CN103343403B - Viscose sodium sulfate waste liquor acid and alkali recycling technology by virtue of bipolar membrane electrodialysis method - Google Patents
Viscose sodium sulfate waste liquor acid and alkali recycling technology by virtue of bipolar membrane electrodialysis method Download PDFInfo
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Abstract
The invention discloses a viscose sodium sulfate waste liquor acid and alkali recycling technology by virtue of a bipolar membrane electrodialysis method. The technology is characterized by sequentially comprising the following steps of: crystallizing, pH regulating, first primary filtering, oxidizing reducing substances with O3, secondary primary filtering, removing organic matters with activated carbon, removing zinc ions with ion exchange resin, refined filtering by a propene polymer (pp) millipore filter, and acid and alkali producing and concentrating. By virtue of the technology, the regenerating and recycling rates of acid and alkali in viscose sodium sulfate waste liquor are improved, the damage of waste liquor impurities to a bipolar membrane is alleviated, the service life of the bipolar membrane is prolonged, and the bipolar membrane electrodialysis and subsequent processes can be successfully carried out.
Description
Technical field
The present invention relates to the method for material process in a kind of Chemical Manufacture, more particularly, the present invention relates to a kind of viscose sodium sulfate waste liquor reclaims soda acid technique through bipolar membrane electrodialysis method, belong to technical field of viscose production.
Background technology
Viscose glue and acid coagulating bath effect in viscose forming process in chemical fibre industry, alkali is neutralized, and sodium cellulose xanghate is decomposed and regeneration cellulose hydrate, the cellulose sulfonate in this process in viscose glue, free NaOH and the Na because of side reaction generation
2cS
3, the side reaction product such as polysulfide all can generate sodium sulphate with the sulfuric acid reaction in coagulating bath.Viscose is produced to comprise and is consumed the acid bath operation of sulfuric acid, also comprise consume NaOH sheet steeping operation, alkali cellulose sulphonic acid ester dissolution process, waste gas absorption operation, concisely compress and wash operation and sour water neutralisation treatment operation.
In coagulating bath the Main Function 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 coagulating bath, spinning operation is easier to, tow not easily breaks end, and the degree of dissociation of sulfuric acid can be reduced, tow is made still to have certain residual ester value when leaving coagulating bath, but the sodium sulphate in coagulating bath is also unsuitable too high, otherwise fibre solidification can be made to overrun, can not fine structure be formed, and generate thick crystalline particle, the ectonexine also heterogeneity of fiber.
In spinning process, sodium sulphate content in coagulating bath constantly increases the requirement making it cannot meet technique, if only cannot store by adding the raw material be consumed in coagulating bath the total amount of coagulating bath will be made to increase with its concentration recycling supplementary, can only coagulating bath be discharged at regular time and quantity, acid wherein, salt, metal ion etc. will cause serious environmental pollution, bring huge pressure and cause the huge waste of resource to sewage disposal.And sodium sulphate unnecessary in acid bath is carried out high temperature crystallization, isolate sodium sulfate crystal, the content of the sodium sulphate in acid bath is made to meet technological requirement, do not need to drain acid every day to balance acid bath, directly continue for spinning workshop after reinforced, acid discharge can be reduced, output glauber salt, reduce environmental protection pressure, but impure many, the own added values of glauber salt produced due to sodium sulphate high temperature crystallization in coagulating bath are low makes it not produce economic benefit, a large amount of solid salts cannot process, and still brings certain pressure to environmental protection.
Bipolar Membrane is a kind of novel ion-exchange composite membranes, 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 DC electric field effect, Bipolar Membrane by hydrolytic dissociation, can obtain hydrogen ion and hydroxide ion in film both sides respectively.Utilize this feature, by the bipolar membrane electrodialysis system that Bipolar Membrane and other anion and cation exchange membranes are combined into, when not introducing new component, the salt in the aqueous solution can be converted into corresponding bronsted lowry acids and bases bronsted lowry, this technology is called bipolar membrane electrodialysis technology.Compared with traditional handicraft, bipolar membrane electrodialysis technology has the outstanding technical advantages such as energy-efficient, environmental friendliness, simple operation.In recent years, bipolar membrane electrodialysis technology technology all obtains fast development in Study and appliance two, membrane preparation technology and operation parameter optimization constantly obtain new progress, range of application is purified from the albumen of the desalination of chemical field and soda acid preparation, biological field and amino acid the fields such as the purifying being extended to industrial wastewater field of Environment Protection, concentrated, preparation of high-purity water, the renovating of traditional work point separating process, develops in cleaner production and recycling economy process and plays the role become more and more important.
About the research report of Bipolar Membrane just occurred from mid-nineties 90 in 20th century 50, its evolution can be divided into three phases: initial stage age mid-nineties 90 to 80 20th century 50 first stage, this is Bipolar Membrane development period very slowly, Bipolar Membrane is only by two panels anion and cation exchange membrane direct pressing, poor performance, the theoretical pressure drop of water decomposition voltage ratio is high tens times, and application study is also in the laboratory stage based on water decomposition; Second stage is from the 80's of 20th century first arrivals beginning of the nineties, due to the improvement of Bipolar Membrane technology of preparing, successfully have developed monolithic type Bipolar Membrane, its performance improves greatly, in relieving haperacidity alkali and desulfur technology, obtaining successful Application, there is commodity Bipolar Membrane in this one-phase.From 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, significant improvement has been carried out from membrane structure, membrane material and preparation process, the performance of Bipolar Membrane is greatly improved, wherein mainly to the improvement of cavity block and anode membrane contact interface, " monolithic type " structure occurred from the beginning of initial simple " pressure stratotype " or " coating type " structure to the 80's of 20th century, occur again subsequently, with the labyrinth of middle " Catalytic Layer ", greatly reducing membrane voltage.
At present, bipolar membrane electrodialysis technology has played original effect in optimization traditional industrial process and new industrial process.Its appearance changes traditional industry and is separated and preparation process, for the technical barrier solved in the fields such as environment, chemical industry, biology, marine chemical industry brings new vigor and vitality into, the problem such as environment, resource, the energy simultaneously for solving facing mankind provides effective means.
It is CN102167293A that State Intellectual Property Office discloses a publication number in 2011.3.10, the patent of invention that name is called " a kind of method using bipolar membrane electrodialysis device to produce sulfuric acid and NaOH ", disclose a kind of method using bipolar membrane electrodialysis device to produce sulfuric acid and NaOH, the method is injected into by metabisulfite solution 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 is formed, under the effect of DC electric field power, NaOH is obtained in the compartment that the compartment selecting face to be formed towards the anion of anode in cation selective membrane and Bipolar Membrane and/or cation selective membrane and negative electrode are formed, sulfuric acid is obtained in the compartment formed towards the cation selective face of negative electrode in anion selective membrane and Bipolar Membrane and/or the compartment of anion selective membrane and anodic formation.The present invention adopt method can re-use sodium sulfate waste liquid, produce can secondary utilize sulfuric acid and NaOH, make it turn waste into wealth, there is significant economic benefit and environmental benefit.
Although above-mentioned patent can accomplish to dispose waste liquid; make acid-alkali regeneration; certain protected effect is served to environment; but it is not high still to there is the soda acid rate of recovery; energy consumption is large, cannot online recycling and recycle, and due to the pre-treatment step not before entering film device; can cause that the runner in film device blocks, film resistance increases, regenerated acid and alkali ability reduces, 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 seawater desalinization pretreatment method by using bipolar membrane through reverse osmosis process ", disclose a kind of chemical treatment method, specifically refer to a kind of to preprocess method before in desalting process.The present invention puts into bipolar membrane device seawater, and Bipolar Membrane is wherein a divalence diffusion barrier; Pole liquid is sodium chloride or the metabisulfite solution of mass concentration 1-10%; Then the alkali lye in bipolar membrane device alkali room is mixed with water inlet, the micro-filtrate membrane filtration of the water inlet 0.1-0.5 micron after above-mentioned alkalization, and then regulating pH by the acid solution of bipolar acid room, adjust ph, to 8.2-8.8, namely can be used as desalinization process and uses.Advantage of the present invention is less investment, operating cost is low, Boron contents that is easy to operate, that produce water meets drinking water standard, the Bipolar Membrane sea-water-desalination water producing hardening and tempering method that can carry out heavy construction application and technique, solves the technical bottleneck of desalinization development.The present invention can be widely used in desalinization occasion.Content disclosed in this patent is not suitable for the sodium sulfate waste liquid process produced in the viscose glue production process containing complicated ingredient impurity.
Summary of the invention
The present invention is intended to solve the existing waste liquid produced in viscose strand forming process that is applied to and reclaims soda acid technology Problems existing and defect through bipolar membrane electrodialysis method, a kind of viscose sodium sulfate waste liquor is provided to reclaim the technique of soda acid through bipolar membrane electrodialysis method, only for the technique being applied to the waste liquid that produces in viscose strand forming process and getting through bipolar membrane electrodialysis legal system soda acid, adopt specific recovery method, pre-treatment step in recovery method processes the waste liquid produced in viscose strand forming process, enter bipolar membrane electrodialysis process again, improve the regeneration rate of recovery of bronsted lowry acids and bases bronsted lowry in viscose waste liquid, decrease the damage that waste liquid impurity causes Bipolar Membrane, improve the service life of Bipolar Membrane, and ensure carrying out smoothly of bipolar membrane electrodialysis and subsequent handling.
In order to realize foregoing invention object, concrete technical scheme of the present invention is as follows:
Viscose sodium sulfate waste liquor reclaims a technique for soda acid through bipolar membrane electrodialysis method, it is characterized in that comprising the following steps successively: crystallization, adjustment pH, prefiltration, an O
3redox, substance, secondary prefiltration, active carbon organics removal, ion exchange resin remove zinc ion, pp micro porous filtration essence is filtered, soda acid is produced and concentrated;
Described crystallization by by viscose strand forming process generation sodium sulphate content be that the waste liquid of 200-400g/L generates sodium sulfate crystal by high temperature crystallization;
Described adjustment pH is for first to dissolve sodium sulfate crystal with demineralized water, obtain the metabisulfite solution that concentration is 3%-15%, sodium carbonate is added again in metabisulfite solution, solution ph is modulated 8-10, add sodium carbonate can by the zinc ion in metabisulfite solution maximized precipitation, Separation of Solid and Liquid, reclaims zinc and reduces zinc ion content in metabisulfite solution;
Described process adds the metabisulfite solution of sodium carbonate depositing zinc ion, through a prefiltration, an i.e. plate filter, removing zinc ion sediment, comparatively pure metabisulfite solution is allowed to enter in bipolar membrane electrodialysis film group device, extend the service life of equipment, improve yield and the quality of product;
Described metabisulfite solution after a prefiltration, adopts O
3oxidizing process removes the reducing substances of metabisulfite solution, comparatively pure metabisulfite solution is allowed to enter in bipolar membrane electrodialysis film group device, avoid bipolar membrane electrodialysis equipment when electrolysis, make film and reducing substances generation redox reaction and damage, extend the service life of equipment, improve the quality of product;
Described through O
3metabisulfite solution after oxidation removal reducing substances filters through secondary flame filter press, the large granular impurity that can effectively go out in metabisulfite solution, comparatively pure metabisulfite solution is allowed to enter in bipolar membrane electrodialysis film group device, extend the service life of equipment, improve the quality of product;
Described metabisulfite solution after secondary prefiltration is again through activated-carbon device, can effectively organics removal matter and some fine particles, avoid organic substance enrichment and affect the performance of film in Bipolar Membrane equipment, extend the service life of equipment, improve yield and the quality of product;
Described metabisulfite solution after charcoal treatment, through ion exchange resin system, is removed the remaining zinc ion in solution, is made the impact of bivalent metal ion on bipolar membrane electrodialysis drop to minimum;
The described metabisulfite solution through ion exchange resin system through the filter of pp millipore filter essence, can obtain meeting the treatment fluid entering bipolar membrane electrodialysis film group device index again;
Described soda acid is produced as treatment fluid obtains through bipolar membrane electrodialysis legal system the sodium hydroxide solution that concentration controls as the sulfuric acid solution of 1-30g/l and concentration control as 5-80g/l;
Concentration controls as the sulfuric acid solution of 1-30g/l adopts hyperfiltration and electroosmose process to concentrate successively by described simmer down to; After concentrated, concentration controls to carry out sulfuric acid in the acid bath operation that viscose produces add for the sulfuric acid solution of 80-320g/l is transported to, and forms online sulfuric acid circulation and stress reutilization system; Concentration is controlled for the sodium hydroxide solution of 5-80g/l adopts hyperfiltration and electroosmose process to concentrate successively; After concentrated, concentration control for the sodium hydroxide solution of 1%-15% be transported to sheet steeping operation that viscose produces, alkali cellulose sulphonic acid ester dissolution process, waste gas absorption operation, concise compressing and washing in operation and sour water neutralisation treatment operation carry out NaOH and add, and forms online alkali circulation and stress reutilization system.Reduce the input amount of sulfuric acid and NaOH, thus reduce viscose production cost.
Described concentration controls as the sodium hydroxide solution of 5-80g/l obtains the sodium hydroxide solution that concentration control is 1%-5% after hyperfiltration concentrates; The sodium hydroxide solution that concentration control is 6%-15% is obtained again after electroosmose process concentrates.
In described treatment fluid, ss concentration is less than 5mg/l, 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 described crystallisation step, crystallization temperature is 40-80 DEG C, and crystallization time is 5-30min, obtains the sodium sulfate crystal of 92%.
In described active carbon organics removal step, adopt corpuscular active carbon adsorption column.
In described pp micro porous filtration essence filter step, in PP filter, the aperture of micropore filtering film is 0.22-1 micron.
Flame filter press and PP filter are physical filtering, and flame filter press filters out a certain size large granular impurity in metabisulfite solution and suspended matter, and PP metre filter falls the material of the small radii in metabisulfite solution.
The Advantageous Effects that the present invention brings:
1, the present invention solves the existing waste liquid produced in viscose strand forming process that is applied to and reclaims soda acid technology Problems existing and defect through bipolar membrane electrodialysis method, adopt specific recovery method, pre-treatment step in recovery method processes the waste liquid produced in viscose strand forming process, enter bipolar membrane electrodialysis process again, improve the regeneration rate of recovery of bronsted lowry acids and bases bronsted lowry in viscose waste liquid, decrease the damage that waste liquid impurity causes Bipolar Membrane, improve the service life of Bipolar Membrane, and ensure carrying out smoothly of bipolar membrane electrodialysis and subsequent handling.
2, the concentration of sodium hydroxide solution of the present invention controls as 5-80g/l, and the concentration of sulfuric acid solution controls as 1-30g/l; Can coordinate with follow-up enrichment process well, realize online recycling sulfuric acid and NaOH.
3, the present invention adopts and sulfuric acid solution and sodium hydroxide solution is concentrated respectively, and after concentrated, the concentration of sulfuric acid solution is 80-320g/l, and the concentration of sodium hydroxide solution is 1%-15%; Sulfuric acid solution can be transported in the acid bath operation that viscose produces and carry out sulfuric acid and add; Sodium hydroxide solution can be transported to sheet steeping operation that viscose produces, alkali cellulose sulphonic acid ester dissolution process, waste gas absorption operation, concise compressing and washing are carried out NaOH in operation and sour water neutralisation treatment operation and added, the circulatory system can be formed, reduce the input amount of sulfuric acid and NaOH, thus reduce viscose production cost.
4, the present invention adopts hyperfiltration and electroosmose process to concentrate soda acid respectively successively, when reclaiming the alkali lye that alkali concn controls as 1%-15%, and Be very effective, cost-saving, can directly reclaim; Concentrate through low-temperature multi-effect method again and can obtain alkali concn and control as the alkali lye of 15%-30%, be recovered to that viscose glue produces with carrying out adding of alkali in alkali operation, reduction production cost, brings benefits.
Detailed description of the invention
Below enforcement of the present invention is illustrated:
Embodiment 1
Viscose sodium sulfate waste liquor reclaims a technique for soda acid through bipolar membrane electrodialysis method, comprises the following steps successively: crystallization, adjustment pH, prefiltration, an O
3redox, substance, secondary prefiltration, active carbon organics removal, ion exchange resin remove zinc ion, pp micro porous filtration essence is filtered, soda acid is produced and concentrated;
Described crystallization by by viscose strand forming process generation sodium sulphate content be that the waste liquid of 200g/L generates sodium sulfate crystal by high temperature crystallization;
Described adjustment pH is for first to dissolve sodium sulfate crystal with demineralized water, obtain the metabisulfite solution that concentration is 3%, sodium carbonate is added again in metabisulfite solution, by solution ph modulation 8, add sodium carbonate can by the zinc ion in metabisulfite solution maximized precipitation, be easy to be separated, the metabisulfite solution of the zinc ion making content few enters in bipolar membrane electrodialysis film group device, extend the service life of equipment, improve yield and the quality of product;
Described process adds the metabisulfite solution of sodium carbonate depositing zinc ion, through a prefiltration, i.e. and a plate filter, removing zinc ion sediment, allow comparatively pure metabisulfite solution enter in bipolar membrane electrodialysis film group device, extend the service life of equipment, improve the quality of product;
Described metabisulfite solution after a prefiltration, adopts O
3oxidizing process removes the reducing substances of metabisulfite solution, comparatively pure metabisulfite solution is allowed to enter in bipolar membrane electrodialysis film group device, avoid bipolar membrane electrodialysis equipment when electrolysis, being reduced property of film substance oxidation is made to reduce and damage, extend the service life of equipment, improve the quality of product;
Described through O
3metabisulfite solution after oxidation removal reducing substances filters through secondary flame filter press, the large granular impurity that can effectively go out in metabisulfite solution, comparatively pure metabisulfite solution is allowed to enter in bipolar membrane electrodialysis film group device, extend the service life of equipment, improve the quality of product;
Described metabisulfite solution after secondary prefiltration is again through activated-carbon device, can effectively organics removal matter and some fine particles, avoid organic substance enrichment and affect the performance of film in Bipolar Membrane equipment, extend the service life of equipment, improve yield and the quality of product;
Described metabisulfite solution after charcoal treatment, through ion exchange resin system, is removed the remaining zinc ion in solution, is made the impact of bivalent metal ion on bipolar membrane electrodialysis drop to minimum;
The described metabisulfite solution through ion exchange resin system through the filter of pp millipore filter essence, can obtain meeting the treatment fluid entering bipolar membrane electrodialysis film group device index again;
Described soda acid is produced as treatment fluid obtains through bipolar membrane electrodialysis legal system the sodium hydroxide solution that concentration controls as the sulfuric acid solution of 1g/l and concentration control as 5g/l;
Concentration controls as the sulfuric acid solution of 1g/l adopts hyperfiltration and electroosmose process to concentrate successively by described simmer down to; After concentrated, concentration is that the sulfuric acid solution of 80g/l is transported to and carries out sulfuric acid in the acid bath operation that viscose produces and add, and forms online sulfuric acid circulation and stress reutilization system; Concentration is controlled for the sodium hydroxide solution of 5g/l adopts hyperfiltration and electroosmose process to concentrate successively; The sodium hydroxide solution that concentration control is 1% is obtained after hyperfiltration concentrates; The sodium hydroxide solution that concentration control is 6% is obtained again after electroosmose process concentrates; Concentration control be 6% sodium hydroxide solution be transported in the sheet steeping operation that viscose produces and carry out NaOH and add, form online alkali circulation and stress reutilization system.
In described treatment fluid, ss concentration is less than 5mg/l, 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 ° of C.
In described crystallisation step, crystallization temperature is 40 DEG C, and crystallization time is 30min, obtains the sodium sulfate crystal of 92%.
In described active carbon organics removal step, adopt corpuscular active carbon adsorption column.
In described pp micro porous filtration essence filter step, in PP filter, the aperture of micropore filtering film is 0.22 micron.
Flame filter press and PP filter are physical filtering, and flame filter press filters out a certain size large granular impurity in metabisulfite solution and suspended matter, and PP metre filter falls the material of the small radii in metabisulfite solution.
Sodium sulfate concentration is that the viscose sodium sulfate waste liquor of 5% is through crystallization, adjustment pH, prefiltration, an O by the method for the present invention adopts applicant to apply for simultaneously a kind of bipolar membrane electrodialysis method process viscose sodium sulfate waste liquor when applying
3redox, substance, secondary prefiltration, active carbon organics removal, ion exchange resin remove zinc ion and the filter of pp micro porous filtration essence, then enter in the sodium sulphate runner of bipolar membrane electrodialysis film group device; In the sour runner entering bipolar membrane electrodialysis film group device respectively as the demineralized water of absorption liquid and alkali runner, obtained 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 using the alloy firm of polyethylene and ethene and octene copolymer elastomer and Oppanol tertiary blending as basilar memebrane, immerse in the solution containing styrene, divinylbenzene and benzoyl peroxide, the film of dipped liquid pressurizes again, and polymerization obtains under heating.
The thickness of described basement membrane is 0.05mm.
When specifically using, select BPM2-2500-3 type bipolar membrane electrodialysis film group device, 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), the concentrated electrodialysis film group device of reverse osmosis concentration equipment, 400*800 acid, 400*800 alkali concentrate electrodialysis film group device and heat exchanger; Heat exchanger is adopted to carry out cooling process to bipolar membrane electrodialysis film group device.
The cleaning step of bipolar membrane electrodialysis film group device comprises: 1, pass into demineralized water toward the sodium sulphate loop exit place of bipolar membrane electrodialysis film group device and carry out backwash to remove equipment runner and the less particle of Bipolar Membrane adhering on surface to bipolar membrane electrodialysis film group device, backwash to operating pressure normally; 2, with temperature be 25 degree, compound concentration be 1% sodium hydroxide solution to Bipolar Membrane surface circulation cleaning to electric current recover.
Embodiment 2
Viscose sodium sulfate waste liquor reclaims a technique for soda acid through bipolar membrane electrodialysis method, comprises the following steps successively: crystallization, adjustment pH, prefiltration, an O
3redox, substance, secondary prefiltration, active carbon organics removal, ion exchange resin remove zinc ion, pp micro porous filtration essence is filtered, soda acid is produced and concentrated;
Described crystallization by by viscose strand forming process generation sodium sulphate content be that the waste liquid of 300g/L generates sodium sulfate crystal by high temperature crystallization;
Described adjustment pH is for first to dissolve sodium sulfate crystal with demineralized water, obtain the metabisulfite solution that concentration is 7%, sodium carbonate is added again in metabisulfite solution, by solution ph modulation 9, add sodium carbonate can by the zinc ion in metabisulfite solution maximized precipitation, be easy to be separated, the metabisulfite solution of the zinc ion making content few enters in bipolar membrane electrodialysis film group device, extend the service life of equipment, improve yield and the quality of product;
Described process adds the metabisulfite solution of sodium carbonate depositing zinc ion, through a prefiltration, i.e. and a plate filter, removing zinc ion sediment, allow comparatively pure metabisulfite solution enter in bipolar membrane electrodialysis film group device, extend the service life of equipment, improve the quality of product;
Described metabisulfite solution after a prefiltration, adopts O
3oxidizing process removes the reducing substances of metabisulfite solution, comparatively pure metabisulfite solution is allowed to enter in bipolar membrane electrodialysis film group device, avoid bipolar membrane electrodialysis equipment when electrolysis, being reduced property of film substance oxidation is made to reduce and damage, extend the service life of equipment, improve the quality of product;
Described through O
3metabisulfite solution after oxidation removal reducing substances filters through secondary flame filter press, the large granular impurity that can effectively go out in metabisulfite solution, comparatively pure metabisulfite solution is allowed to enter in bipolar membrane electrodialysis film group device, extend the service life of equipment, improve the quality of product;
Described metabisulfite solution after secondary prefiltration is again through activated-carbon device, can effectively organics removal matter and some fine particles, avoid organic substance enrichment and affect the performance of film in Bipolar Membrane equipment, extend the service life of equipment, improve yield and the quality of product;
Described metabisulfite solution after charcoal treatment, through ion exchange resin system, is removed the remaining zinc ion in solution, is made the impact of bivalent metal ion on bipolar membrane electrodialysis drop to minimum;
The described metabisulfite solution through ion exchange resin system through the filter of pp millipore filter essence, can obtain meeting the treatment fluid entering bipolar membrane electrodialysis film group device index again;
Described soda acid is produced as treatment fluid obtains through bipolar membrane electrodialysis legal system the sodium hydroxide solution that concentration controls as the sulfuric acid solution of 10g/l and concentration control as 10g/l;
Concentration controls as the sulfuric acid solution of 10g/l adopts hyperfiltration and electroosmose process to concentrate successively by described simmer down to; After concentrated, concentration is that the sulfuric acid solution of 100g/l is transported to and carries out sulfuric acid in the acid bath operation that viscose produces and add, and forms online sulfuric acid circulation and stress reutilization system; Concentration is controlled for the sodium hydroxide solution of 10g/l adopts hyperfiltration and electroosmose process to concentrate successively; The sodium hydroxide solution that concentration control is 2% is obtained after hyperfiltration concentrates; The sodium hydroxide solution that concentration control is 9% is obtained again after electroosmose process concentrates; Concentration control be 9% sodium hydroxide solution be transported in the alkali cellulose sulphonic acid ester dissolution process that viscose produces and carry out NaOH and add, form online alkali circulation and stress reutilization system.
In described treatment fluid, ss concentration is less than 5mg/l, 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 described crystallisation step, crystallization temperature is 60 DEG C, and crystallization time is 15min, obtains the sodium sulfate crystal of 92%.
In described active carbon organics removal step, adopt corpuscular active carbon adsorption column.
In described pp micro porous filtration essence filter step, in PP filter, the aperture of micropore filtering film is 0.22 micron.
Flame filter press and PP filter are physical filtering, and flame filter press filters out a certain size large granular impurity in metabisulfite solution and suspended matter, and PP metre filter falls the material of the small radii in metabisulfite solution.
Sodium sulfate concentration is that the viscose sodium sulfate waste liquor of 10% is through crystallization, adjustment pH, prefiltration, an O by the method for the present invention adopts applicant to apply for simultaneously a kind of bipolar membrane electrodialysis method process viscose sodium sulfate waste liquor when applying
3redox, substance, secondary prefiltration, active carbon organics removal, ion exchange resin remove zinc ion and the filter of pp micro porous filtration essence, then enter in the sodium sulphate runner of bipolar membrane electrodialysis film group device; In the sour runner entering bipolar membrane electrodialysis film group device respectively as the demineralized water of absorption liquid and alkali runner, obtained 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 using the alloy firm of polyethylene and ethene and octene copolymer elastomer and Oppanol tertiary blending as basilar memebrane, immerse in the solution containing styrene, divinylbenzene and benzoyl peroxide, the film of dipped liquid pressurizes again, and polymerization obtains under heating.
The thickness of described basement membrane is 0.05mm.
When specifically using, select BPM2-2500-3 type bipolar membrane electrodialysis film group device, 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), the concentrated electrodialysis film group device of reverse osmosis concentration equipment, 400*800 acid, 400*800 alkali concentrate electrodialysis film group device and heat exchanger; Heat exchanger is adopted to carry out cooling process to bipolar membrane electrodialysis film group device.
The cleaning step of bipolar membrane electrodialysis film group device comprises: 1, pass into demineralized water toward the sodium sulphate loop exit place of bipolar membrane electrodialysis film group device and carry out backwash to remove equipment runner and the less particle of Bipolar Membrane adhering on surface to bipolar membrane electrodialysis film group device, backwash to operating pressure normally; 2, with temperature be 28 degree, compound concentration be 2% sodium hydroxide solution to Bipolar Membrane surface circulation cleaning to electric current recover.
Embodiment 3
Viscose sodium sulfate waste liquor reclaims a technique for soda acid through bipolar membrane electrodialysis method, comprises the following steps successively: crystallization, adjustment pH, prefiltration, an O
3redox, substance, secondary prefiltration, active carbon organics removal, ion exchange resin remove zinc ion, pp micro porous filtration essence is filtered, soda acid is produced and concentrated;
Described crystallization by by viscose strand forming process generation sodium sulphate content be that the waste liquid of 300g/L generates sodium sulfate crystal by high temperature crystallization;
Described adjustment pH is for first to dissolve sodium sulfate crystal with demineralized water, obtain the metabisulfite solution that concentration is 12%, sodium carbonate is added again in metabisulfite solution, by solution ph modulation 9, add sodium carbonate can by the zinc ion in metabisulfite solution maximized precipitation, be easy to be separated, the metabisulfite solution of the zinc ion making content few enters in bipolar membrane electrodialysis film group device, extend the service life of equipment, improve yield and the quality of product;
Described process adds the metabisulfite solution of sodium carbonate depositing zinc ion, through a prefiltration, i.e. and a plate filter, removing zinc ion sediment, allow comparatively pure metabisulfite solution enter in bipolar membrane electrodialysis film group device, extend the service life of equipment, improve the quality of product;
Described metabisulfite solution after a prefiltration, adopts O
3oxidizing process removes the reducing substances of metabisulfite solution, comparatively pure metabisulfite solution is allowed to enter in bipolar membrane electrodialysis film group device, avoid bipolar membrane electrodialysis equipment when electrolysis, being reduced property of film substance oxidation is made to reduce and damage, extend the service life of equipment, improve the quality of product;
Described through O
3metabisulfite solution after oxidation removal reducing substances filters through secondary flame filter press, the large granular impurity that can effectively go out in metabisulfite solution, comparatively pure metabisulfite solution is allowed to enter in bipolar membrane electrodialysis film group device, extend the service life of equipment, improve the quality of product;
Described metabisulfite solution after secondary prefiltration is again through activated-carbon device, can effectively organics removal matter and some fine particles, avoid organic substance enrichment and affect the performance of film in Bipolar Membrane equipment, extend the service life of equipment, improve yield and the quality of product;
Described metabisulfite solution after charcoal treatment, through ion exchange resin system, is removed the remaining zinc ion in solution, is made the impact of bivalent metal ion on bipolar membrane electrodialysis drop to minimum;
The described metabisulfite solution through ion exchange resin system through the filter of pp millipore filter essence, can obtain meeting the treatment fluid entering bipolar membrane electrodialysis film group device index again;
Described soda acid is produced treatment fluid and is obtained through bipolar membrane electrodialysis legal system the sodium hydroxide solution that concentration controls as the sulfuric acid solution of 15g/l and concentration control as 15g/l;
Concentration controls as the sulfuric acid solution of 15g/l adopts hyperfiltration and electroosmose process to concentrate successively by described simmer down to; After concentrated, concentration is that the sulfuric acid solution of 120g/l is transported to and carries out sulfuric acid in the acid bath operation that viscose produces and add, and forms online sulfuric acid circulation and stress reutilization system; Concentration is controlled for the sodium hydroxide solution of 15g/l adopts hyperfiltration and electroosmose process to concentrate successively; The sodium hydroxide solution that concentration control is 4% is obtained after hyperfiltration concentrates; The sodium hydroxide solution that concentration control is 13% is obtained again after electroosmose process concentrates; Concentration control be 13% sodium hydroxide solution be transported in the waste gas absorption operation that viscose produces and carry out NaOH and add, form online alkali circulation and stress reutilization system.
In described treatment fluid, ss concentration is less than 5mg/l, 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 described crystallisation step, crystallization temperature is 60 DEG C, and crystallization time is 15min, obtains the sodium sulfate crystal of 92%.
In described active carbon organics removal step, adopt corpuscular active carbon adsorption column.
In described pp micro porous filtration essence filter step, in PP filter, the aperture of micropore filtering film is 0.22 micron.
Flame filter press and PP filter are physical filtering, and flame filter press filters out a certain size large granular impurity in metabisulfite solution and suspended matter, and PP metre filter falls the material of the small radii in metabisulfite solution.
Sodium sulfate concentration is that the viscose sodium sulfate waste liquor of 15% is through crystallization, adjustment pH, prefiltration, an O by the method for the present invention adopts applicant to apply for simultaneously a kind of bipolar membrane electrodialysis method process viscose sodium sulfate waste liquor when applying
3redox, substance, secondary prefiltration, active carbon organics removal, ion exchange resin remove zinc ion and the filter of pp micro porous filtration essence, then enter in the sodium sulphate runner of bipolar membrane electrodialysis film group device; In the sour runner entering bipolar membrane electrodialysis film group device respectively as the demineralized water of absorption liquid and alkali runner, obtained 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 using the alloy firm of polyethylene and ethene and octene copolymer elastomer and Oppanol tertiary blending as basilar memebrane, immerse in the solution containing styrene, divinylbenzene and benzoyl peroxide, the film of dipped liquid pressurizes again, and polymerization obtains under heating.
The thickness of described basement membrane is 0.05mm.
When specifically using, select BPM2-2500-3 type bipolar membrane electrodialysis film group device, 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), the concentrated electrodialysis film group device of reverse osmosis concentration equipment, 400*800 acid, 400*800 alkali concentrate electrodialysis film group device and heat exchanger; Heat exchanger is adopted to carry out cooling process to bipolar membrane electrodialysis film group device.
The cleaning step of bipolar membrane electrodialysis film group device comprises: 1, pass into demineralized water toward the sodium sulphate loop exit place of bipolar membrane electrodialysis film group device and carry out backwash to remove equipment runner and the less particle of Bipolar Membrane adhering on surface to bipolar membrane electrodialysis film group device, backwash to operating pressure normally; 2, with temperature be 30 degree, compound concentration be 3% sodium hydroxide solution to Bipolar Membrane surface circulation cleaning to electric current recover.
Embodiment 4
Viscose sodium sulfate waste liquor reclaims a technique for soda acid through bipolar membrane electrodialysis method, comprises the following steps successively: crystallization, adjustment pH, prefiltration, an O
3redox, substance, secondary prefiltration, active carbon organics removal, ion exchange resin remove zinc ion, pp micro porous filtration essence is filtered, soda acid is produced and concentrated;
Described crystallization by by viscose strand forming process generation sodium sulphate content be that the waste liquid of 400g/L generates sodium sulfate crystal by high temperature crystallization;
Described adjustment pH is for first to dissolve sodium sulfate crystal with demineralized water, obtain the metabisulfite solution that concentration is 15%, sodium carbonate is added again in metabisulfite solution, by solution ph modulation 10, add sodium carbonate can by the zinc ion in metabisulfite solution maximized precipitation, be easy to be separated, the metabisulfite solution of the zinc ion making content few enters in bipolar membrane electrodialysis film group device, extend the service life of equipment, improve yield and the quality of product;
Described process adds the metabisulfite solution of sodium carbonate depositing zinc ion, through a prefiltration, i.e. and a plate filter, removing zinc ion sediment, allow comparatively pure metabisulfite solution enter in bipolar membrane electrodialysis film group device, extend the service life of equipment, improve the quality of product;
Described metabisulfite solution after a prefiltration, adopts O
3oxidizing process removes the reducing substances of metabisulfite solution, comparatively pure metabisulfite solution is allowed to enter in bipolar membrane electrodialysis film group device, avoid bipolar membrane electrodialysis equipment when electrolysis, being reduced property of film substance oxidation is made to reduce and damage, extend the service life of equipment, improve the quality of product;
Described through O
3metabisulfite solution after oxidation removal reducing substances filters through secondary flame filter press, the large granular impurity that can effectively go out in metabisulfite solution, comparatively pure metabisulfite solution is allowed to enter in bipolar membrane electrodialysis film group device, extend the service life of equipment, improve the quality of product;
Described metabisulfite solution after secondary prefiltration is again through activated-carbon device, can effectively organics removal matter and some fine particles, avoid organic substance enrichment and affect the performance of film in Bipolar Membrane equipment, extend the service life of equipment, improve yield and the quality of product;
Described metabisulfite solution after charcoal treatment, through ion exchange resin system, is removed the remaining zinc ion in solution, is made the impact of bivalent metal ion on bipolar membrane electrodialysis drop to minimum;
The described metabisulfite solution through ion exchange resin system through the filter of pp millipore filter essence, can obtain meeting the treatment fluid entering bipolar membrane electrodialysis film group device index again;
Described soda acid is produced as treatment fluid obtains through bipolar membrane electrodialysis legal system the sodium hydroxide solution that concentration controls as the sulfuric acid solution of 30g/l and concentration control as 80g/l;
Concentration controls as the sulfuric acid solution of 30g/l adopts hyperfiltration and electroosmose process to concentrate successively by described simmer down to; After concentrated, concentration is that the sulfuric acid solution of 320g/l is transported to and carries out sulfuric acid in the acid bath operation that viscose produces and add, and forms online sulfuric acid circulation and stress reutilization system; Concentration is controlled for the sodium hydroxide solution of 80g/l adopts hyperfiltration and electroosmose process to concentrate successively; The sodium hydroxide solution that concentration control is 5% is obtained after hyperfiltration concentrates; The sodium hydroxide solution that concentration control is 15% is obtained again after electroosmose process concentrates; Concentration control be 15% sodium hydroxide solution be transported to concise the compressing and washing in operation of pulp that viscose produces and carry out NaOH and add, form online alkali circulation and stress reutilization system.
In described treatment fluid, ss concentration is less than 5mg/l, 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 described crystallisation step, crystallization temperature is 80 DEG C, and crystallization time is 5min, obtains the sodium sulfate crystal of 92%.
In described active carbon organics removal step, adopt corpuscular active carbon adsorption column.
In described pp micro porous filtration essence filter step, in PP filter, the aperture of micropore filtering film is 0.22 micron.
Flame filter press and PP filter are physical filtering, and flame filter press filters out a certain size large granular impurity in metabisulfite solution and suspended matter, and PP metre filter falls the material of the small radii in metabisulfite solution.
Sodium sulfate concentration is that the viscose sodium sulfate waste liquor of 20% is through crystallization, adjustment pH, prefiltration, an O by the method for the present invention adopts applicant to apply for simultaneously a kind of bipolar membrane electrodialysis method process viscose sodium sulfate waste liquor when applying
3redox, substance, secondary prefiltration, active carbon organics removal, ion exchange resin remove zinc ion and the filter of pp micro porous filtration essence, then enter in the sodium sulphate runner of bipolar membrane electrodialysis film group device; In the sour runner entering bipolar membrane electrodialysis film group device respectively as the demineralized water of absorption liquid and alkali runner, obtained 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 using the alloy firm of polyethylene and ethene and octene copolymer elastomer and Oppanol tertiary blending as basilar memebrane, immerse in the solution containing styrene, divinylbenzene and benzoyl peroxide, the film of dipped liquid pressurizes again, and polymerization obtains under heating.
The thickness of described basement membrane is 0.05mm.
When specifically using, select BPM2-2500-3 type bipolar membrane electrodialysis film group device, 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), the concentrated electrodialysis film group device of reverse osmosis concentration equipment, 400*800 acid, 400*800 alkali concentrate electrodialysis film group device and heat exchanger; Heat exchanger is adopted to carry out cooling process to bipolar membrane electrodialysis film group device.
The cleaning step of bipolar membrane electrodialysis film group device comprises: 1, pass into demineralized water toward the sodium sulphate loop exit place of bipolar membrane electrodialysis film group device and carry out backwash to remove equipment runner and the less particle of Bipolar Membrane adhering on surface to bipolar membrane electrodialysis film group device, backwash to operating pressure normally; 2, with temperature be 35 degree, compound concentration be 5% sodium hydroxide solution to Bipolar Membrane surface circulation cleaning to electric current recover.
Embodiment 5
Concentration also can control as the alkali lye of 6%-15% by the present invention, then controls as 15%-30% through the concentrated alkali concn that can obtain of low-temperature multi-effect method, be recovered to that viscose glue produces with carrying out adding of alkali in alkali operation, reduction production cost, brings benefits.
Claims (6)
1. viscose sodium sulfate waste liquor reclaims a technique for soda acid through bipolar membrane electrodialysis method, it is characterized in that comprising the following steps successively: crystallization, adjustment pH, prefiltration, an O
3redox, substance, secondary prefiltration, active carbon organics removal, ion exchange resin remove zinc ion, pp micro porous filtration essence is filtered, soda acid is produced and concentrated;
Described crystallization by by viscose strand forming process generation sodium sulphate content be that the waste liquid of 200-400g/L generates sodium sulfate crystal by high temperature crystallization;
Described adjustment pH, for first to dissolve sodium sulfate crystal with demineralized water, obtains the metabisulfite solution that concentration is 3%-15%, then add sodium carbonate in metabisulfite solution, solution ph is modulated 8-10 amount;
Described process adds the metabisulfite solution of sodium carbonate depositing zinc ion, through a prefiltration, i.e. and a plate filter, removing zinc ion sediment;
Described metabisulfite solution after a prefiltration, adopts O
3oxidizing process removes the reducing substances of metabisulfite solution;
Described through O
3metabisulfite solution after oxidation removal reducing substances filters through secondary flame filter press, removes the large granular impurity in metabisulfite solution;
Described metabisulfite solution after secondary prefiltration, can effectively organics removal matter and some fine particles again through activated-carbon device;
Described metabisulfite solution after charcoal treatment, through ion exchange resin system, removes the remaining zinc ion in solution;
The described metabisulfite solution through ion exchange resin system through the filter of pp millipore filter essence, can obtain meeting the treatment fluid entering bipolar membrane electrodialysis film group device index again;
Described soda acid is produced as treatment fluid obtains through bipolar membrane electrodialysis legal system the sodium hydroxide solution that concentration controls as the sulfuric acid solution of 1-30g/l and concentration control as 5-80g/l;
Concentration controls as the sulfuric acid solution of 1-30g/l adopts hyperfiltration and electroosmose process to concentrate successively by described simmer down to; After concentrated, obtain the sulfuric acid solution that concentration control is 80-320g/l; Concentration is controlled for the sodium hydroxide solution of 5-80g/l adopts hyperfiltration and electroosmose process to concentrate successively; After concentrated, obtain the sodium hydroxide solution that concentration control is 1%-15%;
In described treatment fluid, ss concentration is less than 5mg/l, 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.
2. a kind of viscose sodium sulfate waste liquor reclaims the technique of soda acid through bipolar membrane electrodialysis method according to claim 1, it is characterized in that: described concentration controls as the sodium hydroxide solution of 5-80g/l obtains the sodium hydroxide solution that concentration control is 1%-5% after hyperfiltration concentrates; The sodium hydroxide solution that concentration control is 6%-15% is obtained again after electroosmose process concentrates.
3. a kind of viscose sodium sulfate waste liquor reclaims the technique of soda acid through bipolar membrane electrodialysis method according to claim 1, and it is characterized in that: in described crystallisation step, crystallization temperature is 40-80 DEG C, and crystallization time is 5-30min, obtains the sodium sulfate crystal of 92%.
4. a kind of viscose sodium sulfate waste liquor reclaims the technique of soda acid through bipolar membrane electrodialysis method according to claim 1, it is characterized in that: in described active carbon organics removal step, adopt corpuscular active carbon adsorption column.
5. a kind of viscose sodium sulfate waste liquor reclaims the technique of soda acid through bipolar membrane electrodialysis method according to claim 1, it is characterized in that: in described pp micro porous filtration essence filter step, in PP filter, the aperture of micropore filtering film is 0.22-1 micron.
6. a kind of viscose sodium sulfate waste liquor reclaims the technique of soda acid through bipolar membrane electrodialysis method according to claim 1, 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 in metabisulfite solution and suspended matter, and PP metre filter falls the material of the small radii in metabisulfite solution.
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| CN102167293A (en) * | 2011-03-10 | 2011-08-31 | 福建省三明汇丰化工有限公司 | Method for producing sulfuric acid and sodium hydroxide by using bipolar membrane electroosmosis device |
| CN103073131A (en) * | 2012-12-28 | 2013-05-01 | 中国环境科学研究院 | Process for treating amantadine bromination waste water and mineral acid and alkali recycling through bipolar membrane electrodialysis process |
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| CN102019195A (en) * | 2009-09-09 | 2011-04-20 | 中国石油天然气股份有限公司 | Modified Y molecular sieve-containing catalytic cracking catalyst |
| CN102167293A (en) * | 2011-03-10 | 2011-08-31 | 福建省三明汇丰化工有限公司 | Method for producing sulfuric acid and sodium hydroxide by using bipolar membrane electroosmosis device |
| CN103073131A (en) * | 2012-12-28 | 2013-05-01 | 中国环境科学研究院 | Process for treating amantadine bromination waste water and mineral acid and alkali recycling through bipolar membrane electrodialysis process |
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