CN103342433B - Method for recovering acid and alkali from viscose sodium sulfate waste liquor through bipolar membrane electrodialysis way - Google Patents
Method for recovering acid and alkali from viscose sodium sulfate waste liquor through bipolar membrane electrodialysis way Download PDFInfo
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- CN103342433B CN103342433B CN201310312036.9A CN201310312036A CN103342433B CN 103342433 B CN103342433 B CN 103342433B CN 201310312036 A CN201310312036 A CN 201310312036A CN 103342433 B CN103342433 B CN 103342433B
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- metabisulfite solution
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- 239000012528 membrane Substances 0.000 title claims abstract description 172
- 238000000034 method Methods 0.000 title claims abstract description 123
- 238000000909 electrodialysis Methods 0.000 title claims abstract description 108
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 title claims abstract description 79
- 229910052938 sodium sulfate Inorganic materials 0.000 title claims abstract description 72
- 235000011152 sodium sulphate Nutrition 0.000 title claims abstract description 72
- 229920000297 Rayon Polymers 0.000 title claims abstract description 65
- 239000002253 acid Substances 0.000 title claims abstract description 48
- 239000002699 waste material Substances 0.000 title claims abstract description 45
- 239000003513 alkali Substances 0.000 title abstract description 40
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 152
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- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims abstract description 23
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- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
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- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
The invention discloses a method for recovering acid and alkali from viscose sodium sulfate waste liquor through a bipolar membrane electrodialysis way. The method is characterized by sequentially comprising the following steps of: crystallizing; adjusting pH (Potential of Hydrogen); initially filtering at the first time; oxidizing reducing substances through O3; initially filtering at the second time; removing organic substances through activated carbon; removing zinc ions through ion exchange resin; filtering and performing refined filtration through pp micropores; preparing acid and alkali; and concentrating. By adopting the method, the regenerative recovery rate of the acid and alkali in the viscose sodium sulfate waste liquor is increased, and the damage of impurities in the waste liquor to a bipolar membrane is reduced, so that the service life of the bipolar membrane is prolonged, and the bipolar membrane electrodialysis and subsequent processes can be able to be carried out smoothly; in addition, sodium hydroxide crystals of which the alkali concentration is controlled to 96%, 98% and 99% can be obtained, which can be directly marketed, thus the benefit is brought.
Description
Technical field
The present invention relates to the method for material processing in a kind of Chemical Manufacture, more particularly, the present invention relates to a kind of viscose fiber sodium sulfate waste liquid and adopt bipolar membrane electrodialysis method to reclaim the method for soda acid, belong to viscose fiber production technical field.
Background technology
In viscose fiber moulding process in chemical fibre industry, viscose glue and acid coagulating bath effect, be neutralized alkali, and sodium cellulose xanghate is decomposed and regeneration cellulose hydrate, cellulose sulfonate, free NaOH and the Na because of side reaction generation in this process in viscose glue
2cS
3, the side reaction product such as polysulfide all can with precipitation bath in sulfuric acid reaction generate sodium sulfate.Viscose fiber is produced and is comprised the acid bath operation that consumes sulfuric acid, also comprises the sheet steeping operation, soda cellulose sulphonate dissolution process, waste gas absorption operation, concise operation and the sour water neutralizing treatment operation of compressing and washing that consume sodium hydroxide.
In precipitation bath the Main Function of sodium sulfate be impel viscose stream to solidify and suppress sulfolysis from, the reproduction speed of cellulose sulfonate is delayed, improve the concentration of sodium sulfate in precipitation bath, spinning operation is easier to, tow is difficult for broken end, and can reduce the dissociation degree of sulfuric acid, make tow in the time leaving precipitation bath, still there is certain residual ester value, but the sodium sulfate in precipitation bath is also unsuitable too high, otherwise can make fiber solidify overruns, can not form microtexture, and generate thick crystalline particle, also heterogeneity of the ectonexine of fiber.
In spinning process, sodium sulphate content in precipitation bath constantly increases and makes it cannot meet the requirement of technique, if only will make the total amount of precipitation bath increase and cannot store to supplement its concentration recycling by adding the raw material being consumed in precipitation bath, can only be at regular time and quantity by precipitation bath discharge, 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 sulfate unnecessary in acid bath is carried out to high temperature crystallization, isolate sodium sulfate crystal, make the content of the sodium sulfate in acid bath meet processing requirement, the acid that do not need to drain every day carrys out balance acid bath, after reinforced, directly continue for spinning workshop, can reduce acid discharge, output Sodium sulfate anhydrous.min(99), reduce environmental protection pressure, but make it can not produce economic benefit because impure many, own added values of Sodium sulfate anhydrous.min(99) that in precipitation bath, sodium sulfate high temperature crystallization is produced are low, a large amount of solid salts cannot be processed, and has still brought certain pressure to environmental protection.
Bipolar Membrane is a kind of novel ion-exchange composite membranes, it is composited by cationic exchange layer (N type film), interface hydrophilic layer (Catalytic Layer) and anionresin layer (P type film) conventionally, is reaction film truly.Under DC electric field effect, Bipolar Membrane can, by hydrolytic dissociation, obtain respectively hydrogen ion and hydroxide ion in film both sides.Utilize this feature, the bipolar membrane electrodialysis system that Bipolar Membrane and other anion and cation exchange membranes are combined into can be converted into corresponding bronsted lowry acids and bases bronsted lowry by the salt in the aqueous solution in the situation that not introducing new component, and this technology is called bipolar membrane electrodialysis technology.Compared with traditional technology, the outstanding technical superiority such as that bipolar membrane electrodialysis technology has is energy-efficient, environmental friendliness, simple operation.In recent years, bipolar membrane electrodialysis technology technology is all obtaining fast development aspect research and application two, membrane preparation technology and operation parameter optimization are constantly obtained new progress, range of application is from the albumen of the desalination of chemical field and soda acid preparation, biological field and the amino acid fields such as being extended to the purifying of trade effluent field of Environment Protection, concentrated, preparation of high-purity water of purifying, traditional chemical separating technique renovate, develop cleaner production and recycling economy process in playing the part of the role who becomes more and more important.
About the research report of 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 first stage, this is Bipolar Membrane development period very slowly, Bipolar Membrane is only by two anion and cation exchange membrane direct pressings, poor performance, the theoretical pressure drop of water decomposition voltage ratio is high tens times, and applied research is also in take water decomposition as basic laboratory stage; Subordinate phase 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 develop monolithic type Bipolar Membrane, its performance improves greatly, in relieving haperacidity alkali and desulfurization technology, having obtained 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 working process mechanism, carry out significant improvement from membrane structure, mould material and preparation process, the performance of Bipolar Membrane is greatly improved, it is mainly wherein the improvement to cavity block and anode membrane contact interface, at the beginning of from initial simple " pressure stratotype " or " coating type " structure to the 80's of 20th century, start " monolithic type " structure occurring, occur again subsequently, with the complex construction of middle " Catalytic Layer ", greatly reducing membrane voltage.
At present, bipolar membrane electrodialysis technology has been brought into play original effect optimizing in traditional industry process and new commercial run.Its appearance has changed traditional industry and has separated and preparation process, for the technical barrier solving in the fields such as environment, chemical industry, biology, marine chemical industry is brought new vigor and vitality into, simultaneously for the problem such as environment, resource, the energy that solves facing mankind provides effective means.
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 that uses bipolar membrane electrodialysis device to produce sulfuric acid and sodium hydroxide ", a kind of method that uses bipolar membrane electrodialysis device to produce sulfuric acid and sodium hydroxide is disclosed, the method is that metabisulfite solution is injected in the compartment of negatively charged ion selective membrane and cation selective membrane formation, water is injected into Bipolar Membrane and negatively charged ion selective membrane, in the compartment that cation selective membrane forms, under the effect of DC electric field power, in the compartment of the negatively charged ion selection face formation of anode and/or the compartment of cation selective membrane and negative electrode formation, obtain sodium hydroxide at cation selective membrane and Bipolar Membrane, in the compartment forming towards the cation selective face of negative electrode in negatively charged ion selective membrane and Bipolar Membrane and/or the compartment of negatively charged ion selective membrane and anodic formation, obtain sulfuric acid.The method that the present invention adopts can re-use sodium sulfate waste liquid, produce can second stage employ sulfuric acid and sodium hydroxide, it is turned 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; environment has been played to certain protection effect; but still exist the soda acid rate of recovery not high; energy consumption is large, cannot online recycling and recycle, and due to the pre-treatment step before entering film device not; can cause runner obstruction, membrane resistance increase, regenerated acid and alkali ability in 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 seawater desalinization pretreatment method by using bipolar membrane through reverse osmosis process ", disclose a kind of chemical treatment method, specifically referred to a kind of to the front pretreatment process in desalting process.The present invention puts into bipolar membrane device seawater, and Bipolar Membrane is wherein a divalence separatory membrane; Utmost point liquid is sodium-chlor or the metabisulfite solution of mass concentration 1-10%; Then the alkali lye in bipolar membrane device alkali chamber is mixed with water inlet, micro-filtrate membrane filtration the water inlet after above-mentioned alkalization with 0.1-0.5 micron, and then regulate pH by the acid solution of bipolar acid chamber, and regulate pH value to 8.2-8.8, can be used as sea water desaltination and process and use.Advantage of the present invention is Bipolar Membrane sea-water-desalination water producing hardening and tempering method and the technique that less investment, running cost boron content low, easy to operate, that produce water meets drinking water standard, can carry out heavy construction application, solves the technical bottleneck of sea water desaltination development.The present invention can be widely used in sea water desaltination occasion.The disclosed content of this patent is not suitable for the sodium sulfate liquid waste disposal producing in the viscose glue production process that contains complicated ingredient impurity.
Summary of the invention
The present invention is intended to solve the existing waste liquid producing in viscose fiber strand moulding process that is applied to and reclaims through bipolar membrane electrodialysis method problem and the defect that soda acid technology exists, provide a kind of viscose fiber sodium sulfate waste liquid to adopt bipolar membrane electrodialysis method to reclaim the method for soda acid, only for the technique that is applied to the waste liquid producing in viscose fiber strand moulding process and gets soda acid through bipolar membrane electrodialysis legal system, adopt specific recovery method, pre-treatment step in recovery method is processed the waste liquid producing in viscose fiber strand moulding process, enter again bipolar membrane electrodialysis process, improve the reclaim recovery efficiency of bronsted lowry acids and bases bronsted lowry in viscose fiber waste liquid, reduce the damage that waste liquid impurity causes Bipolar Membrane, improve the work-ing life of Bipolar Membrane, and guarantee 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 fiber sodium sulfate waste liquid adopts bipolar membrane electrodialysis method to reclaim a method for soda acid, it is characterized in that comprising the following steps successively: crystallization, regulate pH, prefiltration, O
3oxidation-reduction quality material, secondary prefiltration, gac removal organism, ion exchange resin removal zine ion, the filter of pp millipore filtration essence, soda acid are produced and are concentrated;
Described crystallization by by viscose fiber strand moulding process generation sodium sulphate content be 200-400g/L waste liquid generates sodium sulfate crystal by high temperature crystallization;
Described adjusting pH is for first dissolving sodium sulfate crystal with de-mineralized water, obtain the metabisulfite solution that concentration is 3%-15%, in metabisulfite solution, add sodium carbonate again, pH is modulated to 8-10, add the sodium carbonate can be by maximized the zine ion in metabisulfite solution precipitation, solid-liquid separation, 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, remove zine ion throw out, allow comparatively pure metabisulfite solution enter in bipolar membrane electrodialysis film group device, extend the work-ing life of equipment, improved yield and the quality of product;
Described metabisulfite solution after a prefiltration, adopts O
3oxidation style is removed the reducing substances of metabisulfite solution, allow comparatively pure metabisulfite solution enter in bipolar membrane electrodialysis film group device, avoid bipolar membrane electrodialysis equipment in the situation that of electrolysis, make film and reducing substances generation redox reaction and damage, extend the work-ing life of equipment, improved 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, allow comparatively pure metabisulfite solution enter in bipolar membrane electrodialysis film group device, extend the work-ing life of equipment, improved the quality of product;
Described metabisulfite solution after secondary prefiltration passes through activated-carbon device again, can effectively remove organic substance and some fine particles, avoid organic substance enrichment and affect the performance of film in the Bipolar Membrane equipment, extended the work-ing life of equipment, improved yield and the quality of product;
Described metabisulfite solution after activated carbon treatment, through ion exchange resin system, is removed the remaining zine ion in solution, makes divalent-metal ion drop to minimum on the impact of bipolar membrane electrodialysis;
The described metabisulfite solution through ion exchange resin system through the filter of pp millipore filter essence, can obtain meeting the treatment solution that enters bipolar membrane electrodialysis film group device index again;
Described soda acid is produced and is obtained through bipolar membrane electrodialysis legal system the sodium hydroxide solution that sulphuric acid soln that concentration control is 1-30g/l and concentration control are 5-80g/l for treatment solution;
The sulphuric acid soln that described simmer down to is 1-30g/l by concentration control adopts method of evaporation; After concentrated, the sulphuric acid soln that concentration control is 80-320g/l is transported to and in the acid bath operation that viscose fiber produces, carries out sulfuric acid and add, and forms online sulfuric acid circulation recycling system; The sodium hydroxide solution that is 5-80g/l by concentration control adopts method of evaporation to concentrate, the sodium hydroxide solution that concentration control is 50%-100% after method of evaporation is concentrated is transported to sheet steeping operation that viscose fiber produces, soda cellulose sulphonate dissolution process, waste gas absorption operation, concise compressing and washing carried out sodium hydroxide in operation and sour water neutralizing treatment operation and added, and forms online alkali circulation recycling system.Reduce the input amount of sulfuric acid and sodium hydroxide, thereby reduced viscose fiber production cost.
In described treatment solution, 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 solution is 5-35 ° of C.
In described crystallisation step, Tc is 40-80 ℃, and crystallization time is 5-30min, obtains 92% sodium sulfate crystal.
Described gac is removed in organism step, adopts corpuscular active carbon adsorption column.
In described pp millipore filtration essence filter step, in PP strainer, the aperture of micropore filtering film is 0.22-1 micron.
Flame filter press and PP strainer are physical filtering, and flame filter press filters out a certain size large granular impurity and the suspended substance in metabisulfite solution, and PP strainer filters out the material of the small radii in metabisulfite solution.
The useful technique effect that the present invention brings:
1, the present invention solves the existing waste liquid producing in viscose fiber strand moulding process that is applied to and reclaims through bipolar membrane electrodialysis method problem and the defect that soda acid technology exists, adopt specific recovery method, pre-treatment step in recovery method is processed the waste liquid producing in viscose fiber strand moulding process, enter again bipolar membrane electrodialysis process, improve the reclaim recovery efficiency of bronsted lowry acids and bases bronsted lowry in viscose fiber waste liquid, reduce the damage that waste liquid impurity causes Bipolar Membrane, improve the work-ing life of Bipolar Membrane, and guarantee carrying out smoothly of bipolar membrane electrodialysis and subsequent handling.
2, the concentration control that treatment solution is made sodium hydroxide solution by the present invention is 5-80g/l, and the concentration control of sulphuric acid soln is 1-30g/l; Can coordinate with follow-up enrichment process well, realize online recycling sulfuric acid and sodium hydroxide.
3, the present invention adopts sulphuric acid soln and sodium hydroxide solution is concentrated respectively, and after concentrating, the concentration of sulphuric acid soln is 80-320g/l, and the concentration of sodium hydroxide solution is 50%-100%; Sulphuric acid soln can be transported in the acid bath operation that viscose fiber produces and carry out sulfuric acid and add; Sodium hydroxide solution can be transported to sheet steeping operation, soda cellulose sulphonate dissolution process, waste gas absorption operation that viscose fiber produces, concise compressing and washing carried out sodium hydroxide in operation and sour water neutralizing treatment operation and added, can form the recycle system, reduce the input amount of sulfuric acid and sodium hydroxide, thereby reduced viscose fiber production cost.
4, the present invention adopts method of evaporation to concentrate alkali, is reclaiming the alkali that alkali concn control is 50%-100%, and effect is remarkable, cost-saving, can directly reclaim, and further improves the concentration that reclaims alkali; Be recovered to viscose glue produce with carrying out adding of alkali in alkali operation, reduce production costs; Also can obtain alkali concn control and be 96%, 98% and 99% sodium hydroxide crystal, can direct marketing, bring benefits.
Embodiment
Below enforcement of the present invention is illustrated:
Embodiment 1
Viscose fiber sodium sulfate waste liquid adopts bipolar membrane electrodialysis method to reclaim a method for soda acid, comprises the following steps successively: crystallization, regulate pH, prefiltration, O
3oxidation-reduction quality material, secondary prefiltration, gac removal organism, ion exchange resin removal zine ion, the filter of pp millipore filtration essence, soda acid are produced and are concentrated;
Described crystallization by by viscose fiber strand moulding process generation sodium sulphate content be 200g/L waste liquid generates sodium sulfate crystal by high temperature crystallization;
Described adjusting pH is for first dissolving sodium sulfate crystal with de-mineralized water, obtain concentration and be 3% metabisulfite solution, in metabisulfite solution, add sodium carbonate again, by pH modulation 8, add the sodium carbonate can be by maximized the zine ion in metabisulfite solution precipitation, be easy to separate, allow the metabisulfite solution of the few zine ion of content enter in bipolar membrane electrodialysis film group device, extend the work-ing life of equipment, improved 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, remove zine ion throw out, allow comparatively pure metabisulfite solution enter in bipolar membrane electrodialysis film group device, extended the work-ing life of equipment, improved the quality of product;
Described metabisulfite solution after a prefiltration, adopts O
3oxidation style is removed the reducing substances of metabisulfite solution, allow comparatively pure metabisulfite solution enter in bipolar membrane electrodialysis film group device, avoid bipolar membrane electrodialysis equipment in the situation that of electrolysis, make the reduction of being reduced property of film substance oxidation and damage, extend the work-ing life of equipment, improved 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, allow comparatively pure metabisulfite solution enter in bipolar membrane electrodialysis film group device, extend the work-ing life of equipment, improved the quality of product;
Described metabisulfite solution after secondary prefiltration passes through activated-carbon device again, can effectively remove organic substance and some fine particles, avoid organic substance enrichment and affect the performance of film in the Bipolar Membrane equipment, extended the work-ing life of equipment, improved yield and the quality of product;
Described metabisulfite solution after activated carbon treatment, through ion exchange resin system, is removed the remaining zine ion in solution, makes divalent-metal ion drop to minimum on the impact of bipolar membrane electrodialysis;
The described metabisulfite solution through ion exchange resin system through the filter of pp millipore filter essence, can obtain meeting the treatment solution that enters bipolar membrane electrodialysis film group device index again;
The sulphuric acid soln that described simmer down to is 1g/l by concentration control adopts method of evaporation to concentrate; After concentrated, the sulphuric acid soln that concentration control is 80g/l is transported to and in the acid bath operation that viscose fiber produces, carries out sulfuric acid and add, and forms online sulfuric acid circulation recycling system; The sodium hydroxide solution that is 5g/l by concentration control adopts method of evaporation to concentrate, the sodium hydroxide solution that concentration control is 50% after method of evaporation is concentrated is transported to sheet steeping operation that viscose fiber produces, soda cellulose sulphonate dissolution process, waste gas absorption operation, concise compressing and washing carried out sodium hydroxide in operation and sour water neutralizing treatment operation and added, and forms online alkali circulation recycling system.Reduce the input amount of sulfuric acid and sodium hydroxide, thereby reduced viscose fiber production cost.
In described treatment solution, 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 solution is 5 ° of C.
In described crystallisation step, Tc is 40 ℃, and crystallization time is 30min, obtains 92% sodium sulfate crystal.
Described gac is removed in organism step, adopts corpuscular active carbon adsorption column.
In described pp millipore filtration essence filter step, in PP strainer, the aperture of micropore filtering film is 0.22 micron.
Flame filter press and PP strainer are physical filtering, and flame filter press filters out a certain size large granular impurity and the suspended substance in metabisulfite solution, and PP strainer filters out the material of the small radii in metabisulfite solution.
The present invention adopts a kind of bipolar membrane electrodialysis method that applicant applies for simultaneously to process the method for viscose fiber sodium sulfate waste liquid in when application, the viscose fiber sodium sulfate waste liquid that is 5% by sodium sulfate concentration through crystallization, regulate pH, prefiltration, O
3oxidation-reduction quality material, secondary prefiltration, gac are removed organism, ion exchange resin is removed zine ion and the filter of pp millipore filtration essence, then enter in the sodium sulfate runner of bipolar membrane electrodialysis film group device; Enter respectively as the de-mineralized water of absorption liquid in the sour runner and alkali runner of bipolar membrane electrodialysis film group device, make sulphuric acid soln 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 using polyethylene and ethene and octene copolymer elastomerics and polyisobutylene rubber tertiary blending is as basilar membrane, immerse containing in the solution of vinylbenzene, 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.
In the time of concrete use, 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), evaporation concentration equipment and heat pump; Adopt heat pump to the processing of lowering the temperature of bipolar membrane electrodialysis film group device, heat pump can recycle heat recuperation to evaporation concentration equipment.
The cleaning step of bipolar membrane electrodialysis film group device comprises: 1, pass into de-mineralized water toward the sodium sulfate loop exit place of bipolar membrane electrodialysis film group device bipolar membrane electrodialysis film group device is carried out to back flushing to remove equipment runner and the less particulate matter of Bipolar Membrane adhering on surface, till back flushing is normal to working pressure; 2, be till 25 degree, the compound concentration sodium hydroxide solution that is 1% recovers to electric current Bipolar Membrane surface wash cycles by temperature.
Embodiment 2
Viscose fiber sodium sulfate waste liquid adopts bipolar membrane electrodialysis method to reclaim a method for soda acid, comprises the following steps successively: crystallization, regulate pH, prefiltration, O
3oxidation-reduction quality material, secondary prefiltration, gac removal organism, ion exchange resin removal zine ion, the filter of pp millipore filtration essence, soda acid are produced and are concentrated;
Described crystallization by by viscose fiber strand moulding process generation sodium sulphate content be 300g/L waste liquid generates sodium sulfate crystal by high temperature crystallization;
Described adjusting pH is for first dissolving sodium sulfate crystal with de-mineralized water, obtain concentration and be 7% metabisulfite solution, in metabisulfite solution, add sodium carbonate again, by pH modulation 9, add the sodium carbonate can be by maximized the zine ion in metabisulfite solution precipitation, be easy to separate, allow the metabisulfite solution of the few zine ion of content enter in bipolar membrane electrodialysis film group device, extend the work-ing life of equipment, improved 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, remove zine ion throw out, allow comparatively pure metabisulfite solution enter in bipolar membrane electrodialysis film group device, extended the work-ing life of equipment, improved the quality of product;
Described metabisulfite solution after a prefiltration, adopts O
3oxidation style is removed the reducing substances of metabisulfite solution, allow comparatively pure metabisulfite solution enter in bipolar membrane electrodialysis film group device, avoid bipolar membrane electrodialysis equipment in the situation that of electrolysis, make the reduction of being reduced property of film substance oxidation and damage, extend the work-ing life of equipment, improved 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, allow comparatively pure metabisulfite solution enter in bipolar membrane electrodialysis film group device, extend the work-ing life of equipment, improved the quality of product;
Described metabisulfite solution after secondary prefiltration passes through activated-carbon device again, can effectively remove organic substance and some fine particles, avoid organic substance enrichment and affect the performance of film in the Bipolar Membrane equipment, extended the work-ing life of equipment, improved yield and the quality of product;
Described metabisulfite solution after activated carbon treatment, through ion exchange resin system, is removed the remaining zine ion in solution, makes divalent-metal ion drop to minimum on the impact of bipolar membrane electrodialysis;
The described metabisulfite solution through ion exchange resin system through the filter of pp millipore filter essence, can obtain meeting the treatment solution that enters bipolar membrane electrodialysis film group device index again;
The sulphuric acid soln that described simmer down to is 10g/l by concentration control adopts method of evaporation to concentrate; After concentrated, the sulphuric acid soln that concentration control is 100g/l is transported to and in the acid bath operation that viscose fiber produces, carries out sulfuric acid and add, and forms online sulfuric acid circulation recycling system; The sodium hydroxide solution that is 10g/l by concentration control adopts method of evaporation to concentrate, the sodium hydroxide solution that concentration control is 60% after method of evaporation is concentrated is transported to sheet steeping operation that viscose fiber produces, soda cellulose sulphonate dissolution process, waste gas absorption operation, concise compressing and washing carried out sodium hydroxide in operation and sour water neutralizing treatment operation and added, and forms online alkali circulation recycling system.Reduce the input amount of sulfuric acid and sodium hydroxide, thereby reduced viscose fiber production cost.
In described treatment solution, 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 solution is 20 ° of C.
In described crystallisation step, Tc is 60 ℃, and crystallization time is 15min, obtains 92% sodium sulfate crystal.
Described gac is removed in organism step, adopts corpuscular active carbon adsorption column.
In described pp millipore filtration essence filter step, in PP strainer, the aperture of micropore filtering film is 0.22 micron.
Flame filter press and PP strainer are physical filtering, and flame filter press filters out a certain size large granular impurity and the suspended substance in metabisulfite solution, and PP strainer filters out the material of the small radii in metabisulfite solution.
The present invention adopts a kind of bipolar membrane electrodialysis method that applicant applies for simultaneously to process the method for viscose fiber sodium sulfate waste liquid in when application, the viscose fiber sodium sulfate waste liquid that is 10% by sodium sulfate concentration through crystallization, regulate pH, prefiltration, O
3oxidation-reduction quality material, secondary prefiltration, gac are removed organism, ion exchange resin is removed zine ion and the filter of pp millipore filtration essence, then enter in the sodium sulfate runner of bipolar membrane electrodialysis film group device; Enter respectively as the de-mineralized water of absorption liquid in the sour runner and alkali runner of bipolar membrane electrodialysis film group device, make sulphuric acid soln 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 using polyethylene and ethene and octene copolymer elastomerics and polyisobutylene rubber tertiary blending is as basilar membrane, immerse containing in the solution of vinylbenzene, 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.
In the time of concrete use, 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), evaporation concentration equipment and heat pump; Adopt heat pump to the processing of lowering the temperature of bipolar membrane electrodialysis film group device, heat pump can recycle heat recuperation to evaporation concentration equipment.
The cleaning step of bipolar membrane electrodialysis film group device comprises: 1, pass into de-mineralized water toward the sodium sulfate loop exit place of bipolar membrane electrodialysis film group device bipolar membrane electrodialysis film group device is carried out to back flushing to remove equipment runner and the less particulate matter of Bipolar Membrane adhering on surface, till back flushing is normal to working pressure; 2, be till 28 degree, the compound concentration sodium hydroxide solution that is 2% recovers to electric current Bipolar Membrane surface wash cycles by temperature.
Embodiment 3
Viscose fiber sodium sulfate waste liquid adopts bipolar membrane electrodialysis method to reclaim a method for soda acid, comprises the following steps successively: crystallization, regulate pH, prefiltration, O
3oxidation-reduction quality material, secondary prefiltration, gac removal organism, ion exchange resin removal zine ion, the filter of pp millipore filtration essence, soda acid are produced and are concentrated;
Described crystallization by by viscose fiber strand moulding process generation sodium sulphate content be 300g/L waste liquid generates sodium sulfate crystal by high temperature crystallization;
Described adjusting pH is for first dissolving sodium sulfate crystal with de-mineralized water, obtain concentration and be 12% metabisulfite solution, in metabisulfite solution, add sodium carbonate again, by pH modulation 9, add the sodium carbonate can be by maximized the zine ion in metabisulfite solution precipitation, be easy to separate, allow the metabisulfite solution of the few zine ion of content enter in bipolar membrane electrodialysis film group device, extend the work-ing life of equipment, improved 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, remove zine ion throw out, allow comparatively pure metabisulfite solution enter in bipolar membrane electrodialysis film group device, extended the work-ing life of equipment, improved the quality of product;
Described metabisulfite solution after a prefiltration, adopts O
3oxidation style is removed the reducing substances of metabisulfite solution, allow comparatively pure metabisulfite solution enter in bipolar membrane electrodialysis film group device, avoid bipolar membrane electrodialysis equipment in the situation that of electrolysis, make the reduction of being reduced property of film substance oxidation and damage, extend the work-ing life of equipment, improved 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, allow comparatively pure metabisulfite solution enter in bipolar membrane electrodialysis film group device, extend the work-ing life of equipment, improved the quality of product;
Described metabisulfite solution after secondary prefiltration passes through activated-carbon device again, can effectively remove organic substance and some fine particles, avoid organic substance enrichment and affect the performance of film in the Bipolar Membrane equipment, extended the work-ing life of equipment, improved yield and the quality of product;
Described metabisulfite solution after activated carbon treatment, through ion exchange resin system, is removed the remaining zine ion in solution, makes divalent-metal ion drop to minimum on the impact of bipolar membrane electrodialysis;
The described metabisulfite solution through ion exchange resin system through the filter of pp millipore filter essence, can obtain meeting the treatment solution that enters bipolar membrane electrodialysis film group device index again;
The sulphuric acid soln that described simmer down to is 15g/l by concentration control adopts method of evaporation to concentrate; After concentrated, the sulphuric acid soln that concentration control is 150g/l is transported to and in the acid bath operation that viscose fiber produces, carries out sulfuric acid and add, and forms online sulfuric acid circulation recycling system; The sodium hydroxide solution that is 15g/l by concentration control adopts method of evaporation to concentrate, the sodium hydroxide solution that concentration control is 70% after method of evaporation is concentrated is transported to sheet steeping operation that viscose fiber produces, soda cellulose sulphonate dissolution process, waste gas absorption operation, concise compressing and washing carried out sodium hydroxide in operation and sour water neutralizing treatment operation and added, and forms online alkali circulation recycling system.Reduce the input amount of sulfuric acid and sodium hydroxide, thereby reduced viscose fiber production cost.
In described treatment solution, 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 solution is 20 ° of C.
In described crystallisation step, Tc is 60 ℃, and crystallization time is 15min, obtains 92% sodium sulfate crystal.
Described gac is removed in organism step, adopts corpuscular active carbon adsorption column.
In described pp millipore filtration essence filter step, in PP strainer, the aperture of micropore filtering film is 0.22 micron.
Flame filter press and PP strainer are physical filtering, and flame filter press filters out a certain size large granular impurity and the suspended substance in metabisulfite solution, and PP strainer filters out the material of the small radii in metabisulfite solution.
The present invention adopts a kind of bipolar membrane electrodialysis method that applicant applies for simultaneously to process the method for viscose fiber sodium sulfate waste liquid in when application, the viscose fiber sodium sulfate waste liquid that is 15% by sodium sulfate concentration through crystallization, regulate pH, prefiltration, O
3oxidation-reduction quality material, secondary prefiltration, gac are removed organism, ion exchange resin is removed zine ion and the filter of pp millipore filtration essence, then enter in the sodium sulfate runner of bipolar membrane electrodialysis film group device; Enter respectively as the de-mineralized water of absorption liquid in the sour runner and alkali runner of bipolar membrane electrodialysis film group device, make sulphuric acid soln 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 using polyethylene and ethene and octene copolymer elastomerics and polyisobutylene rubber tertiary blending is as basilar membrane, immerse containing in the solution of vinylbenzene, 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.
In the time of concrete use, 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), evaporation concentration equipment and heat pump; Adopt heat pump to the processing of lowering the temperature of bipolar membrane electrodialysis film group device, heat pump can recycle heat recuperation to evaporation concentration equipment.
The cleaning step of bipolar membrane electrodialysis film group device comprises: 1, pass into de-mineralized water toward the sodium sulfate loop exit place of bipolar membrane electrodialysis film group device bipolar membrane electrodialysis film group device is carried out to back flushing to remove equipment runner and the less particulate matter of Bipolar Membrane adhering on surface, till back flushing is normal to working pressure; 2, be till 30 degree, the compound concentration sodium hydroxide solution that is 3% recovers to electric current Bipolar Membrane surface wash cycles by temperature.
Embodiment 4
Viscose fiber sodium sulfate waste liquid adopts bipolar membrane electrodialysis method to reclaim a method for soda acid, comprises the following steps successively: crystallization, regulate pH, prefiltration, O
3oxidation-reduction quality material, secondary prefiltration, gac removal organism, ion exchange resin removal zine ion, the filter of pp millipore filtration essence, soda acid are produced and are concentrated;
Described crystallization by by viscose fiber strand moulding process generation sodium sulphate content be 400g/L waste liquid generates sodium sulfate crystal by high temperature crystallization;
Described adjusting pH is for first dissolving sodium sulfate crystal with de-mineralized water, obtain concentration and be 15% metabisulfite solution, in metabisulfite solution, add sodium carbonate again, by pH modulation 10, add the sodium carbonate can be by maximized the zine ion in metabisulfite solution precipitation, be easy to separate, allow the metabisulfite solution of the few zine ion of content enter in bipolar membrane electrodialysis film group device, extend the work-ing life of equipment, improved 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, remove zine ion throw out, allow comparatively pure metabisulfite solution enter in bipolar membrane electrodialysis film group device, extended the work-ing life of equipment, improved the quality of product;
Described metabisulfite solution after a prefiltration, adopts O
3oxidation style is removed the reducing substances of metabisulfite solution, allow comparatively pure metabisulfite solution enter in bipolar membrane electrodialysis film group device, avoid bipolar membrane electrodialysis equipment in the situation that of electrolysis, make the reduction of being reduced property of film substance oxidation and damage, extend the work-ing life of equipment, improved 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, allow comparatively pure metabisulfite solution enter in bipolar membrane electrodialysis film group device, extend the work-ing life of equipment, improved the quality of product;
Described metabisulfite solution after secondary prefiltration passes through activated-carbon device again, can effectively remove organic substance and some fine particles, avoid organic substance enrichment and affect the performance of film in the Bipolar Membrane equipment, extended the work-ing life of equipment, improved yield and the quality of product;
Described metabisulfite solution after activated carbon treatment, through ion exchange resin system, is removed the remaining zine ion in solution, makes divalent-metal ion drop to minimum on the impact of bipolar membrane electrodialysis;
The described metabisulfite solution through ion exchange resin system through the filter of pp millipore filter essence, can obtain meeting the treatment solution that enters bipolar membrane electrodialysis film group device index again;
The sulphuric acid soln that described simmer down to is 30g/l by concentration control adopts method of evaporation to concentrate; After concentrated, the sulphuric acid soln that concentration control is 320g/l is transported to and in the acid bath operation that viscose fiber produces, carries out sulfuric acid and add, and forms online sulfuric acid circulation recycling system; The sodium hydroxide solution that is 80g/l by concentration control adopts method of evaporation to concentrate, the sodium hydroxide solution that concentration control is 95% after method of evaporation is concentrated is transported to sheet steeping operation that viscose fiber produces, soda cellulose sulphonate dissolution process, waste gas absorption operation, concise compressing and washing carried out sodium hydroxide in operation and sour water neutralizing treatment operation and added, and forms online alkali circulation recycling system.Reduce the input amount of sulfuric acid and sodium hydroxide, thereby reduced viscose fiber production cost.
In described treatment solution, 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 solution is 35 ° of C.
In described crystallisation step, Tc is 80 ℃, and crystallization time is 5min, obtains 92% sodium sulfate crystal.
Described gac is removed in organism step, adopts corpuscular active carbon adsorption column.
In described pp millipore filtration essence filter step, in PP strainer, the aperture of micropore filtering film is 0.22 micron.
Flame filter press and PP strainer are physical filtering, and flame filter press filters out a certain size large granular impurity and the suspended substance in metabisulfite solution, and PP strainer filters out the material of the small radii in metabisulfite solution.
The present invention adopts a kind of bipolar membrane electrodialysis method that applicant applies for simultaneously to process the method for viscose fiber sodium sulfate waste liquid in when application, the viscose fiber sodium sulfate waste liquid that is 20% by sodium sulfate concentration through crystallization, regulate pH, prefiltration, O
3oxidation-reduction quality material, secondary prefiltration, gac are removed organism, ion exchange resin is removed zine ion and the filter of pp millipore filtration essence, then enter in the sodium sulfate runner of bipolar membrane electrodialysis film group device; Enter respectively as the de-mineralized water of absorption liquid in the sour runner and alkali runner of bipolar membrane electrodialysis film group device, make sulphuric acid soln 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 using polyethylene and ethene and octene copolymer elastomerics and polyisobutylene rubber tertiary blending is as basilar membrane, immerse containing in the solution of vinylbenzene, 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.
In the time of concrete use, 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), evaporation concentration equipment and heat pump; Adopt heat pump to the processing of lowering the temperature of bipolar membrane electrodialysis film group device, heat pump can recycle heat recuperation to evaporation concentration equipment.
The cleaning step of bipolar membrane electrodialysis film group device comprises: 1, pass into de-mineralized water toward the sodium sulfate loop exit place of bipolar membrane electrodialysis film group device bipolar membrane electrodialysis film group device is carried out to back flushing to remove equipment runner and the less particulate matter of Bipolar Membrane adhering on surface, till back flushing is normal to working pressure; 2, be till 35 degree, the compound concentration sodium hydroxide solution that is 5% recovers to electric current Bipolar Membrane surface wash cycles by temperature.
Embodiment 5
The present invention can obtain between alkali lye or crystal that alkali concn control is 50%-100% method of evaporation is concentrated, can carry out successively that reverse osmosis method is concentrated, electroosmose process concentrated, low-temperature multi-effect method is concentrated and multiple-effect evaporation method is concentrated is concentrated to the concentration of alkali lye in the scope of 30%-50% gradually, can obtain through method of evaporation is concentrated alkali lye or the crystal that alkali concn control is 50%-100% again, further improve the concentration that reclaims alkali; Be recovered to that viscose glue produces with carrying out adding of alkali in alkali operation, reduce production costs, particularly alkali concn control is that 96%, 98% and 99% sodium hydroxide crystal can direct marketing, brings benefits.
Claims (6)
1. viscose fiber sodium sulfate waste liquid adopts bipolar membrane electrodialysis method to reclaim a method for soda acid, it is characterized in that comprising the following steps successively: crystallization, regulate pH, prefiltration, O
3oxidation-reduction quality material, secondary prefiltration, gac removal organism, ion exchange resin removal zine ion, the filter of pp millipore filtration essence, soda acid are produced and are concentrated;
Described crystallization by by viscose fiber strand moulding process generation sodium sulphate content be 200-400g/L waste liquid generates sodium sulfate crystal by high temperature crystallization;
Described adjusting pH, for first dissolving sodium sulfate crystal with de-mineralized water, obtains the metabisulfite solution that concentration is 3%-15%, then adds sodium carbonate in metabisulfite solution, and pH is modulated to 8-10;
Described process adds the metabisulfite solution of sodium carbonate depositing zinc ion, and through a prefiltration, a plate filter, removes zine ion throw out;
Described metabisulfite solution after a prefiltration, adopts O
3oxidation style is removed 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 passes through activated-carbon device again, removes organic substance and some fine particles;
Described metabisulfite solution after activated carbon treatment, through ion exchange resin system, is removed the remaining zine ion in solution;
The described metabisulfite solution through ion exchange resin system through the filter of pp millipore filter essence, obtains meeting the treatment solution that enters bipolar membrane electrodialysis film group device index again;
Described soda acid is produced and is obtained through bipolar membrane electrodialysis legal system the sodium hydroxide solution that sulphuric acid soln that concentration control is 1-30g/l and concentration control are 5-80g/l for treatment solution;
The sulphuric acid soln that described simmer down to is 1-30g/l by concentration control adopts method of evaporation; After concentrated, obtain the sulphuric acid soln that concentration control is 80-320g/l; The sodium hydroxide solution that is 5-80g/l by concentration control adopts method of evaporation to concentrate, and after method of evaporation is concentrated, obtains the sodium hydroxide solution that concentration control is 50%-100%.
2. a kind of viscose fiber sodium sulfate waste liquid adopts bipolar membrane electrodialysis method to reclaim the method for soda acid according to claim 1, it is characterized in that: in described treatment solution, ss concentration is less than 5mg/l, COD is less than 60mg/l, and zinc ion concentration is less than 5mg/l, and the temperature for the treatment of solution is 5-35 ℃.
3. a kind of viscose fiber sodium sulfate waste liquid adopts bipolar membrane electrodialysis method to reclaim the method for soda acid according to claim 1, it is characterized in that: in described crystallisation step, Tc is 40-80 ℃, and crystallization time is 5-30min, obtains 92% sodium sulfate crystal.
4. a kind of viscose fiber sodium sulfate waste liquid adopts bipolar membrane electrodialysis method to reclaim the method for soda acid according to claim 1, it is characterized in that: described gac is removed in organism step, adopts corpuscular active carbon adsorption column.
5. a kind of viscose fiber sodium sulfate waste liquid adopts bipolar membrane electrodialysis method to reclaim the method for soda acid according to claim 1, it is characterized in that: in described pp millipore filtration essence filter step, in PP strainer, the aperture of micropore filtering film is 0.22-1 micron.
6. a kind of viscose fiber sodium sulfate waste liquid adopts bipolar membrane electrodialysis method to reclaim the method for soda acid according to claim 1, it is characterized in that: flame filter press and PP strainer are physical filtering, flame filter press filters out a certain size large granular impurity and the suspended substance in metabisulfite solution, and PP strainer filters out the material of the small radii in 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 |
| CN109133446A (en) * | 2018-11-06 | 2019-01-04 | 宜宾海丝特纤维有限责任公司 | A kind of on-line control system and method for viscose glue waste liquid |
| CN109437213A (en) * | 2018-12-10 | 2019-03-08 | 四川绿沃创新环保工程有限公司 | A kind of process for reclaiming producing white carbon black using rice hull ash as raw material |
| CN109731534B (en) * | 2018-12-28 | 2021-05-11 | 中国纺织科学研究院有限公司 | Method for purifying soluble fiber coagulating bath |
| 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 |
| CN112758957A (en) * | 2020-12-28 | 2021-05-07 | 宜宾丝丽雅股份有限公司 | Process for purifying sodium hydroxide concentration by electrodialysis |
| CN112853550A (en) * | 2020-12-28 | 2021-05-28 | 宜宾丝丽雅股份有限公司 | Treatment method for recycling alkali liquor |
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| US6627061B2 (en) * | 1999-05-05 | 2003-09-30 | Archer-Daniels-Midland Company | Apparatus and process for electrodialysis of salts |
| CN101928084B (en) * | 2009-06-23 | 2012-06-27 | 笹仓机械工程有限公司 | Treatment method and device of liquid waste containing inorganic salt |
| CN102107972B (en) * | 2010-12-01 | 2012-05-23 | 杭州水处理技术研究开发中心有限公司 | Seawater desalinization pretreatment method by using bipolar membrane through reverse osmosis process |
| 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 |
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Denomination of invention: A method for recovering acid and alkali from sodium sulfate waste liquid of viscose fiber using bipolar membrane electrodialysis Granted publication date: 20140702 Pledgee: Yibin Development Holding Group Co.,Ltd. Pledgor: YIBIN GRACE GROUP Co.,Ltd.|YIBIN GRACE Co.,Ltd.|YIBIN HIEST FIBRE Ltd.,Corp.|YIBIN HAIXIANG CHEMICAL CO.,LTD. Registration number: Y2024980030863 |