CN103361769B - Viscose sodium sulfate waste liquor reclaims the method for soda acid through bipolar membrane electrodialysis method - Google Patents
Viscose sodium sulfate waste liquor reclaims the method for soda acid through bipolar membrane electrodialysis method Download PDFInfo
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- 239000012528 membrane Substances 0.000 title claims abstract description 174
- 238000000909 electrodialysis Methods 0.000 title claims abstract description 119
- 238000000034 method Methods 0.000 title claims abstract description 118
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 title claims abstract description 93
- 229910052938 sodium sulfate Inorganic materials 0.000 title claims abstract description 69
- 235000011152 sodium sulphate Nutrition 0.000 title claims abstract description 69
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 title claims abstract description 68
- 229920000297 Rayon Polymers 0.000 title claims abstract description 57
- 239000002253 acid Substances 0.000 title claims abstract description 56
- 239000002699 waste material Substances 0.000 title claims abstract description 44
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims abstract description 45
- 238000002425 crystallisation Methods 0.000 claims abstract description 43
- 238000011045 prefiltration Methods 0.000 claims abstract description 40
- 239000000126 substance Substances 0.000 claims abstract description 39
- 230000008025 crystallization Effects 0.000 claims abstract description 37
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000007788 liquid Substances 0.000 claims abstract description 30
- 238000001914 filtration Methods 0.000 claims abstract description 29
- 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
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 23
- 239000003456 ion exchange resin Substances 0.000 claims abstract description 23
- 229920003303 ion-exchange polymer Polymers 0.000 claims abstract description 23
- 239000012535 impurity Substances 0.000 claims abstract description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 141
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 94
- WBZKQQHYRPRKNJ-UHFFFAOYSA-L disulfite Chemical compound [O-]S(=O)S([O-])(=O)=O WBZKQQHYRPRKNJ-UHFFFAOYSA-L 0.000 claims description 94
- 230000008569 process Effects 0.000 claims description 63
- 239000012530 fluid Substances 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000013078 crystal Substances 0.000 claims description 19
- 239000012141 concentrate Substances 0.000 claims description 18
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 17
- 230000003647 oxidation Effects 0.000 claims description 10
- 238000007254 oxidation reaction Methods 0.000 claims description 10
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- 238000001179 sorption measurement Methods 0.000 claims description 6
- 238000011084 recovery Methods 0.000 abstract description 8
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- 150000007516 brønsted-lowry acids Chemical class 0.000 abstract description 3
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- 239000003513 alkali Substances 0.000 description 31
- 239000000047 product Substances 0.000 description 24
- 238000005516 engineering process Methods 0.000 description 12
- 230000001112 coagulating effect Effects 0.000 description 11
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 8
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 8
- 210000002469 basement membrane Anatomy 0.000 description 8
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- 238000004140 cleaning Methods 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- -1 sulphonic acid ester Chemical class 0.000 description 8
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- 239000004342 Benzoyl peroxide Substances 0.000 description 4
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- 235000001018 Hibiscus sabdariffa Nutrition 0.000 description 4
- 229920005987 OPPANOL® Polymers 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 4
- 235000005291 Rumex acetosa Nutrition 0.000 description 4
- 240000007001 Rumex acetosella Species 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 4
- 235000019400 benzoyl peroxide Nutrition 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 229920001971 elastomer Polymers 0.000 description 4
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- 238000010438 heat treatment Methods 0.000 description 4
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- 229920000573 polyethylene Polymers 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
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- 235000003513 sheep sorrel Nutrition 0.000 description 4
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- 238000005349 anion exchange Methods 0.000 description 3
- 238000005341 cation exchange Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000009987 spinning Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
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- 238000006243 chemical reaction Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010612 desalination reaction Methods 0.000 description 2
- 238000010494 dissociation reaction Methods 0.000 description 2
- 230000005593 dissociations Effects 0.000 description 2
- 239000010446 mirabilite Substances 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 239000013535 sea water Substances 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229920002488 Hemicellulose Polymers 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
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- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000011033 desalting Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000002384 drinking water standard Substances 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000005685 electric field effect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000003203 everyday effect Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000005496 tempering Methods 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
- Y02P70/62—Manufacturing or production processes characterised by the final manufactured product related technologies for production or treatment of textile or flexible materials or products thereof, including footwear
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
The invention discloses viscose sodium sulfate waste liquor reclaims soda acid method through bipolar membrane electrodialysis method, comprise 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; Invention increases 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 service life of Bipolar Membrane, and ensure carrying out smoothly of bipolar membrane electrodialysis and subsequent handling.
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 viscose sodium sulfate waste liquor reclaims soda acid method 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, and it is composited by cation exchange layer (N-type film), interface hydrophilic layer (Catalytic Layer) and anion exchange layer (P type film) usually, is reaction film truly.Under 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-term the 1950's, its evolution can be divided into three phases: mid-term the 1950's first stage is to the initial stage eighties, 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 early 1980s to the 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 early 1990s 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 initial simple " pressure stratotype " or " coating type " structure to early 1980s, 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, viscose sodium sulfate waste liquor is provided to reclaim the method for 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 the method 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 electroosmose process to concentrate 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 electroosmose process to concentrate; After concentrated, concentration control for the sodium hydroxide solution of 6%-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.
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 acid in viscose waste liquid, the rate of recovery of alkali and hemicellulose, decrease the damage that waste liquid causes Bipolar Membrane, improve the service life of Bipolar Membrane, and ensure carrying out smoothly of bipolar membrane electrodialysis and subsequent handling, improve the organic efficiency of soda acid.
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 6%-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 electroosmose process to concentrate soda acid respectively, when reclaiming the alkali lye that concentration controls as 6%-15%, and Be very effective, cost-saving, can directly reclaim; Also alkali concn can be increased to and be applicable in the concentrated concentration range of low-temperature multi-effect method, then after low-temperature multi-effect method concentrates, reclaim the alkali lye that concentration control is 15%-30%.
Detailed description of the invention
Below enforcement of the present invention is illustrated:
Embodiment 1
Viscose sodium sulfate waste liquor reclaims the method 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 electroosmose process to concentrate 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 electroosmose process to concentrate; After concentrated, concentration control be 6% sodium hydroxide solution be transported to and carry out NaOH in the sheet steeping operation that viscose produces 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 5-35 ° 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 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 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 the method 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 electroosmose process to concentrate 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 electroosmose process to concentrate; After concentrated, concentration control be 9% sodium hydroxide solution be transported to and carry out NaOH in the alkali cellulose sulphonic acid ester dissolution process that viscose produces 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 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 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 the method 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 electroosmose process to concentrate 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 electroosmose process to concentrate; After concentrated, concentration control be 13% sodium hydroxide solution be transported to and carry out NaOH in the waste gas absorption operation that viscose produces 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 0.06MPa.
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 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 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 the method 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 electroosmose process to concentrate 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 electroosmose process to concentrate; After concentrated, 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 0.08MPa.
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 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 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.
Claims (4)
1. viscose sodium sulfate waste liquor reclaims the method 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;
Described process adds the metabisulfite solution of sodium carbonate depositing zinc ion, through a prefiltration, an i.e. flame filter press, 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;
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 electroosmose process to concentrate 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 electroosmose process to concentrate; After concentrated, obtain the sodium hydroxide solution that concentration control is 6%-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 DEG 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%.
2. viscose sodium sulfate waste liquor reclaims the method for 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.
3. viscose sodium sulfate waste liquor reclaims the method for 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 millipore filter, the aperture of micropore filtering film is 0.22-1 micron.
4. viscose sodium sulfate waste liquor reclaims the method for soda acid through bipolar membrane electrodialysis method according to claim 1, it is characterized in that: flame filter press and pp millipore filter are physical filtering, flame filter press filters out a certain size large granular impurity in metabisulfite solution and suspended matter, and pp millipore filter filters out the material of the small radii in metabisulfite solution.
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| CN102874958A (en) * | 2011-07-11 | 2013-01-16 | 凯膜过滤技术(上海)有限公司 | Method for treating and reusing sodium sulfate containing organic waste water |
| CN102584606A (en) * | 2011-12-28 | 2012-07-18 | 浙江工业大学 | Method for preparing aminopropanol by bipolar membrane electrodialysis |
| 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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Denomination of invention: Method for recovering acid and alkali from sodium sulfate waste liquid of viscose fiber by bipolar membrane electrodialysis Granted publication date: 20160210 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 |
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