable for the sodium sulphate liquid waste processing that produces in the viscose glue production process that contains complicated ingredient impurity.
Summary of the invention
The present invention is intended to solve the waste liquid that existing application produces and reclaims problem and the defective that the soda acid technology exists through the bipolar membrane electrodialysis method in viscose rayon strand forming process, provide viscose rayon sodium sulphate waste liquid to reclaim the new technology of soda acid through the bipolar membrane electrodialysis method, the technology of getting soda acid through the bipolar membrane electrodialysis legal system at the waste liquid that is applied to produce in the viscose rayon strand forming process only, adopt specific recovery method, pre-treatment step in the recovery method is handled the waste liquid that produces in the viscose rayon strand forming process, enter the bipolar membrane electrodialysis process again, improved the regeneration rate of recovery of bronsted lowry acids and bases bronsted lowry in the viscose rayon waste liquid, reduced the damage that waste liquid impurity causes Bipolar Membrane, improve the service life of Bipolar Membrane, and guarantee carrying out smoothly of bipolar membrane electrodialysis and subsequent handling.
In order to realize the foregoing invention purpose, concrete technical scheme of the present invention is as follows:
Viscose rayon sodium sulphate waste liquid reclaims the new technology of soda acid through the bipolar membrane electrodialysis method, it is characterized in that may further comprise the steps successively: crystallization, regulate pH, prefiltration, O
3Oxidation-reduction quality material, secondary prefiltration, active carbon are removed that organic matter, ion exchange resin are removed zinc ion, the smart filter of pp micro porous filtration, soda acid is produced and are concentrated;
Described crystallization by with in the viscose rayon strand forming process the generation sodium sulphate content be that the waste liquid of 200-400g/L generates sodium sulfate crystal by high temperature crystallization;
Described adjusting pH is for dissolving sodium sulfate crystal with demineralized water earlier, obtain the metabisulfite solution that concentration is 3%-15%, in metabisulfite solution, add sodium carbonate again, with pH value of solution value modulation 8-10, adding sodium carbonate can be with the maximized precipitation of the zinc ion in the metabisulfite solution, Separation of Solid and Liquid reclaims zinc and reduces zinc ion content in the metabisulfite solution;
Described through adding the metabisulfite solution of sodium carbonate depositing zinc ion, through a prefiltration, i.e. plate filter, remove the zinc ion sediment, allow comparatively pure metabisulfite solution enter in the bipolar membrane electrodialysis film group device, prolong the service life of equipment, improved yield and the quality of product;
Described through the metabisulfite solution behind prefiltration, adopt O
3Oxidizing process is removed the reducing substances of metabisulfite solution, allow comparatively pure metabisulfite solution enter in the bipolar membrane electrodialysis film group device, avoided bipolar membrane electrodialysis equipment under the situation of electrolysis, make film and reducing substances generation redox reaction and damage, prolong the service life of equipment, improved the quality of product;
Described through O
3Metabisulfite solution behind the oxidation removal reducing substances filters through the secondary flame filter press, can go out large granular impurity in the metabisulfite solution effectively, allow comparatively pure metabisulfite solution enter in the bipolar membrane electrodialysis film group device, prolong the service life of equipment, improved the quality of product;
Metabisulfite solution behind the described process secondary prefiltration passes through the active carbon device again, can effectively remove organic substance and some fine particles, avoid organic substance enrichment and influence the performance of film in the Bipolar Membrane equipment, prolonged the service life of equipment, improved yield and the quality of product;
Described through the process of the metabisulfite solution after charcoal treatment ion exchange resin system, the remaining zinc ion in the removal solution makes bivalent metal ion drop to minimum to the influence of bipolar membrane electrodialysis;
Described metabisulfite solution through the ion exchange resin system is filtered through the pp millipore filter is smart again, can obtain meeting the treatment fluid that enters bipolar membrane electrodialysis film group device index;
Described soda acid is produced to treatment fluid gets concentration through the bipolar membrane electrodialysis legal system and is controlled to be the sulfuric acid solution of 1-30g/l and the sodium hydroxide solution that concentration is controlled to be 5-80g/l;
Described simmer down to adopts hyperfiltration, electroosmose process, low-temperature multi-effect method and multiple-effect evaporation method to concentrate the sulfuric acid solution that concentration is controlled to be 1-30g/l successively; After concentrating, the sulfuric acid solution that concentration is controlled to be 80-320g/l is transported to and carries out sulfuric acid in the acid bath operation of viscose rayon production and add, and forms online sulfuric acid circulation recycling system; The sodium hydroxide solution that concentration is controlled to be 5-80g/l adopts hyperfiltration, electroosmose process, low-temperature multi-effect method, multiple-effect evaporation method and evaporation to concentrate successively; After concentrating, sheet steeping operation, alkali cellulose sulphonic acid ester dissolution process, the waste gas that the sodium hydroxide solution that concentration is controlled to be 1%-100% is transported to viscose rayon production absorbs operation, concise compressing and washing carried out NaOH in operation and the sour water neutralisation treatment operation and added, and forms online alkali circulation recycling system.Reduce the input amount of sulfuric acid and NaOH, thereby reduced the viscose rayon production cost.
The sodium hydroxide solution that described concentration is controlled to be 5-80g/l obtains the sodium hydroxide solution that concentration is controlled to be 1%-5% after hyperfiltration concentrates; After concentrating, electroosmose process obtains the sodium hydroxide solution that concentration is controlled to be 6%-15% again; After concentrating, the low-temperature multi-effect method obtains the sodium hydroxide solution that concentration is controlled to be 15%-30% again; After concentrating, the multiple-effect evaporation method obtains the sodium hydroxide solution that concentration is controlled to be 30%-50% again; After concentrating, evaporation obtains the sodium hydroxide solution that concentration is controlled to be 50%-100% again.
Ss concentration is less than 5mg/l in the described treatment fluid, and COD is less than 60mg/l, and zinc ion concentration is less than 5mg/l, and the temperature for the treatment of fluid is 5-35 ° of C.
In the described crystallisation step, crystallization temperature is 40-80 ℃, and crystallization time is 5-30min, obtains 92% sodium sulfate crystal.
Described active carbon is removed in the organic matter step, adopts corpuscular active carbon adsorption column.
In the smart filter of the described pp micro porous filtration step, the aperture of micropore filtering film is the 0.22-1 micron in the PP filter.
Flame filter press and PP filter are physical filtering, and flame filter press filters out a certain size large granular impurity and the suspension in the metabisulfite solution, and the PP filter filters out the material of the small radii in the metabisulfite solution.
The useful technique effect that the present invention brings:
1, the present invention solves the waste liquid that existing application produces and reclaims problem and the defective that the soda acid technology exists through the bipolar membrane electrodialysis method in viscose rayon strand forming process, adopt specific recovery method, pre-treatment step in the recovery method is handled the waste liquid that produces in the viscose rayon strand forming process, enter the bipolar membrane electrodialysis process again, improved acid in the viscose rayon waste liquid, the rate of recovery of alkali and hemicellulose, reduced the damage that waste liquid causes Bipolar Membrane, improve the service life of Bipolar Membrane, and guarantee carrying out smoothly of bipolar membrane electrodialysis and subsequent handling, improved the organic efficiency of soda acid.
2, the concentration of sodium hydroxide solution of the present invention is controlled to be 5-80g/l, and the concentration of sulfuric acid solution is controlled to be 1-30g/l; Can be well cooperate with follow-up enrichment process, realize online reclaim sulfuric acid and NaOH.
3, the present invention adopts sulfuric acid solution and sodium hydroxide solution is concentrated respectively, and after concentrating, the concentration of sulfuric acid solution is 80-320g/l, and the concentration of sodium hydroxide solution is 1%-100%; Sulfuric acid solution can be transported to and carry out sulfuric acid in the acid bath operation of viscose rayon production and add; The sheet steeping operation, alkali cellulose sulphonic acid ester dissolution process, waste gas that sodium hydroxide solution can be transported to viscose rayon production absorbs operation, concise compressing and washing carried out NaOH in operation and the sour water neutralisation treatment operation and added, can form the circulatory system, reduce the input amount of sulfuric acid and NaOH, thereby reduced the viscose rayon production cost.
4, the present invention adopts hyperfiltration, electroosmose process, low-temperature multi-effect method, multiple-effect evaporation method and evaporation that alkali is concentrated successively, reclaiming the alkali that alkali concn is controlled to be 1%-100%, effect is remarkable, saves cost, can directly reclaim, further improve the concentration that reclaims alkali; Be recovered to viscose glue production with carrying out adding of alkali in the alkali operation, reduce production costs; Can obtain alkali concn and be controlled to be 96%, 98% and 99% NaOH crystal direct marketing but also can concentrate by evaporation, to bring benefits.
The specific embodiment
Below enforcement of the present invention is specified:
Embodiment 1
Viscose rayon sodium sulphate waste liquid reclaims the new technology of soda acid through the bipolar membrane electrodialysis method, may further comprise the steps successively: crystallization, regulate pH, prefiltration, O
3Oxidation-reduction quality material, secondary prefiltration, active carbon are removed that organic matter, ion exchange resin are removed zinc ion, the smart filter of pp micro porous filtration, soda acid is produced and are concentrated;
Described crystallization by with in the viscose rayon strand forming process the generation sodium sulphate content be that the waste liquid of 200g/L generates sodium sulfate crystal by high temperature crystallization;
Described adjusting pH is for dissolving sodium sulfate crystal with demineralized water earlier, obtain concentration and be 3% metabisulfite solution, in metabisulfite solution, add sodium carbonate again, with pH value of solution value modulation 8, adding sodium carbonate can be easy to the maximized precipitation of the zinc ion in the metabisulfite solution to separate, and allows the metabisulfite solution of the few zinc ion of content enter in the bipolar membrane electrodialysis film group device, prolong the service life of equipment, improved yield and the quality of product;
Described through adding the metabisulfite solution of sodium carbonate depositing zinc ion, through a prefiltration, i.e. plate filter, remove the zinc ion sediment, allow comparatively pure metabisulfite solution enter in the bipolar membrane electrodialysis film group device, prolonged the service life of equipment, improved the quality of product;
Described through the metabisulfite solution behind prefiltration, adopt O
3Oxidizing process is removed the reducing substances of metabisulfite solution, allow comparatively pure metabisulfite solution enter in the bipolar membrane electrodialysis film group device, avoided bipolar membrane electrodialysis equipment under the situation of electrolysis, make the material redox of being reduced property of film and damage, prolong the service life of equipment, improved the quality of product;
Described through O
3Metabisulfite solution behind the oxidation removal reducing substances filters through the secondary flame filter press, can go out large granular impurity in the metabisulfite solution effectively, allow comparatively pure metabisulfite solution enter in the bipolar membrane electrodialysis film group device, prolong the service life of equipment, improved the quality of product;
Metabisulfite solution behind the described process secondary prefiltration passes through the active carbon device again, can effectively remove organic substance and some fine particles, avoid organic substance enrichment and influence the performance of film in the Bipolar Membrane equipment, prolonged the service life of equipment, improved yield and the quality of product;
Described through the process of the metabisulfite solution after charcoal treatment ion exchange resin system, the remaining zinc ion in the removal solution makes bivalent metal ion drop to minimum to the influence of bipolar membrane electrodialysis;
Described metabisulfite solution through the ion exchange resin system is filtered through the pp millipore filter is smart again, can obtain meeting the treatment fluid that enters bipolar membrane electrodialysis film group device index;
Described soda acid is produced to treatment fluid gets concentration through the bipolar membrane electrodialysis legal system and is controlled to be the sulfuric acid solution of 1g/l and the sodium hydroxide solution that concentration is controlled to be 5g/l;
Described simmer down to adopts hyperfiltration, electroosmose process, low-temperature multi-effect method and multiple-effect evaporation method to concentrate the sulfuric acid solution that concentration is controlled to be 1g/l successively, after concentrating, concentration is that the sulfuric acid solution of 80g/l is transported to and carries out sulfuric acid in the acid bath operation of viscose rayon production and add, and forms online sulfuric acid circulation recycling system; The sodium hydroxide solution that concentration is controlled to be 5g/l adopts hyperfiltration, electroosmose process, low-temperature multi-effect method, multiple-effect evaporation method and evaporation to concentrate successively, obtains concentration and be controlled to be 1% sodium hydroxide solution after hyperfiltration concentrates; After electroosmose process concentrates, obtain concentration again and be controlled to be 6% sodium hydroxide solution, after the low-temperature multi-effect method concentrates, obtain concentration again and be controlled to be 15% sodium hydroxide solution; After the multiple-effect evaporation method concentrates, obtain concentration again and be controlled to be 30% sodium hydroxide solution; After evaporation concentrates, obtain concentration again and be controlled to be 50% sodium hydroxide solution; Concentration is controlled to be carries out NaOH in the sheet steeping operation that 50% sodium hydroxide solution is transported to viscose rayon production and adds, and forms online alkali circulation recycling system.
Ss concentration is less than 5mg/l in the described treatment fluid, and COD is less than 60mg/l, and zinc ion concentration is less than 5mg/l, and the temperature for the treatment of fluid is 5-35 ° of C.
In the described crystallisation step, crystallization temperature is 40 ℃, and crystallization time is 30min, obtains 92% sodium sulfate crystal.
Described active carbon is removed in the organic matter step, adopts corpuscular active carbon adsorption column.
In the smart filter of the described pp micro porous filtration step, the aperture of micropore filtering film is 0.22 micron in the PP filter.
Flame filter press and PP filter are physical filtering, and flame filter press filters out a certain size large granular impurity and the suspension in the metabisulfite solution, and the PP filter filters out the material of the small radii in the metabisulfite solution.
A kind of bipolar membrane electrodialysis method that the present invention adopts the applicant to apply for simultaneously when using is handled the method for viscose rayon sodium sulphate waste liquid, is 5% viscose rayon sodium sulphate waste liquid with sodium sulfate concentration through crystallization, regulates pH, prefiltration, O
3Oxidation-reduction quality material, secondary prefiltration, active carbon are removed organic matter, ion exchange resin is removed zinc ion and the smart filter of pp micro porous filtration, enter then in the sodium sulphate runner of bipolar membrane electrodialysis film group device; Demineralized water as absorption liquid enters respectively in the sour runner and alkali runner of bipolar membrane electrodialysis film group device, makes sulfuric acid solution and sodium hydroxide solution; The work gauge pressure of described bipolar membrane electrodialysis film group device is 0.03MPa.
The basement membrane of described Bipolar Membrane is that alloy firm with polyethylene and ethene and octene copolymer elastomer and Oppanol tertiary blending is as basilar memebrane, immersion contains in the solution of styrene, divinylbenzene and benzoyl peroxide, the film that soaked liquid pressurizes again, and polymerization obtains under heating.
The thickness of described basement membrane is 0.05mm.
When concrete the use, select BPM2-2500-3 type bipolar membrane electrodialysis device for use, comprising: 120V*150A D.C. regulated power supply, 400*800 bipolar membrane electrodialysis film group device (comprising resistance sorrel, resistance alkali film and Bipolar Membrane), reverse osmosis concentration equipment, 400*800 acid concentrate the electrodialysis film group device, 400*800 alkali concentrates electrodialysis film group device, low-temperature multi-effect concentrator, multiple-effect evaporation concentrator, evaporation concentration equipment and heat pump; Adopt heat pump to processings of lowering the temperature of bipolar membrane electrodialysis film group device, heat pump can carry out recycling to low-temperature multi-effect concentrator or multiple-effect evaporation concentrator or evaporation concentration equipment with heat recovery.
The cleaning step of bipolar membrane electrodialysis film group device comprises: 1, the sodium sulphate loop exit place feeding demineralized water toward the bipolar membrane electrodialysis film group device carries out backwash to remove equipment runner and the less particle of Bipolar Membrane adhering on surface to the bipolar membrane electrodialysis film group device, till backwash is normal to operating pressure; 2, be that 25 degree, compound concentration are till 1% sodium hydroxide solution recovers to electric current Bipolar Membrane surface wash cycles with temperature.
Embodiment 2
Viscose rayon sodium sulphate waste liquid reclaims the new technology of soda acid through the bipolar membrane electrodialysis method, may further comprise the steps successively: crystallization, regulate pH, prefiltration, O
3Oxidation-reduction quality material, secondary prefiltration, active carbon are removed that organic matter, ion exchange resin are removed zinc ion, the smart filter of pp micro porous filtration, soda acid is produced and are concentrated;
Described crystallization by with in the viscose rayon strand forming process the generation sodium sulphate content be that the waste liquid of 300g/L generates sodium sulfate crystal by high temperature crystallization;
Described adjusting pH is for dissolving sodium sulfate crystal with demineralized water earlier, obtain concentration and be 7% metabisulfite solution, in metabisulfite solution, add sodium carbonate again, with pH value of solution value modulation 9, adding sodium carbonate can be easy to the maximized precipitation of the zinc ion in the metabisulfite solution to separate, and allows the metabisulfite solution of the few zinc ion of content enter in the bipolar membrane electrodialysis film group device, prolong the service life of equipment, improved yield and the quality of product;
Described through adding the metabisulfite solution of sodium carbonate depositing zinc ion, through a prefiltration, i.e. plate filter, remove the zinc ion sediment, allow comparatively pure metabisulfite solution enter in the bipolar membrane electrodialysis film group device, prolonged the service life of equipment, improved the quality of product;
Described through the metabisulfite solution behind prefiltration, adopt O
3Oxidizing process is removed the reducing substances of metabisulfite solution, allow comparatively pure metabisulfite solution enter in the bipolar membrane electrodialysis film group device, avoided bipolar membrane electrodialysis equipment under the situation of electrolysis, make the material redox of being reduced property of film and damage, prolong the service life of equipment, improved the quality of product;
Described through O
3Metabisulfite solution behind the oxidation removal reducing substances filters through the secondary flame filter press, can go out large granular impurity in the metabisulfite solution effectively, allow comparatively pure metabisulfite solution enter in the bipolar membrane electrodialysis film group device, prolong the service life of equipment, improved the quality of product;
Metabisulfite solution behind the described process secondary prefiltration passes through the active carbon device again, can effectively remove organic substance and some fine particles, avoid organic substance enrichment and influence the performance of film in the Bipolar Membrane equipment, prolonged the service life of equipment, improved yield and the quality of product;
Described through the process of the metabisulfite solution after charcoal treatment ion exchange resin system, the remaining zinc ion in the removal solution makes bivalent metal ion drop to minimum to the influence of bipolar membrane electrodialysis;
Described metabisulfite solution through the ion exchange resin system is filtered through the pp millipore filter is smart again, can obtain meeting the treatment fluid that enters bipolar membrane electrodialysis film group device index;
Described soda acid is produced to treatment fluid gets concentration through the bipolar membrane electrodialysis legal system and is controlled to be the sulfuric acid solution of 10g/l and the sodium hydroxide solution that concentration is controlled to be 10g/l;
Described simmer down to adopts hyperfiltration, electroosmose process, low-temperature multi-effect method and multiple-effect evaporation method to concentrate the sulfuric acid solution that concentration is controlled to be 10g/l successively, after concentrating, concentration is that the sulfuric acid solution of 100g/l is transported to and carries out sulfuric acid in the acid bath operation of viscose rayon production and add, and forms online sulfuric acid circulation recycling system; The sodium hydroxide solution that concentration is controlled to be 10g/l adopts hyperfiltration, electroosmose process, low-temperature multi-effect method, multiple-effect evaporation method and evaporation to concentrate successively, obtains concentration and be controlled to be 2% sodium hydroxide solution after hyperfiltration concentrates; After electroosmose process concentrates, obtain concentration again and be controlled to be 9% sodium hydroxide solution, after the low-temperature multi-effect method concentrates, obtain concentration again and be controlled to be 20% sodium hydroxide solution; After the multiple-effect evaporation method concentrates, obtain concentration again and be controlled to be 35% sodium hydroxide solution; After evaporation concentrates, obtain concentration again and be controlled to be 55% sodium hydroxide solution; Concentration is controlled to be carries out NaOH in the alkali cellulose sulphonic acid ester dissolution process that 55% sodium hydroxide solution is transported to viscose rayon production and adds, and forms online alkali circulation recycling system.
Ss concentration is less than 5mg/l in the described treatment fluid, and COD is less than 60mg/l, and zinc ion concentration is less than 5mg/l, and the temperature for the treatment of fluid is 20 ° of C.
In the described crystallisation step, crystallization temperature is 60 ℃, and crystallization time is 15min, obtains 92% sodium sulfate crystal.
Described active carbon is removed in the organic matter step, adopts corpuscular active carbon adsorption column.
In the smart filter of the described pp micro porous filtration step, the aperture of micropore filtering film is 0.22 micron in the PP filter.
Flame filter press and PP filter are physical filtering, and flame filter press filters out a certain size large granular impurity and the suspension in the metabisulfite solution, and the PP filter filters out the material of the small radii in the metabisulfite solution.
A kind of bipolar membrane electrodialysis method that the present invention adopts the applicant to apply for simultaneously when using is handled the method for viscose rayon sodium sulphate waste liquid, is 10% viscose rayon sodium sulphate waste liquid with sodium sulfate concentration through crystallization, regulates pH, prefiltration, O
3Oxidation-reduction quality material, secondary prefiltration, active carbon are removed organic matter, ion exchange resin is removed zinc ion and the smart filter of pp micro porous filtration, enter then in the sodium sulphate runner of bipolar membrane electrodialysis film group device; Demineralized water as absorption liquid enters respectively in the sour runner and alkali runner of bipolar membrane electrodialysis film group device, makes sulfuric acid solution and sodium hydroxide solution; The work gauge pressure of described bipolar membrane electrodialysis film group device is 0.04MPa.
The basement membrane of described Bipolar Membrane is that alloy firm with polyethylene and ethene and octene copolymer elastomer and Oppanol tertiary blending is as basilar memebrane, immersion contains in the solution of styrene, divinylbenzene and benzoyl peroxide, the film that soaked liquid pressurizes again, and polymerization obtains under heating.
The thickness of described basement membrane is 0.05mm.
When concrete the use, select BPM2-2500-3 type bipolar membrane electrodialysis device for use, comprising: 120V*150A D.C. regulated power supply, 400*800 bipolar membrane electrodialysis film group device (comprising resistance sorrel, resistance alkali film and Bipolar Membrane), reverse osmosis concentration equipment, 400*800 acid concentrate the electrodialysis film group device, 400*800 alkali concentrates electrodialysis film group device, low-temperature multi-effect concentrator, multiple-effect evaporation concentrator, evaporation concentration equipment and heat pump; Adopt heat pump to processings of lowering the temperature of bipolar membrane electrodialysis film group device, heat pump can carry out recycling to low-temperature multi-effect concentrator or multiple-effect evaporation concentrator or evaporation concentration equipment with heat recovery.
The cleaning step of bipolar membrane electrodialysis film group device comprises: 1, the sodium sulphate loop exit place feeding demineralized water toward the bipolar membrane electrodialysis film group device carries out backwash to remove equipment runner and the less particle of Bipolar Membrane adhering on surface to the bipolar membrane electrodialysis film group device, till backwash is normal to operating pressure; 2, be that 28 degree, compound concentration are till 2% sodium hydroxide solution recovers to electric current Bipolar Membrane surface wash cycles with temperature.
Embodiment 3
Viscose rayon sodium sulphate waste liquid reclaims the new technology of soda acid through the bipolar membrane electrodialysis method, may further comprise the steps successively: crystallization, regulate pH, prefiltration, O
3Oxidation-reduction quality material, secondary prefiltration, active carbon are removed that organic matter, ion exchange resin are removed zinc ion, the smart filter of pp micro porous filtration, soda acid is produced and are concentrated;
Described crystallization by with in the viscose rayon strand forming process the generation sodium sulphate content be that the waste liquid of 300g/L generates sodium sulfate crystal by high temperature crystallization;
Described adjusting pH is for dissolving sodium sulfate crystal with demineralized water earlier, obtain concentration and be 12% metabisulfite solution, in metabisulfite solution, add sodium carbonate again, with pH value of solution value modulation 9, adding sodium carbonate can be easy to the maximized precipitation of the zinc ion in the metabisulfite solution to separate, and allows the metabisulfite solution of the few zinc ion of content enter in the bipolar membrane electrodialysis film group device, prolong the service life of equipment, improved yield and the quality of product;
Described through adding the metabisulfite solution of sodium carbonate depositing zinc ion, through a prefiltration, i.e. plate filter, remove the zinc ion sediment, allow comparatively pure metabisulfite solution enter in the bipolar membrane electrodialysis film group device, prolonged the service life of equipment, improved the quality of product;
Described through the metabisulfite solution behind prefiltration, adopt O
3Oxidizing process is removed the reducing substances of metabisulfite solution, allow comparatively pure metabisulfite solution enter in the bipolar membrane electrodialysis film group device, avoided bipolar membrane electrodialysis equipment under the situation of electrolysis, make the material redox of being reduced property of film and damage, prolong the service life of equipment, improved the quality of product;
Described through O
3Metabisulfite solution behind the oxidation removal reducing substances filters through the secondary flame filter press, can go out large granular impurity in the metabisulfite solution effectively, allow comparatively pure metabisulfite solution enter in the bipolar membrane electrodialysis film group device, prolong the service life of equipment, improved the quality of product;
Metabisulfite solution behind the described process secondary prefiltration passes through the active carbon device again, can effectively remove organic substance and some fine particles, avoid organic substance enrichment and influence the performance of film in the Bipolar Membrane equipment, prolonged the service life of equipment, improved yield and the quality of product;
Described through the process of the metabisulfite solution after charcoal treatment ion exchange resin system, the remaining zinc ion in the removal solution makes bivalent metal ion drop to minimum to the influence of bipolar membrane electrodialysis;
Described metabisulfite solution through the ion exchange resin system is filtered through the pp millipore filter is smart again, can obtain meeting the treatment fluid that enters bipolar membrane electrodialysis film group device index;
Described soda acid is produced treatment fluid and is got concentration through the bipolar membrane electrodialysis legal system and be controlled to be the sulfuric acid solution of 15g/l and the sodium hydroxide solution that concentration is controlled to be 15g/l;
Described simmer down to adopts hyperfiltration, electroosmose process and low-temperature multi-effect method and multiple-effect evaporation method to concentrate the sulfuric acid solution that concentration is controlled to be 15g/l successively, after concentrating, concentration is that the sulfuric acid solution of 120g/l is transported to and carries out sulfuric acid in the acid bath operation of viscose rayon production and add, and forms online sulfuric acid circulation recycling system; The sodium hydroxide solution that concentration is controlled to be 15g/l adopts hyperfiltration, electroosmose process, low-temperature multi-effect method, multiple-effect evaporation method and evaporation to concentrate successively, obtains concentration and be controlled to be 4% sodium hydroxide solution after hyperfiltration concentrates; After electroosmose process concentrates, obtain concentration again and be controlled to be 13% sodium hydroxide solution, after the low-temperature multi-effect method concentrates, obtain concentration again and be controlled to be 25% sodium hydroxide solution; After the multiple-effect evaporation method concentrates, obtain concentration again and be controlled to be 40% sodium hydroxide solution; After evaporation concentrates, obtain concentration again and be controlled to be 60% sodium hydroxide solution; Concentration is controlled to be waste gas that 60% sodium hydroxide solution is transported to viscose rayon production and absorbs and carry out NaOH in the operation and add, and forms online alkali circulation recycling system.
Ss concentration is less than 5mg/l in the described treatment fluid, and COD is less than 60mg/l, and zinc ion concentration is less than 5mg/l, and the temperature for the treatment of fluid is 20 ° of C.
In the described crystallisation step, crystallization temperature is 60 ℃, and crystallization time is 15min, obtains 92% sodium sulfate crystal.
Described active carbon is removed in the organic matter step, adopts corpuscular active carbon adsorption column.
In the smart filter of the described pp micro porous filtration step, the aperture of micropore filtering film is 0.22 micron in the PP filter.
Flame filter press and PP filter are physical filtering, and flame filter press filters out a certain size large granular impurity and the suspension in the metabisulfite solution, and the PP filter filters out the material of the small radii in the metabisulfite solution.
A kind of bipolar membrane electrodialysis method that the present invention adopts the applicant to apply for simultaneously when using is handled the method for viscose rayon sodium sulphate waste liquid, is 15% viscose rayon sodium sulphate waste liquid with sodium sulfate concentration through crystallization, regulates pH, prefiltration, O
3Oxidation-reduction quality material, secondary prefiltration, active carbon are removed organic matter, ion exchange resin is removed zinc ion and the smart filter of pp micro porous filtration, enter then in the sodium sulphate runner of bipolar membrane electrodialysis film group device; Demineralized water as absorption liquid enters respectively in the sour runner and alkali runner of bipolar membrane electrodialysis film group device, makes sulfuric acid solution and sodium hydroxide solution; The work gauge pressure of described bipolar membrane electrodialysis film group device is 0.06MPa.
The basement membrane of described Bipolar Membrane is that alloy firm with polyethylene and ethene and octene copolymer elastomer and Oppanol tertiary blending is as basilar memebrane, immersion contains in the solution of styrene, divinylbenzene and benzoyl peroxide, the film that soaked liquid pressurizes again, and polymerization obtains under heating.
The thickness of described basement membrane is 0.05mm.
When concrete the use, select BPM2-2500-3 type bipolar membrane electrodialysis device for use, comprising: 120V*150A D.C. regulated power supply, 400*800 bipolar membrane electrodialysis film group device (comprising resistance sorrel, resistance alkali film and Bipolar Membrane), reverse osmosis concentration equipment, 400*800 acid concentrate the electrodialysis film group device, 400*800 alkali concentrates electrodialysis film group device, low-temperature multi-effect concentrator, multiple-effect evaporation concentrator, evaporation concentration equipment and heat pump; Adopt heat pump to processings of lowering the temperature of bipolar membrane electrodialysis film group device, heat pump can carry out recycling to low-temperature multi-effect concentrator or multiple-effect evaporation concentrator or evaporation concentration equipment with heat recovery.
The cleaning step of bipolar membrane electrodialysis film group device comprises: 1, the sodium sulphate loop exit place feeding demineralized water toward the bipolar membrane electrodialysis film group device carries out backwash to remove equipment runner and the less particle of Bipolar Membrane adhering on surface to the bipolar membrane electrodialysis film group device, till backwash is normal to operating pressure; 2, be that 30 degree, compound concentration are till 3% sodium hydroxide solution recovers to electric current Bipolar Membrane surface wash cycles with temperature.
Embodiment 4
Viscose rayon sodium sulphate waste liquid reclaims the new technology of soda acid through the bipolar membrane electrodialysis method, may further comprise the steps successively: crystallization, regulate pH, prefiltration, O
3Oxidation-reduction quality material, secondary prefiltration, active carbon are removed that organic matter, ion exchange resin are removed zinc ion, the smart filter of pp micro porous filtration, soda acid is produced and are concentrated;
Described crystallization by with in the viscose rayon strand forming process the generation sodium sulphate content be that the waste liquid of 400g/L generates sodium sulfate crystal by high temperature crystallization;
Described adjusting pH is for dissolving sodium sulfate crystal with demineralized water earlier, obtain concentration and be 15% metabisulfite solution, in metabisulfite solution, add sodium carbonate again, with pH value of solution value modulation 10, adding sodium carbonate can be easy to the maximized precipitation of the zinc ion in the metabisulfite solution to separate, and allows the metabisulfite solution of the few zinc ion of content enter in the bipolar membrane electrodialysis film group device, prolong the service life of equipment, improved yield and the quality of product;
Described through adding the metabisulfite solution of sodium carbonate depositing zinc ion, through a prefiltration, i.e. plate filter, remove the zinc ion sediment, allow comparatively pure metabisulfite solution enter in the bipolar membrane electrodialysis film group device, prolonged the service life of equipment, improved the quality of product;
Described through the metabisulfite solution behind prefiltration, adopt O
3Oxidizing process is removed the reducing substances of metabisulfite solution, allow comparatively pure metabisulfite solution enter in the bipolar membrane electrodialysis film group device, avoided bipolar membrane electrodialysis equipment under the situation of electrolysis, make the material redox of being reduced property of film and damage, prolong the service life of equipment, improved the quality of product;
Described through O
3Metabisulfite solution behind the oxidation removal reducing substances filters through the secondary flame filter press, can go out large granular impurity in the metabisulfite solution effectively, allow comparatively pure metabisulfite solution enter in the bipolar membrane electrodialysis film group device, prolong the service life of equipment, improved the quality of product;
Metabisulfite solution behind the described process secondary prefiltration passes through the active carbon device again, can effectively remove organic substance and some fine particles, avoid organic substance enrichment and influence the performance of film in the Bipolar Membrane equipment, prolonged the service life of equipment, improved yield and the quality of product;
Described through the process of the metabisulfite solution after charcoal treatment ion exchange resin system, the remaining zinc ion in the removal solution makes bivalent metal ion drop to minimum to the influence of bipolar membrane electrodialysis;
Described metabisulfite solution through the ion exchange resin system is filtered through the pp millipore filter is smart again, can obtain meeting the treatment fluid that enters bipolar membrane electrodialysis film group device index;
Described soda acid is produced to treatment fluid gets concentration through the bipolar membrane electrodialysis legal system and is controlled to be the sulfuric acid solution of 30g/l and the sodium hydroxide solution that concentration is controlled to be 80g/l;
Described simmer down to adopts hyperfiltration, electroosmose process and low-temperature multi-effect method and multiple-effect evaporation method to concentrate the sulfuric acid solution that concentration is controlled to be 30g/l successively, after concentrating, concentration is that the sulfuric acid solution of 320g/l is transported to and carries out sulfuric acid in the acid bath operation of viscose rayon production and add, and forms online sulfuric acid circulation recycling system; The sodium hydroxide solution that concentration is controlled to be 80g/l adopts hyperfiltration, electroosmose process, low-temperature multi-effect method, multiple-effect evaporation method and evaporation to concentrate successively, obtains concentration and be controlled to be 5% sodium hydroxide solution after hyperfiltration concentrates; After electroosmose process concentrates, obtain concentration again and be controlled to be 15% sodium hydroxide solution, after the low-temperature multi-effect method concentrates, obtain concentration again and be controlled to be 30% sodium hydroxide solution; After the multiple-effect evaporation method concentrates, obtain concentration again and be controlled to be 99% NaOH crystal; Concentration is controlled to be 99% NaOH crystal and is transported to concise the compressing and washing of the pulp of viscose rayon production and carries out NaOH in the operation and add, and form online alkali circulation recycling system, but also direct marketing brings benefits.
Ss concentration is less than 5mg/l in the described treatment fluid, and COD is less than 60mg/l, and zinc ion concentration is less than 5mg/l, and the temperature for the treatment of fluid is 35 ° of C.
In the described crystallisation step, crystallization temperature is 80 ℃, and crystallization time is 5min, obtains 92% sodium sulfate crystal.
Described active carbon is removed in the organic matter step, adopts corpuscular active carbon adsorption column.
In the smart filter of the described pp micro porous filtration step, the aperture of micropore filtering film is 0.22 micron in the PP filter.
Flame filter press and PP filter are physical filtering, and flame filter press filters out a certain size large granular impurity and the suspension in the metabisulfite solution, and the PP filter filters out the material of the small radii in the metabisulfite solution.
A kind of bipolar membrane electrodialysis method that the present invention adopts the applicant to apply for simultaneously when using is handled the method for viscose rayon sodium sulphate waste liquid, is 20% viscose rayon sodium sulphate waste liquid with sodium sulfate concentration through crystallization, regulates pH, prefiltration, O
3Oxidation-reduction quality material, secondary prefiltration, active carbon are removed organic matter, ion exchange resin is removed zinc ion and the smart filter of pp micro porous filtration, enter then in the sodium sulphate runner of bipolar membrane electrodialysis film group device; Demineralized water as absorption liquid enters respectively in the sour runner and alkali runner of bipolar membrane electrodialysis film group device, makes sulfuric acid solution and sodium hydroxide solution; The work gauge pressure of described bipolar membrane electrodialysis film group device is 0.08MPa.
The basement membrane of described Bipolar Membrane is that alloy firm with polyethylene and ethene and octene copolymer elastomer and Oppanol tertiary blending is as basilar memebrane, immersion contains in the solution of styrene, divinylbenzene and benzoyl peroxide, the film that soaked liquid pressurizes again, and polymerization obtains under heating.
The thickness of described basement membrane is 0.05mm.
When concrete the use, select BPM2-2500-3 type bipolar membrane electrodialysis device for use, comprising: 120V*150A D.C. regulated power supply, 400*800 bipolar membrane electrodialysis film group device (comprising resistance sorrel, resistance alkali film and Bipolar Membrane), reverse osmosis concentration equipment, 400*800 acid concentrate the electrodialysis film group device, 400*800 alkali concentrates electrodialysis film group device, low-temperature multi-effect concentrator, multiple-effect evaporation concentrator, evaporation concentration equipment and heat pump; Adopt heat pump to processings of lowering the temperature of bipolar membrane electrodialysis film group device, heat pump can carry out recycling to low-temperature multi-effect concentrator or multiple-effect evaporation concentrator or evaporation concentration equipment with heat recovery.
The cleaning step of bipolar membrane electrodialysis film group device comprises: 1, the sodium sulphate loop exit place feeding demineralized water toward the bipolar membrane electrodialysis film group device carries out backwash to remove equipment runner and the less particle of Bipolar Membrane adhering on surface to the bipolar membrane electrodialysis film group device, till backwash is normal to operating pressure; 2, be that 35 degree, compound concentration are till 5% sodium hydroxide solution recovers to electric current Bipolar Membrane surface wash cycles with temperature.
Embodiment 5
But the present invention can concentrate out alkali concn and be controlled to be 96%, 98% and 99% NaOH crystal direct marketing, brings benefits.
Claims (7)
1. viscose rayon sodium sulphate waste liquid reclaims the new technology of soda acid through the bipolar membrane electrodialysis method, it is characterized in that may further comprise the steps successively: crystallization, regulate pH, prefiltration, O
3Oxidation-reduction quality material, secondary prefiltration, active carbon are removed that organic matter, ion exchange resin are removed zinc ion, the smart filter of pp micro porous filtration, soda acid is produced and are concentrated;
Described crystallization by with in the viscose rayon strand forming process the generation sodium sulphate content be that the waste liquid of 200-400g/L generates sodium sulfate crystal by high temperature crystallization;
Described adjusting pH obtains the metabisulfite solution that concentration is 3%-15% for dissolving sodium sulfate crystal with demineralized water earlier, adds sodium carbonate again in metabisulfite solution, with pH value of solution value modulation 8-10;
Described through adding the metabisulfite solution of sodium carbonate depositing zinc ion, through a prefiltration, namely a plate filter is removed the zinc ion sediment;
Described through the metabisulfite solution behind prefiltration, adopt O
3Oxidizing process is removed the reducing substances of metabisulfite solution;
Described through O
3Metabisulfite solution behind the oxidation removal reducing substances filters through the secondary flame filter press, removes the large granular impurity in the metabisulfite solution;
Metabisulfite solution behind the described process secondary prefiltration passes through the active carbon device again, can effectively remove organic substance and some fine particles;
Described through the process of the metabisulfite solution after charcoal treatment ion exchange resin system, remove the remaining zinc ion in the solution;
Described metabisulfite solution through the ion exchange resin system is filtered through the pp millipore filter is smart again, can obtain meeting the treatment fluid that enters bipolar membrane electrodialysis film group device index;
Described soda acid is produced to treatment fluid gets concentration through the bipolar membrane electrodialysis legal system and is controlled to be the sulfuric acid solution of 1-30g/l and the sodium hydroxide solution that concentration is controlled to be 5-80g/l;
Described simmer down to adopts hyperfiltration, electroosmose process, low-temperature multi-effect method and multiple-effect evaporation method to concentrate the sulfuric acid solution that concentration is controlled to be 1-30g/l successively; After concentrating, obtain the sulfuric acid solution that concentration is controlled to be 80-320g/l; The sodium hydroxide solution that concentration is controlled to be 5-80g/l adopts hyperfiltration, electroosmose process, low-temperature multi-effect method, multiple-effect evaporation method and evaporation to concentrate successively; After concentrating, obtain the sodium hydroxide solution that concentration is controlled to be 1%-100%.
2. according to the new technology of the described viscose rayon sodium sulphate of claim 1 waste liquid through bipolar membrane electrodialysis method recovery soda acid, it is characterized in that: the sodium hydroxide solution that described concentration is controlled to be 5-80g/l obtains the sodium hydroxide solution that concentration is controlled to be 1%-5% after hyperfiltration concentrates; After concentrating, electroosmose process obtains the sodium hydroxide solution that concentration is controlled to be 6%-15% again; After concentrating, the low-temperature multi-effect method obtains the sodium hydroxide solution that concentration is controlled to be 15%-30% again; After concentrating, the multiple-effect evaporation method obtains the sodium hydroxide solution that concentration is controlled to be 30%-50% again; After concentrating, evaporation obtains the sodium hydroxide solution that concentration is controlled to be 50%-100% again.
3. reclaim the new technology of soda acid through the bipolar membrane electrodialysis method according to the described viscose rayon sodium sulphate of claim 1 waste liquid, it is characterized in that: ss concentration is less than 5mg/l in the described treatment fluid, COD is less than 60mg/l, and zinc ion concentration is less than 5mg/l, and the temperature for the treatment of fluid is 5-35 ° of C.
4. according to the new technology of the described viscose rayon sodium sulphate of claim 1 waste liquid through bipolar membrane electrodialysis method recovery soda acid, it is characterized in that: in the described crystallisation step, crystallization temperature is 40-80 ℃, and crystallization time is 5-30min, obtains 92% sodium sulfate crystal.
5. according to the new technology of the described viscose rayon sodium sulphate of claim 1 waste liquid through bipolar membrane electrodialysis method recovery soda acid, it is characterized in that: described active carbon is removed in the organic matter step, adopts corpuscular active carbon adsorption column.
6. according to the new technology of the described viscose rayon sodium sulphate of claim 1 waste liquid through bipolar membrane electrodialysis method recovery soda acid, it is characterized in that: in the smart filter of the described pp micro porous filtration step, the aperture of micropore filtering film is the 0.22-1 micron in the PP filter.
7. reclaim the new technology of soda acid through the bipolar membrane electrodialysis method according to the described viscose rayon sodium sulphate of claim 1 waste liquid, it is characterized in that: flame filter press and PP filter are physical filtering, flame filter press filters out a certain size large granular impurity and the suspension in the metabisulfite solution, and the PP filter filters out the material of the small radii in the metabisulfite solution.
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| CN103787523A (en) * | 2014-01-17 | 2014-05-14 | 四川顺应金属材料科技有限公司 | Process for processing hydrometallurgy wastewater through bipolar membrane |
| CN105833698A (en) * | 2015-01-15 | 2016-08-10 | 北京中天元环境工程有限责任公司 | Method for production of concentrated sulfuric acid from sulfur-containing flue gas |
| CN106007110A (en) * | 2016-06-17 | 2016-10-12 | 浙江奇彩环境科技股份有限公司 | Low-salt wastewater recycled treatment and recycling method |
| CN106865832A (en) * | 2015-12-10 | 2017-06-20 | 宜宾丝丽雅集团有限公司 | A kind of Bipolar Membrane alkali recovery process in viscose rayon production |
| CN107215996A (en) * | 2017-07-19 | 2017-09-29 | 北京中科康仑环境科技研究院有限公司 | A kind of recycling treatment system, processing method and the application of high concentration sodium salt waste water |
| CN108026553A (en) * | 2015-09-11 | 2018-05-11 | 科莱恩国际有限公司 | For producing the self-centered method of the biomass hydrolysate with the salt content reduced |
| CN112408431A (en) * | 2020-11-25 | 2021-02-26 | 赛得利(九江)纤维有限公司 | Method for preparing anhydrous sodium sulphate by acid bath evaporation of viscose |
| CN115259103A (en) * | 2022-08-17 | 2022-11-01 | 四川省银河化学股份有限公司 | Process for preparing acid-base from chromium-containing sodium sulfate solution |
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| CN103787523A (en) * | 2014-01-17 | 2014-05-14 | 四川顺应金属材料科技有限公司 | Process for processing hydrometallurgy wastewater through bipolar membrane |
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| CN108026553A (en) * | 2015-09-11 | 2018-05-11 | 科莱恩国际有限公司 | For producing the self-centered method of the biomass hydrolysate with the salt content reduced |
| CN106865832A (en) * | 2015-12-10 | 2017-06-20 | 宜宾丝丽雅集团有限公司 | A kind of Bipolar Membrane alkali recovery process in viscose rayon production |
| CN106007110A (en) * | 2016-06-17 | 2016-10-12 | 浙江奇彩环境科技股份有限公司 | Low-salt wastewater recycled treatment and recycling method |
| CN107215996A (en) * | 2017-07-19 | 2017-09-29 | 北京中科康仑环境科技研究院有限公司 | A kind of recycling treatment system, processing method and the application of high concentration sodium salt waste water |
| CN112408431A (en) * | 2020-11-25 | 2021-02-26 | 赛得利(九江)纤维有限公司 | Method for preparing anhydrous sodium sulphate by acid bath evaporation of viscose |
| CN112408431B (en) * | 2020-11-25 | 2023-01-17 | 赛得利(九江)纤维有限公司 | Method for preparing anhydrous sodium sulphate by acid bath evaporation of viscose |
| CN115259103A (en) * | 2022-08-17 | 2022-11-01 | 四川省银河化学股份有限公司 | Process for preparing acid-base from chromium-containing sodium sulfate solution |
| CN115259103B (en) * | 2022-08-17 | 2023-11-10 | 四川省银河化学股份有限公司 | Acid-base preparation process for chromium-containing sodium sulfate solution |
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