CN208667350U - Multi-membrane integrated pulping and papermaking wastewater zero-discharge treatment device - Google Patents
Multi-membrane integrated pulping and papermaking wastewater zero-discharge treatment device Download PDFInfo
- Publication number
- CN208667350U CN208667350U CN201821121501.5U CN201821121501U CN208667350U CN 208667350 U CN208667350 U CN 208667350U CN 201821121501 U CN201821121501 U CN 201821121501U CN 208667350 U CN208667350 U CN 208667350U
- Authority
- CN
- China
- Prior art keywords
- membrane
- water
- nanofiltration
- reverse osmosis
- concentration
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000012528 membrane Substances 0.000 title claims abstract description 130
- 239000002351 wastewater Substances 0.000 title claims abstract description 95
- 238000004537 pulping Methods 0.000 title claims abstract description 15
- 208000028659 discharge Diseases 0.000 title abstract description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 153
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 141
- 238000001728 nano-filtration Methods 0.000 claims abstract description 83
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 78
- 239000011780 sodium chloride Substances 0.000 claims abstract description 71
- 238000001223 reverse osmosis Methods 0.000 claims abstract description 69
- 150000003839 salts Chemical class 0.000 claims abstract description 56
- 238000002425 crystallisation Methods 0.000 claims abstract description 52
- 230000008025 crystallization Effects 0.000 claims abstract description 47
- 238000000108 ultra-filtration Methods 0.000 claims abstract description 47
- 239000013505 freshwater Substances 0.000 claims abstract description 36
- 239000007788 liquid Substances 0.000 claims abstract description 14
- 239000012535 impurity Substances 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims description 145
- 230000008569 process Effects 0.000 claims description 79
- 239000013078 crystal Substances 0.000 claims description 51
- 239000012452 mother liquor Substances 0.000 claims description 22
- 239000011734 sodium Substances 0.000 claims description 21
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 18
- 239000012141 concentrate Substances 0.000 claims description 13
- 238000007254 oxidation reaction Methods 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 9
- 230000003647 oxidation Effects 0.000 claims description 9
- 229910052708 sodium Inorganic materials 0.000 claims description 9
- 238000000909 electrodialysis Methods 0.000 claims description 8
- 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 claims description 7
- 230000007717 exclusion Effects 0.000 claims description 6
- 239000003814 drug Substances 0.000 claims description 5
- 238000001704 evaporation Methods 0.000 claims description 5
- 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 description 4
- 239000003546 flue gas Substances 0.000 claims description 4
- 239000003456 ion exchange resin Substances 0.000 claims description 4
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 4
- 239000000706 filtrate Substances 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 abstract description 78
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 abstract description 73
- 235000011152 sodium sulphate Nutrition 0.000 abstract description 49
- 239000007832 Na2SO4 Substances 0.000 abstract description 29
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 35
- 239000002253 acid Substances 0.000 description 31
- 238000004519 manufacturing process Methods 0.000 description 27
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 22
- 235000011121 sodium hydroxide Nutrition 0.000 description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 18
- 239000010842 industrial wastewater Substances 0.000 description 17
- 238000011084 recovery Methods 0.000 description 16
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 12
- 238000001914 filtration Methods 0.000 description 11
- 238000005516 engineering process Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 229910052799 carbon Inorganic materials 0.000 description 8
- 238000009287 sand filtration Methods 0.000 description 7
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 6
- 229910000019 calcium carbonate Inorganic materials 0.000 description 6
- 230000004907 flux Effects 0.000 description 6
- 239000010413 mother solution Substances 0.000 description 6
- 239000012267 brine Substances 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 5
- 238000010168 coupling process Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 5
- 238000004065 wastewater treatment Methods 0.000 description 5
- 239000004952 Polyamide Substances 0.000 description 4
- 239000004642 Polyimide Substances 0.000 description 4
- 229920002301 cellulose acetate Polymers 0.000 description 4
- 238000005660 chlorination reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229920002647 polyamide Polymers 0.000 description 4
- 229920001721 polyimide Polymers 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000003825 pressing Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- 230000008878 coupling Effects 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- -1 deliming Chemical class 0.000 description 3
- 238000010612 desalination reaction Methods 0.000 description 3
- WBZKQQHYRPRKNJ-UHFFFAOYSA-L disulfite Chemical compound [O-]S(=O)S([O-])(=O)=O WBZKQQHYRPRKNJ-UHFFFAOYSA-L 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 230000011218 segmentation Effects 0.000 description 3
- PANBYUAFMMOFOV-UHFFFAOYSA-N sodium;sulfuric acid Chemical compound [Na].OS(O)(=O)=O PANBYUAFMMOFOV-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- PALNZFJYSCMLBK-UHFFFAOYSA-K magnesium;potassium;trichloride;hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[Cl-].[Cl-].[Cl-].[K+] PALNZFJYSCMLBK-UHFFFAOYSA-K 0.000 description 2
- 229920002492 poly(sulfone) Polymers 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 238000007781 pre-processing Methods 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 229940001584 sodium metabisulfite Drugs 0.000 description 2
- 235000010262 sodium metabisulphite Nutrition 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- WFLOTYSKFUPZQB-UHFFFAOYSA-N 1,2-difluoroethene Chemical group FC=CF WFLOTYSKFUPZQB-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 241000372132 Hydrometridae Species 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 206010044565 Tremor Diseases 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 235000012489 doughnuts Nutrition 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- YECIFGHRMFEPJK-UHFFFAOYSA-N lidocaine hydrochloride monohydrate Chemical compound O.[Cl-].CC[NH+](CC)CC(=O)NC1=C(C)C=CC=C1C YECIFGHRMFEPJK-UHFFFAOYSA-N 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000006396 nitration reaction Methods 0.000 description 1
- 238000012946 outsourcing Methods 0.000 description 1
- 239000010893 paper waste Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
A multi-membrane integrated pulping and papermaking wastewater zero-discharge treatment device comprises: the device comprises a pretreatment impurity removal device, an ultrafiltration membrane, a low-pressure reverse osmosis membrane, a first softening device, a high-pressure reverse osmosis membrane and a second softening device; and a first concentrating device connected to the second softening device for concentratingThe wastewater softened by the second softening device is concentrated; the nanofiltration membrane is connected with the first concentration device and is used for separating divalent salt from the produced water treated by the first concentration device; a sodium sulfate crystallization system connected to the concentrated solution side of the nanofiltration membrane for crystallizing the nanofiltration concentrated solution to obtain Na2SO4(ii) a The sodium chloride crystallization system is connected to the dilute liquid side of the nanofiltration membrane and is used for carrying out crystallization treatment on the nanofiltration dilute liquid to obtain NaCl; a first bipolar membrane electrodialyzer connected to the concentrated solution side of the nanofiltration membrane and used for preparing H from part of the concentrated water of the nanofiltration membrane2SO4And NaOH; and the second bipolar membrane electrodialyzer is connected to the fresh water side of the nanofiltration membrane and is used for preparing HCl and NaOH from a part of the fresh water of the nanofiltration membrane.
Description
Technical field
The utility model relates to the pulp and paper making wastewater zero discharge processing units that a kind of multimembrane integrates, and in particular to multimembrane collection
At the zero discharge of industrial waste water technique coupled with co-producing sodium chloride, sodium sulphate, and soda acid is prepared using bipolar membrane process and is supplied
The soda acid that system uses reduces the operating cost of entire wastewater zero discharge process.Belong to environmentally friendly water treatment field.
Background technique
The industrial wastewater treatment of the fields such as petrochemical industry, coal chemical industry, printing and dyeing, pulping and paper-making discharge is water prevention and cure of pollution action plan
In the improvement field that brings forward.This kind of industrial wastewater is with wastewater flow rate is big, salt content is high, hardness is high, sulphates content is high, difficult
The features such as COD content of degrading is high.This kind of technical scale enterprise qualified discharge water day discharge amount is more than 10,000 tons, conductivity of waste water is super
Cross 3000 μ S/cm, sulphates content is greater than 500mg/L.
Above-mentioned industrial wastewater reduces COD and SS using the techniques such as biochemistry, coarse filtration, advanced oxidation, ultrafiltration, and use is reverse osmosis
Film is concentrated, and waste water recycling can be greater than 50%.For if you need to industrial wastewater carry out zero discharge treatment, with cycles of concentration
Rise, the hardness in waste water also gradually rises.Waste water after concentrated can soften the hardness in removing waste water.Through removing hardness
Waste water obtains Nacl using evaporative crystallization technique, but should after high pressure is reverse osmosis or the techniques such as electrodialysis are further concentrated
What technique obtained is usually carnallite, and reuse ratio is low.The clear water that film concentration process generates is used for each production work according to water quality difference
Section.Such brine waste zero emission technique Chinese utility model patent (CN103508602A, CN104071808A) has been reported.
Saliferous zero discharge of industrial waste water technique is divided into circulation pretreatment, circulation minimizing by Chinese patent CN105540972A
And three parts of zero-emission unit.Sodium chloride and sulfate crystal separation are realized during evaporative crystallization technique.Technique master
It will be for monovalent salt in brine waste and divalent salts concentration difference away from greatly different system.The operating condition of control crystallization processes can be passed through
Obtain technical grade monovalent salt and divalent salts.
Chinese patent CN106517606A carries out processing to the concentrate of desulfurization wastewater using Bipolar membrane water splitting and prepares soda acid.
The technique does not separate the divalent salts in waste water, and bipolar membrane process operation is more demanding, and obtaining acid is nitration mixture.
Chinese patent CN106745076A reports a kind of process for refining of carnallite in process without drainage of waste water, by will be miscellaneous
After salt calcination processing, it is dissolved in the sodium chloride that water goes the foreign ions such as deliming, sulfate radical to obtain high-purity by dosing.The technique
Implement to obtain the sodium chloride of high-purity and need to carry out double evaporation-cooling to waste water.
Utility model content
The content of the utility model is for industrial wastewater, using multimembrane integrated technique and sodium chloride and sulfate crystal phase
In conjunction with process implementing industrial wastewater zero-emission.The concentration ratio that inorganic salts are controlled by film blending technology, meets sodium chloride
With sulfate crystal requirement.By using bipolar film preparation soda acid, drop using high concentration sodium chloride, the metabisulfite solution in system
The operating cost of low wastewater zero discharge process.
To achieve the above objectives, the present invention adopts the following technical solutions:
A kind of pulp and paper making wastewater zero discharge processing method that multimembrane is integrated, includes the following steps:
Step 1, to the preprocessed removal of impurities of the tail water of pulping and papermaking processes；
Step 2 successively carries out ultra-filtration filters and low pressure reverse osmosis filtering to waste water after pretreatment；
Step 3 successively carries out the first sofening treatment and high pressure osmosis filtration to the concentrated water of low pressure reverse osmosis；
Step 4, the concentrated water reverse osmosis to high pressure successively carry out the second sofening treatment and concentration；
Step 5, to after step 4 concentration waste water or the reverse osmosis concentrated water of step 3 high pressure use nanofiltration membrane
Processing adjusts NaCl and Na in waste water2SO4Concentration ratio；
The concentrated water of step 6, nanofiltration membrane is sent into Na2SO4Crystal system obtains Na by Crystallization Separation2SO4Nacl and
First mother liquor；The fresh water of nanofiltration membrane is concentrated and then is sent into NaCl crystal system, obtains NaCl work by Crystallization Separation
Industry salt and the second mother liquor；
Step 7, the first mother liquor, which is sent into NaCl crystal system, carries out crystallization treatment, and the second mother liquor is sent into Na2SO4System of crystallization
System carries out crystallization treatment；
The concentrated water of nanofiltration membrane a part of in step 6 is used bipolar film preparation H by step 82SO4And NaOH, by step 6 one
The fresh water of part nanofiltration membrane uses bipolar film preparation HCl and NaOH.
In one embodiment, in the step 1, pre-treatment step includes coarse filtration and advanced oxidation.
In one embodiment, in step 1 pretreatment removal of impurities water outlet COD between 10~200mg/L, SS 3~
50mg/L。
In one embodiment, ultrafiltration membrane makes waste water SDI less than 3 in step 2, and low pressure reverse osmosis makes fresh-water recovery rate
50%~75%.
In one embodiment, the first melded system water production control hardness is less than 200mg/L, high pressure reverse osmosis in step 3
Membrane system controls concentrated water salt content 5~6%.
In one embodiment, the second sofening treatment control hardness is less than 1mg/L in step 4, and concentration control is dense
Water salt content 12~20%.
In one embodiment, concentration described in step 4 refers to super-pressure reverse osmosis concentration, dish tubular type reverse osmosis
(DTRO) concentration or electrodialytic membranes concentration thoroughly.
In one embodiment, the first sofening treatment and the second sofening treatment are using film softening, lime-flue gas method, medicine
One of agent softening or ion exchange resin softening or kinds of processes combination.
In one embodiment, in step 5 nanofiltration membrane concentrated water sodium sulfate quality concentration be higher than 8%, preferred concentration 12%~
Between 20%.
In one embodiment, the first mother liquor is carried out by being concentrated to be re-fed into NaCl crystal system later in step 7
Crystallization treatment, the second mother liquor are re-fed into Na after crossing concentration2SO4Crystal system carries out crystallization treatment.
In the step 8, NaOH is used for Membrane cleaning, HCl and H2SO4It is adjusted for the pH of Membrane cleaning and waste water.
In the step 8, NaOH mass concentration is 6~8%；Control HCl mass concentration 5~7%, H2SO4Mass concentration 17
~19%.
A kind of pulp and paper making wastewater zero discharge processing unit that multimembrane is integrated, comprising:
Exclusion device is pre-processed, carries out pretreatment removal of impurities processing for the tail water to pulping and papermaking processes；
Ultrafiltration membrane is connected to pretreatment exclusion device, for carrying out hyperfiltration treatment to pretreatment removal of impurities treated waste water；
Low-pressure reverse osmosis membrane is connected to ultrafiltration membrane, carries out reverse osmosis concentration processing for the filtrate to ultrafiltration membrane；
First softening plant, is connected to low-pressure reverse osmosis membrane, carries out at softening for the concentrate to low-pressure reverse osmosis membrane
Reason；
High pressure reverse osmosis membrane is connected to the first softening plant, for useless after the first softening plant progress sofening treatment
Water carries out reverse osmosis concentration processing；
Second softening plant is connected to high pressure reverse osmosis membrane, carries out at softening for the concentrate to high pressure reverse osmosis membrane
Reason；
First enrichment facility is connected to the second softening plant, for useless after the second softening plant progress sofening treatment
Water carries out concentration；
Nanofiltration membrane is connected to the first enrichment facility, for the first enrichment facility treated produce water carry out a divalent salts
Separation；
Sulfate crystal system is connected to the dope side of nanofiltration membrane, for obtaining Na to nanofiltration dope crystallization treatment2SO4；
Sodium chloride crystal system is connected to the light liquid side of nanofiltration membrane, for obtaining NaCl to the light liquid crystallization treatment of nanofiltration；
First bipolar membrane electrodialysis device is connected to the dope side of nanofiltration membrane, for preparing the concentrated water of a part of nanofiltration membrane
H2SO4And NaOH；
Second bipolar membrane electrodialysis device is connected to the light liquid side of nanofiltration membrane, for preparing the fresh water of a part of nanofiltration membrane
HCl and NaOH.
In one embodiment, pretreatment exclusion device includes sequentially connected coarse filter device and advanced oxidation dress
It sets.
In one embodiment, the first softening plant and the second softening plant refer to film softening plant, lime-flue gas
One of method softening plant, ion exchange resin softening plant or medicament softening softening plant.
In one embodiment, the mother liquor outlet of sulfate crystal system is connected to sodium chloride by the second enrichment facility
The mother liquor outlet of crystal system, sodium chloride crystal system is connected to sulfate crystal system by third enrichment facility.
In one embodiment, first enrichment facility, the second enrichment facility and third enrichment facility refer to height
Press one or more of reverse osmosis membrane apparatus, DTRO device, electrodialysis plant, MVR vaporising device or multi-effect evaporating device
Combination.
Beneficial effect
The targeted brine waste wide adaptability of the utility model is adjusted by control nanofiltration cycles of concentration and rejection
The ratio for saving monovalent salt and divalent salts, meets subsequent NaCl and Na2SO4The requirement for crystallizing reuse technology respectively, realizes waste water zero-emission
It puts, and obtains the monovalent salt and divalent product salt of the technical grade of purity is high, have the advantages that energy-efficient emission reduction.
The zero-emission that industrial wastewater is realized using multimembrane integrated technique and co-producing sodium chloride, sodium sulphate of the utility model.
Minimizing processing is carried out to waste water using filtration-reverse osmosis technique in multimembrane integrated system；Using membrane technology to industrial wastewater into
Row inorganic salts proportion adjustment meets the requirement of bipolar film preparation soda acid after the concentration of membranous system fresh water；Using bipolar film preparation soda acid
Reduce the operating cost of the technique of zero discharge of industrial waste water.High-purity is finally obtained while realizing zero discharge of industrial waste water
Monovalent salt and divalent salts realize the resource utilization of water and inorganic salts in waste water, and obtain and can be used for wastewater zero discharge system
Internal and technical process high-quality acid and alkali.
In addition, due in NaCl and Na2SO4During crystallizing respectively, the NaCl and Na in feed liquid are crystallized2SO4Concentration
It is bigger than differing, more it is conducive to the crystal salt that crystallization process forms high-purity.And since the salinity in high-salt wastewater can be sent out
Raw periodically fluctuation, is easy to cause the fluctuation for obtaining the generating period of the concentration in light liquid and dope in nanofiltration process, influences
To crystallization process.Therefore, by being returned again to later to upper level to the mother liquor after crystallization using the further concentrate of reverse osmosis membrane
Crystal system can effectively make NaCl and Na2SO4Concentration ratio fluctuation numerical value reduce, it is suppressed that the shakiness in crystallization process
Qualitatively occur.
The targeted industrial wastewater of the utility model has the characteristics that discharge amount is big, processing difficulty is big.For its feature
Using passing through the integrated beneficial effect for obtaining three aspects with co-producing sodium chloride, sodium sulphate technique of multimembrane.First, industrial process
The a large amount of difficult waste water generated realize zero-emission；Second, a large amount of high-quality industry is obtained by the implementation of zero-emission process
Salt can be used for industrial processes；Third, the soda acid that the bipolar membrane process in multimembrane integrated technique obtains can be used for film process
It can be used for industrial process in system.The outsourcing amount for recycling reduction inorganic salts, soda acid of inorganic salts, soda acid, realizes nothing
It is recycled in the system of machine salt, reduces influence of the production process to environment.
Detailed description of the invention
Fig. 1 is the process flow chart of the utility model；
Fig. 2 is the device figure of the utility model.
Specific embodiment
The utility model is described in further detail below by specific embodiment.But those skilled in the art will
Understand, the following example is merely to illustrate the utility model, and should not be regarded as limiting the scope of the utility model.In embodiment not
Indicate particular technique or condition person, according to the literature in the art described technology or conditions or according to product description into
Row.Reagents or instruments used without specified manufacturer, being can be with conventional products that are commercially available.
The value expressed using range format should be interpreted as not only including clearly enumerating as range in a flexible way
The numerical value of limit value, but also including covering all single numbers or subinterval in the range, like each numerical value and sub-district
Between be expressly recited out.For example, the concentration range of " about 0.1% to about 5% " should be understood as not only including clearly enumerating
4%) and subinterval (example the concentration of about 0.1% to about 5% further includes the single concentration in how (e.g., 1%, 2%, 3% and
Such as, 0.1% to 0.5%, 1% to 2.2%, 3.3% to 4.4%).
" one embodiment " for addressing in the present specification, " another embodiment ", " embodiment " etc., refer to
In conjunction with the specific features of embodiment description, structure or it is included at least one embodiment generally described herein.
It is not centainly to refer to the same embodiment that statement of the same race, which occur, in multiple places in the description.Furthermore, it is understood that in conjunction with any
When embodiment describes a specific features, structure or feature, what is advocated is that this spy is realized in conjunction with other embodiments
Sign, structure or feature are also fallen in the application scope of the claimed.
It should be understood that it can be direct with other elements when an element is mentioned with another element " connection "
It is connected or is indirectly connected with other elements, and inserted with element between them.Unless there are clearly opposite explanation, otherwise term
It includes listed element that " comprising " and " having ", which is interpreted as statement, and non-excluded any other elements.
Word "include", "comprise" used herein, " having " or its any other variant are intended to cover non-exclusionism
Including.E.g., including technique, method, article or the equipment for listing element are not necessarily limited by those elements, but may include
Other are not explicitly listed or belong to this technique, method, article or the intrinsic element of equipment.
The characteristics of for industrial wastewater, the utility model is by the integrated acquisition purified water of multimembrane and using nanofiltration to system
It starches the inorganic salt concentration in paper waste and carries out ratio allotment, and the sodium chloride and metabisulfite solution that high concentration high-purity will be obtained
It is used to prepare soda acid, the requirement of subsequent sodium chloride and sulfate crystal technique had both been met using the technique, is obtained recycling
Sodium chloride and sodium sulphate can also reduce the operating cost of pulp and paper making wastewater zero discharge process.
The utility model relates to a kind of integrated zero discharge of industrial waste water techniques with sodium chloride and sulfate crystal of multimembrane.It should
Technique includes the following steps: 1, pretreatment removal of impurities workshop section: mainly including coarse filtration system and advanced oxidation system, control COD exists
20~60mg/L, SS are in 5~15mg/L；2, Shuan Mo workshop section: mainly including ultrafiltration system and low pressure reverse osmosis system, ultrafiltration membrane system
For system so that waste water SDI is less than 3, low pressure reverse osmosis system desalination makes fresh-water recovery rate between 50%~75%；3, film concentrate workshop section:
It mainly include melded system and high pressure reverse osmosis membrane system, melded system water production control 20~200mg/L of hardness, high pressure is reverse osmosis
Membranous system controls concentrated water salt content 5~6%；4, film minimizing workshop section: mainly including depth melded system, superelevation film pressing system
Or electrodialytic membranes system, depth melded system control hardness and are less than 1mg/L, superelevation film pressing system or the control of electrodialytic membranes system are dense
Water salt content 12~20%, reuse after fresh water is formulated；5, film deploys workshop section: mainly including multistage nanofiltration system or ion exchange
Membranous system is divided into rich sodium chloride waste water and rich sodium sulfate wastewater；6, salt manufacturing workshop section: rich sodium chloride waste water and rich sodium sulfate wastewater point
Other condensing crystallizing is sodium chloride and sodium sulphate；7, Acid-And Base-making By Bipolar Membrane workshop section: the sodium hydroxide mass concentration of preparation is 6~8%,
The hydrochloric acid mass concentration 5~7% of preparation, h 2 so 4 concentration 17~19%.
More specific embodiment is as follows:
Step 1, pretreatment removal of impurities workshop section: including coarse filtration system and advanced oxidation system, for removing in industrial wastewater
The impurity such as part COD, SS, control COD in 20~60mg/L, SS in 5~15mg/L；
Step 2, Shuan Mo workshop section: including ultrafiltration system and low pressure reverse osmosis system, for the waste water desalination after cleaning, ultrafiltration
Membranous system makes waste water SDI less than 3, and low pressure reverse osmosis system desalination makes fresh-water recovery rate between 50%~75%, can reuse work
For boiler feedwater or process water；The ultrafiltration used, which refers to, carried out the colloid in water, big molecular impurity by ultrafiltration membrane
The process of filter, " ultrafiltration membrane " in this specification refer to, the filter membrane and/or molecular cut off that aperture is 0.001~0.01 μm
For 1000~300000 or so filter membrane, the material of ultrafiltration membrane can use inoranic membrane and organic film, be further divided into thin
Aqueous and hydrophily.As hydrophobic organic film, it is not limited to this, polysulfones can be enumerated, polyether sulfone, polyethers, gathered partially
Difluoroethylene, polyethylene, polypropylene etc..As hydrophilic organic film, be not limited to this, can enumerate polyacrylonitrile,
Polyamide, polyimides, cellulose acetate etc..Its filter core shape includes that flat membrane, tubular film, spiral membrane, doughnut are (hollow
Silk) film etc..The ultrafiltration workshop section includes external-compression type, inner pressed, immersion etc. using ultrafiltration membrance filter form；The utility model
In reverse osmosis membrane, it is contour that cellulose acetate quasi polymer, polyamide, polyester, polyimides, polyvinyl can be used
Molecular material.The operating pressure of nanofiltration membrane can control in 0.5~4.0MPa, and the operating pressure of reverse osmosis membrane can control
The range of 1.0MPa~10MPa, a reverse osmosis workshop section described in step 2 produce water due to the favorable factors such as hardness is low, conductivity is low
It is preference for boiler of power plant make-up water, but is not limited to use in boiler feedwater；A reverse osmosis workshop section produce the water rate of recovery according to
Industrial wastewater water quality generally preferably 65~70%.
Step 3, film concentrate workshop section: including melded system and high pressure reverse osmosis membrane system, melded system water production control hardness
Less than 200mg/L, high pressure reverse osmosis membrane system controls concentrated water salt content 5~6%, reuse after fresh water is formulated；Film concentrate workshop section
Multistage reverse osmosis process can be used, it is reverse osmosis preferably to use two sections or three segment process；
Step 4, film minimizing workshop section: soft including depth melded system, superelevation film pressing system or electrodialytic membranes system, depth
Change system controls hardness and is less than 1mg/L, and superelevation film pressing system or electrodialytic membranes system control concentrated water salt content 12~20%, fresh water
Reuse after formulated；
In step 3 and step 4, the purpose of softening workshop section's softening process gets rid of the Ca in waste water2+、Mg2+Ion, softening
Method include medicament softening (such as be added NaOH and Na2CO3) and mechanical stirring sedimentation basin coupling technique, resin tenderizer, stone
Grey flue gas method, ion exchange resin softening, medicament softening and supermicro filtration membrane coupling technique；
Step 5, film deploy workshop section: including multistage nanofiltration system or ion exchange membranous system, to from film concentrate workshop section or
Film minimizing workshop section's waste water carries out the concentration allotment of sodium chloride and sodium sulphate, is divided into rich sodium chloride waste water and rich sodium sulfate wastewater.
Workshop section is deployed, concentrated water sodium sulfate concentration is higher than 8%, between preferred concentration 12%~20%.NaCl and Na in common middle water2SO4
Concentration proportion be not able to satisfy respectively crystallization obtain NaCl and Na2SO4Requirement when, nanofiltration membrane is used for height by the utility model
Monovalent salt and divalent salts ratio in salt waste water are adjusted, and meet NaCl and Na2SO4The requirement crystallized respectively, by crystallization process
Mother liquor recycled, reduce mother liquor amount, improve the efficiency that sodium chloride and sulfate crystal process salt utilize.Finally in reality
The monovalent salt and divalent salts that high-purity is obtained while existing brine waste zero emission, realize the resource utilization of water and inorganic salts.
The utility model involved in nanofiltration membrane, be defined as " preventing the pressure-driven less than the particle of 2nm and the macromolecular of dissolution
Cellulose acetate based polymer, polyamide, sulfonated polysulfone, polyacrylonitrile, polyester, polyimides and second can be used in the film of film "
The high molecular materials such as alkenyl polymer.Cellulose acetate quasi polymer, polyamides can be used in reverse osmosis membrane in the utility model
The high molecular materials such as amine, polyester, polyimides, polyvinyl.The operating pressure of nanofiltration membrane can control 0.5~
4.0MPa, the operating pressure of reverse osmosis membrane can control the range in 1.0MPa~10MPa.
Step 6, salt manufacturing workshop section: mainly sodium chloride crystal system processed, Sulphuric acid sodium crystal system, from film allotment workshop section
Rich sodium chloride waste water enters chlorination sodium system processed after concentrate again and obtains industrial product salt, returns to Sulphuric acid after mother liquor drop COD
Sodium crystal system；Rich sodium sulfate wastewater from film allotment workshop section enters Sulphuric acid sodium system and obtains sodium sulphate product, mother liquor
Sodium chloride crystal system processed is returned to after drop COD；
Step 7, film relieving haperacidity alkali workshop section: the sodium chloride and metabisulfite solution of part high concentration are used to prepare soda acid.Film preparation
Soda acid workshop section mainly includes bipolar membranous system, and control sodium hydroxide mass concentration is 6~8%, for preparing Membrane cleaning liquid or production
Technique；Hydrochloric acid mass concentration 5~7% is controlled, h 2 so 4 concentration 17~19%, above acid base concentration is preferred concentration, but is worked as
Acid base concentration can corresponding change when preparing the brine strength variation of workshop section into soda acid.For Membrane cleaning or production process pH value tune
It is whole.Wherein bipolar film device can be two chamber-type or the three bipolar membrane process of Room type, preferably three Room type bipolar membrane electrodialysis techniques.
Na2SO4Crystal system mother liquor is re-fed into NaCl crystal system after concentration and carries out crystallization treatment, NaCl knot
Brilliant the systematic stock solution is re-fed into Na after crossing concentration2SO4Crystal system carries out crystallization treatment.Due to the monovalence and divalent salts in waste water
Concentration can occur constantly to fluctuate, and then the process of subsequent nanofiltration, crystallization is influenced whether, so that technological parameter needs to carry out
It is constantly adapted to the variation of salinity in water, therefore will lead to that operating process is unstable, purity of crystal salt cannot reach
To requirement.Meanwhile in NaCl and Na2SO4During crystallizing respectively, the NaCl and Na in feed liquid are crystallized2SO4Concentration compare phase
Difference is bigger, is more conducive to the crystal salt that crystallization process forms high-purity.Such as: during being crystallized to NaCl, crystal solution
In NaCl and Na2SO4Concentration proportion be C1(NaCl)/C1(Na2SO4), when by Na2SO4What is obtained after crystallization mainly contains
(concentration is calculated as C to the mother liquor of NaCl2And C (NaCl),2(NaCl)> C1(NaCl)) further concentration after add to NaCl into
During row crystallization, it can increase the concentration on the molecule of ratio, improve concentration proportion；Being calculated according to numerical value can be with
Know, as 10 < C1(NaCl)/C1(Na2SO4) < 100 when fluctuation, makes molecular concentration increase that can make whole ratio in ranges
Fluctuating range be obviously reduced, play the effect for stabilizing fluctuation.Similarly Na2SO4Crystallization process in, the concentration of a divalent salts
Ratio is C1(Na2SO4)/C1(NaCl), what is obtained after crystallizing NaCl mainly contains Na2SO4Mother liquor concentrations after, will obtain
C2(Na2SO4) concentrate is back to Na2SO4Crystallization process in after, due to C2(Na2SO4)> C1(Na2SO4), similarly
Play the role of stabilizing crystallization process fluctuation of concentration.Therefore, by further being mentioned to the mother liquor after crystallization using reverse osmosis membrane
It returns again to after dense to the crystal system of upper level, can effectively make NaCl and Na2SO4Concentration ratio fluctuation numerical value reduce,
Inhibit the instable generation in crystallization process.
The integrated technique coupled with sodium chloride, sulfate crystal of multimembrane realizes pulp and paper making wastewater zero discharge.The water of acquisition
For boiler of power plant make-up water front end, also with water can effectively feed for production technology and reduce fresh water consumption.The technique is also
The sodium chloride and sodium sulphate of high-purity are obtained, realizes the resource utilization of inorganic salts in waste water, and real by soda acid preparation process
Show from sodium chloride solution and prepared hydrochloric acid and sodium hydroxide, be used for wastewater treatment and pulping process, has reduced process without drainage of waste water
Operating cost, inorganic salts and soda acid realize the part in system and recycle.
Concentration described in the utility model refers to mass concentration in the absence of special instructions.It is described in the utility model
" salinity " refer to the total concentration of sodium chloride and sodium sulphate without specializing.
Embodiment 1
It is crystallized for the waste water of certain enterprises in pulp and paper industry Pulping Line discharge using multimembrane integrated technique and sodium sulphate, sodium chloride
The process without drainage of waste water of PROCESS COUPLING.Pulp-making waste-water raw water day output is 20000 tons.Its waste water first passes around biochemical workshop section
It is handled, biochemical workshop section's process is first heavy-anaerobic biological-oxidation ditch-secondary settling tank-advanced treatment process, after biochemical treatment
Water meets qualified discharge requirement, and main water quality parameter see the table below:
Biochemical tail water carries out water using Sand Filtration System and Ozone-Biological Activated Carbon Process after the homogeneous of homogeneous pond pre-
Processing, turbidity of wastewater is down to 0.9~1.3NTU after sand filtration pre-processes, and is visible by naked eyes suspended matter.Using ozone and activated carbon
Technique handles the waste water handled through sand filtration, ozone dosage 20mg/L, the technique that staged oxidation is added using segmentation,
Active carbon use fixed bed filtering technique, bed height 2.0m, 25~30 DEG C for the treatment of temperature, air-land combat 20min；COD is dense
Degree is down to 38~48mg/L, the pretreated water rate of recovery 96%.
Enter ultrafiltration workshop section, the molecular cut off 100kDa of ultrafiltration membrane, ultrafiltration work by the filtered waste water of active carbon
Pressure 0.3MPa, ultrafiltration operating flux 60L/(m2H), ultrafiltration membrane backwash cycle 60min, water SDI is less than 2.0 for ultrafiltration production, turbid
Degree is lower than 0.2NTU, and ultrafiltration system designs the rate of recovery 92%, and ultrafiltration concentrated water returns to homogeneous pond.
Ultrafiltration produces water and enters low pressure reverse osmosis workshop section, the reverse osmosis rate of recovery 60%, 16 L/(m of average flux2H), water is produced
TDS is in 120~150mg/L, and hardness is lower than 3mg/L(with calcium carbonate), water quality is better than boiler of power plant make-up water raw water, for electricity
Factory's boiler feedwater, mixed-bed system regeneration times reduce by 40%.Water yield per day is 11200m3.First-stage reverse osmosis concentrated water TDS exists
Between 13500~15000mg/L, hardness is greater than 1500mg/L(with calcium carbonate), this burst of concentrated water enter " two alkaline process (NaOH,
Na2CO3) " softening workshop section, 140~180mg/L is down in 1550~1770mg/L by softening workshop section's processed waste water hardness.
Treated reverse osmosis workshop section's concentrated water the enters film minimizing of softened workshop section, water inlet TDS is 12400~13270mg/
L, COD48~67mg/L, 1150~1240mg/L of sodium chloride concentration, 10500~11730mg/L of sodium sulfate concentration, day output
For 7450m3.Waste water enters film upgrading system, and the water rate of recovery is 75%, fresh water yield 5580m3/ d, concentrated water amount 1870m3/d.It produces
Water 280~330mg/L of TDS, the water quality is suitable with process water water quality used in pulping process, can meet requirement.Concentrated water
TDS is 46900~48800mg/L, 4500~4750mg/L of sodium chloride concentration in concentrated water, sodium sulfate concentration 41800~
43200mg/L, 392~420mg/L of hardness.Concentrated water hardness after the softening of nanofiltration membrane melded system depth is reduced to 0.9~
1.5mg/L carries out concentration minimizing processing to the production water after depth softening using high pressure reverse osmosis membrane.
Film minimizing workshop section concentrated water enters nanofiltration workshop section and carries out the allotment of salt component, and nanofiltration workshop section uses two-stage nanofiltration technique,
Wherein level-one nanofiltration operating pressure 59bar, after level-one nanofiltration processing, fresh water amount is 1250m3/ d, sodium chloride concentration 4650~
4820mg/L, 420~447mg/L of fresh water sodium sulfate concentration.Nanofiltration fresh water is handled using second level nanofiltration technique, light after processing
Water 4660~4840mg/L of sodium chloride concentration, 41~47mg/L of sodium sulfate concentration.23100~25000mg/ of concentrated water sodium sulfate concentration
L, concentrated water are back to nanofiltration workshop section level-one nanofiltration membrane.It is carried out using reverse osmosis membrane and homogeneous membrane electrodialytic technique second level nanofiltration fresh water dense
Contracting, concentration liquid measure are 31.2m3/ d, 186400~204500mg/L of sodium chloride concentration, 1620~1730mg/L of sodium sulfate concentration.
Level-one nanofiltration concentrated water amount is 620m3/ d, 4470~4610mg/L of sodium chloride concentration, 125400~132100mg/ of sodium sulfate concentration
L。
Enter Bipolar Membrane soda acid after the nanofiltration fresh water of a part is concentrated and prepare workshop section, the bipolar membrane process of use obtains dense
Spend 6.5% hydrochloric acid of 7% caustic soda and concentration.Another part nanofiltration fresh water meets the production requirement for entering NaCl crystallization processes section.Chlorination
Sodium crystal system uses triple effect evaporation, imitates out salt-mother liquor reflux mode of operation, control crystallization temperature using advection charging-is every
Degree is between 40~50 DEG C, Na in crystalline mother solution2SO4Mass concentration 4920mg/L, send to sulfate crystal system reuse, day
Obtain 39.9 tons of 98.7% sodium chloride.A part of nanofiltration concentrated water enters Bipolar Membrane soda acid preparation workshop section, and the bipolar membrane process of use is dense
Spend 8~8.2% caustic soda and 17~17.3% sulfuric acid of concentration.Another part nanofiltration concentrated water enters sulfate crystal system, sodium sulphate knot
Crystallographic system system carries out Na using MVR technique2SO4Crystallization controls crystallization temperature between 90~105 DEG C, Na2SO4With the quality of NaCl
Concentration meets than being about 28:1 and enters Na2SO4The technique of crystallization requires, the mass concentration 28900mg/L of NaCl in crystalline mother solution,
It send to sodium chloride crystal system reuse, which produces 64.5 tons of 99.1% anhydrous sodium sulfate daily.
The integrated technique coupled with sodium sulphate, sodium chloride crystallization process of multimembrane realizes pulp and paper making wastewater zero discharge.It obtains
Water for boiler of power plant make-up water front end, can also be carried out feeding the fresh water consumption of reduction with water effectively for production technology.The work
Skill also obtains the sodium chloride and sodium sulphate of high-purity, realizes the resource utilization of inorganic salts in waste water, and prepares work by soda acid
Skill realizes from sodium chloride solution and prepares hydrochloric acid and sodium hydroxide, is used for wastewater treatment and pulping process, reduces wastewater zero discharge
The operating cost of technique, inorganic salts and soda acid realize the part in system and recycle.
Embodiment 2
It is crystallized for the waste water of certain enterprises in pulp and paper industry Pulping Line discharge using multimembrane integrated technique and sodium sulphate, sodium chloride
The process without drainage of waste water of PROCESS COUPLING.Pulp-making waste-water raw water day output is 15000 tons.Its waste water first passes around biochemical workshop section
It is handled, biochemical workshop section's process is first heavy-anaerobic biological-oxidation ditch-secondary settling tank-advanced treatment process, after biochemical treatment
Water meets qualified discharge requirement, and main water quality parameter see the table below:
Biochemical tail water pre-processes qualified discharge tail water using Sand Filtration System and Ozone-Biological Activated Carbon Process, passes through
Turbidity of wastewater is down to 1.5NTU after crossing fabric filter depth-type filtration, is visible by naked eyes suspended matter.Using ozone and activated carbon technique
The waste water handled through fabric filter is handled, ozone dosage 25mg/L, the work of staged oxidation is added using segmentation
Skill, active carbon use fixed bed filtering technique, bed height 2.2m, 25~30 DEG C for the treatment of temperature, air-land combat 25min；COD
Concentration is down to 15~24mg/L, the pretreated water rate of recovery 96%.
Enter ultrafiltration workshop section, the molecular cut off 50kDa of ultrafiltration membrane, ultrafiltration work pressure by the filtered waste water of active carbon
Power 0.25MPa, ultrafiltration operating flux 50L/(m2H), ultrafiltration membrane backwash cycle 60min, water SDI is less than 2.5 for ultrafiltration production, turbidity
Lower than 0.3NTU, ultrafiltration system designs the rate of recovery 92%, and ultrafiltration concentrated water returns to homogeneous pond.
Ultrafiltration produces water and enters low pressure reverse osmosis workshop section, the reverse osmosis rate of recovery 65%, 15 L/(m of average flux2H), water is produced
TDS is in 140~160mg/L, and hardness is lower than 2mg/L(with calcium carbonate), water quality is better than production clear water, reuse to production technology,
Water yield per day is 9700m3.TDS is between 18100~18500mg/L for first-stage reverse osmosis concentrated water, hardness be greater than 1200mg/L(with
Calcium carbonate), this burst of concentrated water enters " two alkaline process (NaOH, Na2CO3) " softening workshop section, by softening workshop section's processed waste water hardness
90mg/L or less is down in 1200~1340mg/L.
Treated reverse osmosis workshop section's concentrated water the enters film minimizing of softened workshop section, water inlet TDS is 18500~20140mg/
L, COD are 43~57mg/L, sodium chloride concentration 2800mg/L, 14880~15930mg/L of sodium sulfate concentration, and day output is
5250m3.Softened waste water enters film concentrate unit, and the water rate of recovery is 70%, fresh water yield 3670m3/ d, concentrated water amount
1580m3/d.Requirement can be met after the water is mixed with one section of reverse osmosis freshwater lower than 370~420mg/L by producing water TDS.It is dense
Water TDS is 60800~62410mg/L, 9200~10320mg/L of sodium chloride concentration in concentrated water, sodium sulfate concentration 49580~
51470mg/L, 135~153mg/L of hardness.Concentrated water hardness after the softening of nanofiltration membrane melded system depth is reduced to 0.8~
1.4mg/L carries out concentration minimizing processing to the production water after depth softening using high pressure reverse osmosis membrane.
Film minimizing workshop section concentrated water enters nanofiltration workshop section and carries out the allotment of salt component, nanofiltration operating pressure 60bar, at nanofiltration
After reason, fresh water amount is 1050m3/ d, 9660~10860mg/L of sodium chloride concentration, 980~1070mg/L of sodium sulfate concentration.Concentrated water
Measure 600m3/ d, concentrated water 145500~156200mg/L of sodium sulfate concentration, 9050~10050mg/L of sodium chloride concentration.
Enter Bipolar Membrane soda acid after the nanofiltration fresh water of a part is concentrated and prepare workshop section, the bipolar membrane process of use obtains dense
Spend 6.5% hydrochloric acid of 8% caustic soda and concentration.Another part nanofiltration fresh water meets the production requirement for entering NaCl crystallization processes section.Chlorination
Sodium crystal system uses triple effect evaporation, imitates out salt-mother liquor reflux mode of operation, control crystallization temperature using advection charging-is every
Degree is between 40~50 DEG C, Na in crystalline mother solution2SO4Mass concentration 4685mg/L, send to sulfate crystal system reuse, day
Obtain 5.3 tons of 98.3% sodium chloride.A part of nanofiltration concentrated water enters Bipolar Membrane soda acid preparation workshop section, and the bipolar membrane process of use is dense
Spend 17% sulfuric acid of 8% caustic soda and concentration.Another part nanofiltration concentrated water enters sulfate crystal system, and sulfate crystal system uses
MVR technique carries out Na2SO4Crystallization controls crystallization temperature between 90~105 DEG C, Na2SO4Mass concentration ratio with NaCl is about
16:1 meets and enters Na2SO4The technique of crystallization requires, and the mass concentration 48750mg/L of NaCl, send to sodium chloride in crystalline mother solution
Crystal system reuse, the technique produce 58.3 tons of 99.1% anhydrous sodium sulfate daily.
The integrated technique coupled with sodium sulphate, sodium chloride crystallization process of multimembrane realizes pulp and paper making wastewater zero discharge.It obtains
Water for boiler of power plant make-up water front end, can also be carried out feeding the fresh water consumption of reduction with water effectively for production technology.The work
Skill also obtains the sodium chloride and sodium sulphate of high-purity, realizes the resource utilization of inorganic salts in waste water, and prepares work by soda acid
Skill realizes from sodium chloride solution and prepares hydrochloric acid and sodium hydroxide, is used for wastewater treatment and pulping process, reduces wastewater zero discharge
The operating cost of technique, inorganic salts and soda acid realize the part in system and recycle.
Embodiment 3
It is crystallized for the waste water of certain enterprises in pulp and paper industry Pulping Line discharge using multimembrane integrated technique and sodium sulphate, sodium chloride
The process without drainage of waste water of PROCESS COUPLING.Pulp-making waste-water raw water day output is 20000 tons.Its waste water first passes around biochemical workshop section
It is handled, biochemical workshop section's process is first heavy-anaerobic biological-oxidation ditch-secondary settling tank-advanced treatment process, after biochemical treatment
Water meets qualified discharge requirement, and main water quality parameter see the table below:
Biochemical tail water carries out water using Sand Filtration System and Ozone-Biological Activated Carbon Process after the homogeneous of homogeneous pond pre-
Processing, turbidity of wastewater is down to 0.9~1.3NTU after sand filtration pre-processes, and is visible by naked eyes suspended matter.Using ozone and activated carbon
Technique handles the waste water handled through sand filtration, ozone dosage 20mg/L, the technique that staged oxidation is added using segmentation,
Active carbon use fixed bed filtering technique, bed height 2.0m, 25~30 DEG C for the treatment of temperature, air-land combat 20min；COD is dense
Degree is down to 38~48mg/L, the pretreated water rate of recovery 96%.
Enter ultrafiltration workshop section, the molecular cut off 100kDa of ultrafiltration membrane, ultrafiltration work by the filtered waste water of active carbon
Pressure 0.3MPa, ultrafiltration operating flux 60L/(m2H), ultrafiltration membrane backwash cycle 60min, water SDI is less than 2.0 for ultrafiltration production, turbid
Degree is lower than 0.2NTU, and ultrafiltration system designs the rate of recovery 92%, and ultrafiltration concentrated water returns to homogeneous pond.
Ultrafiltration produces water and enters low pressure reverse osmosis workshop section, the reverse osmosis rate of recovery 60%, 16 L/(m of average flux2H), water is produced
TDS is in 120~150mg/L, and hardness is lower than 3mg/L(with calcium carbonate), water quality is better than boiler of power plant make-up water raw water, for electricity
Factory's boiler feedwater, mixed-bed system regeneration times reduce by 40%.Water yield per day is 11200m3.First-stage reverse osmosis concentrated water TDS exists
Between 13500~15000mg/L, hardness is greater than 1500mg/L(with calcium carbonate), this burst of concentrated water enter " two alkaline process (NaOH,
Na2CO3) " softening workshop section, 140~180mg/L is down in 1550~1770mg/L by softening workshop section's processed waste water hardness.
Treated reverse osmosis workshop section's concentrated water the enters film minimizing of softened workshop section, water inlet TDS is 12400~13270mg/
L, COD48~67mg/L, 1150~1240mg/L of sodium chloride concentration, 10500~11730mg/L of sodium sulfate concentration, day output
For 7450m3.Waste water enters film upgrading system, and the water rate of recovery is 75%, fresh water yield 5580m3/ d, concentrated water amount 1870m3/d.It produces
Water 280~330mg/L of TDS, the water quality is suitable with process water water quality used in pulping process, can meet requirement.Concentrated water
TDS is 46900~48800mg/L, 4500~4750mg/L of sodium chloride concentration in concentrated water, sodium sulfate concentration 41800~
43200mg/L, 392~420mg/L of hardness.Concentrated water hardness after the softening of nanofiltration membrane melded system depth is reduced to 0.9~
1.5mg/L carries out concentration minimizing processing to the production water after depth softening using high pressure reverse osmosis membrane.
Film minimizing workshop section concentrated water enters nanofiltration workshop section and carries out the allotment of salt component, and nanofiltration workshop section uses two-stage nanofiltration technique,
Wherein level-one nanofiltration operating pressure 59bar, after level-one nanofiltration processing, fresh water amount is 1250m3/ d, sodium chloride concentration 4650~
4820mg/L, 420~447mg/L of fresh water sodium sulfate concentration.Nanofiltration fresh water is handled using second level nanofiltration technique, light after processing
Water 4660~4840mg/L of sodium chloride concentration, 41~47mg/L of sodium sulfate concentration.23100~25000mg/ of concentrated water sodium sulfate concentration
L, concentrated water are back to nanofiltration workshop section level-one nanofiltration membrane.It is carried out using reverse osmosis membrane and homogeneous membrane electrodialytic technique second level nanofiltration fresh water dense
Contracting, concentration liquid measure are 31.2m3/ d, 186400~204500mg/L of sodium chloride concentration, 1620~1730mg/L of sodium sulfate concentration.
Level-one nanofiltration concentrated water amount is 620m3/ d, 4470~4610mg/L of sodium chloride concentration, 125400~132100mg/ of sodium sulfate concentration
L。
Enter Bipolar Membrane soda acid after the nanofiltration fresh water of a part is concentrated and prepare workshop section, the bipolar membrane process of use obtains dense
Spend 6.5% hydrochloric acid of 7% caustic soda and concentration.Another part nanofiltration fresh water meets the production requirement for entering NaCl crystallization processes section.Chlorination
Sodium crystal system uses triple effect evaporation, imitates out salt-mother liquor reflux mode of operation, control crystallization temperature using advection charging-is every
Degree is between 40~50 DEG C, crystalline mother solution Na after high pressure reverse osmosis concentration2SO4Mass concentration 224500mg/L, send to sulfuric acid
Sodium crystal system reuse, day obtain 41.7 tons of 98.7% sodium chloride.A part of nanofiltration concentrated water enters Bipolar Membrane soda acid preparation workshop section,
Bipolar 8% caustic soda of membrane process concentration and 17% sulfuric acid of concentration used.Another part nanofiltration concentrated water enters sulfate crystal system, sulphur
Sour sodium crystal system carries out Na using MVR technique2SO4Crystallization controls crystallization temperature between 90~105 DEG C, Na2SO4And NaCl
Mass concentration ratio be about 28:1, meet enter Na2SO4The technique requirement of crystallization, crystalline mother solution is after high pressure reverse osmosis concentration
The mass concentration 78420mg/L of NaCl is sent to sodium chloride crystal system reuse, which produces 99.5% anhydrous sodium sulfate 66.3 daily
Ton.
The integrated technique coupled with sodium sulphate, sodium chloride crystallization process of multimembrane realizes pulp and paper making wastewater zero discharge.It obtains
Water for boiler of power plant make-up water front end, can also be carried out feeding the fresh water consumption of reduction with water effectively for production technology.The work
Skill also obtains the sodium chloride and sodium sulphate of high-purity, realizes the resource utilization of inorganic salts in waste water, and prepares work by soda acid
Skill realizes from sodium chloride solution and prepares hydrochloric acid and sodium hydroxide, is used for wastewater treatment and pulping process, reduces wastewater zero discharge
The operating cost of technique, inorganic salts and soda acid realize the part in system and recycle.
Claims (5)
1. a kind of integrated pulp and paper making wastewater zero discharge processing unit of multimembrane characterized by comprising
Exclusion device is pre-processed, carries out pretreatment removal of impurities processing for the tail water to pulping and papermaking processes；
Ultrafiltration membrane is connected to pretreatment exclusion device, for carrying out hyperfiltration treatment to pretreatment removal of impurities treated waste water；
Low-pressure reverse osmosis membrane is connected to ultrafiltration membrane, carries out reverse osmosis concentration processing for the filtrate to ultrafiltration membrane；
First softening plant is connected to low-pressure reverse osmosis membrane, carries out sofening treatment for the concentrate to low-pressure reverse osmosis membrane；
High pressure reverse osmosis membrane is connected to the first softening plant, for carrying out to the waste water after the first softening plant progress sofening treatment
Reverse osmosis concentration processing；
Second softening plant is connected to high pressure reverse osmosis membrane, carries out sofening treatment for the concentrate to high pressure reverse osmosis membrane；
First enrichment facility is connected to the second softening plant, for carrying out to the waste water after the second softening plant progress sofening treatment
Concentration；
Nanofiltration membrane is connected to the first enrichment facility, for the first enrichment facility treated produce water carry out a divalent salts divide
From；
Sulfate crystal system is connected to the dope side of nanofiltration membrane, for obtaining Na to nanofiltration dope crystallization treatment2SO4；
Sodium chloride crystal system is connected to the light liquid side of nanofiltration membrane, for obtaining NaCl to the light liquid crystallization treatment of nanofiltration；
First bipolar membrane electrodialysis device is connected to the dope side of nanofiltration membrane, for the concentrated water of a part of nanofiltration membrane to be prepared H2SO4With
NaOH；
Second bipolar membrane electrodialysis device is connected to the light liquid side of nanofiltration membrane, for by the fresh water of a part of nanofiltration membrane preparation HCl and
NaOH。
2. the integrated pulp and paper making wastewater zero discharge processing unit of multimembrane according to claim 1, which is characterized in that pre- place
Managing exclusion device includes sequentially connected coarse filter device and advanced oxidation device.
3. the integrated pulp and paper making wastewater zero discharge processing unit of multimembrane according to claim 1, which is characterized in that first
Softening plant and the second softening plant refer to film softening plant, lime-flue gas method softening plant, ion exchange resin softening dress
It sets or medicament softens one of softening plant.
4. the integrated pulp and paper making wastewater zero discharge processing unit of multimembrane according to claim 1, which is characterized in that sulfuric acid
The mother liquor outlet of sodium crystal system is connected to sodium chloride crystal system, the mother liquor of sodium chloride crystal system by the second enrichment facility
Outlet is connected to sulfate crystal system by third enrichment facility.
5. the integrated pulp and paper making wastewater zero discharge processing unit of multimembrane according to claim 1, which is characterized in that described
The first enrichment facility, the second enrichment facility and third enrichment facility refer to high pressure reverse osmosis membrane apparatus, DTRO device, electrodialysis
The combination of one or more of device, MVR vaporising device or multi-effect evaporating device.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201821121501.5U CN208667350U (en) | 2018-07-16 | 2018-07-16 | Multi-membrane integrated pulping and papermaking wastewater zero-discharge treatment device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201821121501.5U CN208667350U (en) | 2018-07-16 | 2018-07-16 | Multi-membrane integrated pulping and papermaking wastewater zero-discharge treatment device |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN208667350U true CN208667350U (en) | 2019-03-29 |
Family
ID=65828662
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201821121501.5U Active CN208667350U (en) | 2018-07-16 | 2018-07-16 | Multi-membrane integrated pulping and papermaking wastewater zero-discharge treatment device |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN208667350U (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI715974B (en) * | 2019-05-06 | 2021-01-11 | 中國鋼鐵股份有限公司 | Method for removing chlorine-containing salt from industrial wastewater and apparatus thereof |
| CN112939295A (en) * | 2021-03-25 | 2021-06-11 | 四川恩特普环保科技有限公司 | Method for preparing acid and alkali by sodium sulfate bipolar membrane electrodialysis |
| CN112960839A (en) * | 2021-04-16 | 2021-06-15 | 宝武水务科技有限公司 | Zero-discharge treatment system and treatment method for acid-making wastewater from purification of active coke flue gas |
| CN115557574A (en) * | 2022-10-20 | 2023-01-03 | 徐州水处理研究所 | Process for recycling ammonium sulfate and ammonium chloride wastewater by full membrane method |
-
2018
- 2018-07-16 CN CN201821121501.5U patent/CN208667350U/en active Active
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI715974B (en) * | 2019-05-06 | 2021-01-11 | 中國鋼鐵股份有限公司 | Method for removing chlorine-containing salt from industrial wastewater and apparatus thereof |
| CN112939295A (en) * | 2021-03-25 | 2021-06-11 | 四川恩特普环保科技有限公司 | Method for preparing acid and alkali by sodium sulfate bipolar membrane electrodialysis |
| CN112960839A (en) * | 2021-04-16 | 2021-06-15 | 宝武水务科技有限公司 | Zero-discharge treatment system and treatment method for acid-making wastewater from purification of active coke flue gas |
| CN115557574A (en) * | 2022-10-20 | 2023-01-03 | 徐州水处理研究所 | Process for recycling ammonium sulfate and ammonium chloride wastewater by full membrane method |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108623054B (en) | Multi-membrane integrated pulping and papermaking wastewater zero-discharge treatment method and device | |
| CN208667350U (en) | Multi-membrane integrated pulping and papermaking wastewater zero-discharge treatment device | |
| CN108623104B (en) | High-salinity wastewater zero-emission treatment method and device based on nanofiltration membrane allocation | |
| CN105540967B (en) | A kind of organic wastewater minimizing, recycling processing method and processing system | |
| CN108275817A (en) | A kind of processing method of the high salinity waste water reclaiming of high rigidity | |
| CN108117207B (en) | Zero-discharge treatment process method for salt-containing wastewater | |
| CN105439395A (en) | Zero-discharge treatment method of salt-containing organic wastewater | |
| CN108117206B (en) | Zero-discharge treatment process method for salt-containing wastewater | |
| CN108529802A (en) | Titanium white production discharges high slat-containing wastewater zero-emission technique | |
| CN108623105B (en) | Zero discharge treatment method and device for pulping industrial wastewater | |
| CN110734166B (en) | Method for efficient desalination and comprehensive utilization of seawater | |
| CN111362283B (en) | Viscose wastewater recycling treatment method | |
| CN207933209U (en) | A kind of middle water zero discharge processing unit | |
| WO2022143014A1 (en) | Resourceful treatment system and method for sodium nitrate wastewater | |
| CN108117222A (en) | A kind of coal chemical industry brine waste zero emission processing method | |
| CN208667421U (en) | High salt waste water zero release processing apparatus based on receive filter membrane allotment | |
| CN110526512A (en) | A kind of high-COD waste water with high salt recycling Zero discharging system and technique | |
| CN108623055B (en) | Zero-discharge softening process and device for pulping and papermaking wastewater | |
| CN108658345A (en) | A kind of method and system of high-salt wastewater purified salt | |
| CN104817134A (en) | Full-membrane method seawater desalting integration system adopting ultrafiltration-nanofiltration-reverse osmosis, and full-membrane method seawater desalting integration process adopting ultrafiltration-nanofiltration-reverse osmosis | |
| CN109293112A (en) | A kind of processing method of viscose rayon acid waste water resource utilization | |
| CN106315910A (en) | Method for treating waste water of titanium dioxide | |
| CN107522350A (en) | Waste Water Treatment and method of wastewater treatment | |
| CN109970262A (en) | A kind of middle water zero discharge processing method and processing device | |
| CN105439347B (en) | A kind of mother liquor treatment process and system for the concentration of clopyralid feed separation |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| GR01 | Patent grant | ||
| GR01 | Patent grant |