CN108218038A - A kind of method of resin adsorption desorption-diffusion dialysis processing heavy metal-containing waste water - Google Patents
A kind of method of resin adsorption desorption-diffusion dialysis processing heavy metal-containing waste water Download PDFInfo
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- CN108218038A CN108218038A CN201810095494.4A CN201810095494A CN108218038A CN 108218038 A CN108218038 A CN 108218038A CN 201810095494 A CN201810095494 A CN 201810095494A CN 108218038 A CN108218038 A CN 108218038A
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- Prior art keywords
- heavy metal
- resin
- waste water
- desorption
- diffusion dialysis
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- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 103
- 239000011347 resin Substances 0.000 title claims abstract description 81
- 229920005989 resin Polymers 0.000 title claims abstract description 81
- 238000000034 method Methods 0.000 title claims abstract description 64
- 239000002351 wastewater Substances 0.000 title claims abstract description 44
- 238000000502 dialysis Methods 0.000 title claims abstract description 38
- 238000009792 diffusion process Methods 0.000 title claims abstract description 34
- 238000001179 sorption measurement Methods 0.000 title claims abstract description 34
- 239000007788 liquid Substances 0.000 claims abstract description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 46
- 150000003839 salts Chemical class 0.000 claims abstract description 38
- 238000003795 desorption Methods 0.000 claims abstract description 37
- 238000009938 salting Methods 0.000 claims abstract description 21
- 230000008929 regeneration Effects 0.000 claims abstract description 14
- 238000011069 regeneration method Methods 0.000 claims abstract description 14
- 238000004064 recycling Methods 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 6
- 239000002184 metal Substances 0.000 claims abstract description 6
- 238000002336 sorption--desorption measurement Methods 0.000 claims abstract 9
- 150000002500 ions Chemical class 0.000 claims description 53
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 22
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 17
- 239000003795 chemical substances by application Substances 0.000 claims description 17
- 230000008569 process Effects 0.000 claims description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 14
- 238000009388 chemical precipitation Methods 0.000 claims description 11
- 239000011780 sodium chloride Substances 0.000 claims description 11
- 239000010949 copper Substances 0.000 claims description 9
- 238000004070 electrodeposition Methods 0.000 claims description 9
- 238000009825 accumulation Methods 0.000 claims description 8
- 230000035515 penetration Effects 0.000 claims description 8
- 239000001103 potassium chloride Substances 0.000 claims description 7
- 235000011164 potassium chloride Nutrition 0.000 claims description 7
- 239000011651 chromium Substances 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 239000011572 manganese Substances 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052793 cadmium Inorganic materials 0.000 claims description 4
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 125000000524 functional group Chemical group 0.000 claims description 4
- 239000011133 lead Substances 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- 229920002125 Sokalan® Polymers 0.000 claims description 3
- 239000006227 byproduct Substances 0.000 claims description 3
- 125000002843 carboxylic acid group Chemical group 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 125000001841 imino group Chemical group [H]N=* 0.000 claims description 3
- 239000002105 nanoparticle Substances 0.000 claims description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- 239000004584 polyacrylic acid Substances 0.000 claims description 3
- 229920003053 polystyrene-divinylbenzene Polymers 0.000 claims description 3
- 239000002910 solid waste Substances 0.000 claims description 3
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims 1
- 240000005572 Syzygium cordatum Species 0.000 claims 1
- 235000006650 Syzygium cordatum Nutrition 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- 239000000460 chlorine Substances 0.000 claims 1
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- 229910052738 indium Inorganic materials 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 229910052700 potassium Inorganic materials 0.000 claims 1
- 239000011591 potassium Substances 0.000 claims 1
- 238000011084 recovery Methods 0.000 abstract description 4
- 238000004065 wastewater treatment Methods 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000003912 environmental pollution Methods 0.000 abstract 1
- 230000001172 regenerating effect Effects 0.000 abstract 1
- 239000012528 membrane Substances 0.000 description 12
- 239000000243 solution Substances 0.000 description 9
- 239000003011 anion exchange membrane Substances 0.000 description 8
- 238000000926 separation method Methods 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 239000003463 adsorbent Substances 0.000 description 4
- 150000001450 anions Chemical class 0.000 description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 238000001223 reverse osmosis Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003456 ion exchange resin Substances 0.000 description 3
- 229920003303 ion-exchange polymer Polymers 0.000 description 3
- 229910001414 potassium ion Inorganic materials 0.000 description 3
- 239000002594 sorbent Substances 0.000 description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 231100000570 acute poisoning Toxicity 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- -1 ion exchange resin compound Chemical class 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 238000001728 nano-filtration Methods 0.000 description 2
- 235000021110 pickles Nutrition 0.000 description 2
- BITYAPCSNKJESK-UHFFFAOYSA-N potassiosodium Chemical compound [Na].[K] BITYAPCSNKJESK-UHFFFAOYSA-N 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 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 description 1
- 239000004912 1,5-cyclooctadiene Substances 0.000 description 1
- PXFBZOLANLWPMH-UHFFFAOYSA-N 16-Epiaffinine Natural products C1C(C2=CC=CC=C2N2)=C2C(=O)CC2C(=CC)CN(C)C1C2CO PXFBZOLANLWPMH-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 241000233866 Fungi Species 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
- 241001062009 Indigofera Species 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 208000005374 Poisoning Diseases 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 230000007059 acute toxicity Effects 0.000 description 1
- 231100000403 acute toxicity Toxicity 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000001458 anti-acid effect Effects 0.000 description 1
- 231100000693 bioaccumulation Toxicity 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- 235000012255 calcium oxide Nutrition 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000009297 electrocoagulation Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910001338 liquidmetal Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000001471 micro-filtration Methods 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 239000003403 water pollutant Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/463—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrocoagulation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/16—Regeneration of sorbents, filters
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Treatment Of Water By Ion Exchange (AREA)
Abstract
The invention discloses a kind of methods of resin adsorption desorption diffusion dialysis processing heavy metal-containing waste water, belong to wastewater treatment and recycling reuse field, specifically, being related to a kind of method of resource of resin adsorption desorption and diffusion dialysis combination to heavy metal-containing waste water.The method includes with resin adsorption heavy metal-containing waste water, then regenerating resin desorption with salting liquid, then with diffusive dialysis method separating beavy metal and salt, wherein salt recovery is in desorption and regeneration step.In the method for the present invention, in addition to detaching heavy metal and being enriched with, salting liquid can recovery again, heavy metal concentration is down to below 0.01mg/L in last discharge water, production cost and environmental pollution are significantly reduced, meets the energy-saving and emission-reduction industrial policy of current country, suitable for industrialization promotion.
Description
Technical field
The invention belongs to wastewater treatment industry production fields, are related to the recycling of heavy metal and salt in a kind of resin desorption liquid
Reuse method, specifically, being related to a kind of method of resin adsorption desorption-diffusion dialysis processing heavy metal-containing waste water.
Background technology
With the development of industry and mining and the quickening of urbanization process, heavy metal exploitation, smelting, processing, electronics finishing, process hides
Deng the waste water generated in the process and the not appropriately processed sanitary sewage with regard to direct emission, the water bodys such as rivers and lakes are caused
Heavy metal pollution.The heavy metal includes the one or more such as copper, nickel, zinc, lead, chromium, manganese, cadmium.Even if concentration very little, but because
The bioaccumulation of heavy metal, they have acute toxicity to environment, organism and the mankind, can cause human body acute poisoning, Asia
Acute poisoning, slow poisoning etc. cause human body very big harm.To effectively remove the pollution of this kind of heavy metal ion in water body,
Countries in the world develop a variety of methods, are sealed up for safekeeping including chemical precipitation method, electrolysis, electrocoagulation, flocculence, modified oxidized fungi
Method, absorption method and liquid-film method etc., wherein the use of the absorption method of anions and canons resin compounded adsorbent being considered most economical
One of effective method.In order to improve resin utilization rate and recycle heavy metal ion, generally required after heavy metal ion is adsorbed
Resin desorption is regenerated using eluent.
Common anions and canons resin sorbent adsorption capacity is big, but heavy metal ion content is still in the raffinate adsorbed
It is so higher.In order to carry out deep purifying to the waste water containing heavy metal ion, make contained heavy metal ion in the discharge liquor after absorption
Concentration is down to 0.01mg/L hereinafter, supported nano-gold category oxide can be used to the waste water that heavy metal ion content is 1-5mg/L
Or the ion exchange resin compound adsorbent of hydrous oxide is handled.The desorption and regeneration needs of common resin cation adsorbent make
It is eluted with strong acid, but the desorption and regeneration of the ion exchange resin compound adsorbent of supported nano-gold category oxide and hydrous oxide is not
It can be eluted using strong acid, when using pickling, loaded oxide can be caused to be detached from the duct of ion exchange resin, influence to adsorb
Efficiency.At this moment salting liquid must be used also therefore to face in desorption liquid the problem of containing a large amount of salt as eluant, eluent.
Chinese invention patent, application No. is：200910264219.1 it discloses in a kind of membrane separating recycling pickle liquor
The technique of heavy metallic salt and inorganic acid, the specific steps are:Solid in removal pickle liquor is filtered by inorganic ceramic membrane to suspend
Object；Ceramic membrane penetrating fluid realizes the separation of acid and salt by diffusion dialysis, and the patent is directed in highly acid waste liquid, heavy metal
With the technique of inorganic acid.
Chinese invention patent, application No. is：201610557950.3 disclose a kind of zero-emission side of heavy metal wastewater thereby
Method is passed through air in balancing tank and waste water is stirred, and quick lime is added in during being passed through air and stirring, pure
Alkali, sulfuric acid or hydrochloric acid add sodium hydroxide and are stirred, then so that hydroxide precipitation realizes solid-liquid in sedimentation basin
Separation adjusts pH to 7 to the water after separation, will be adjusted to neutral water successively by quartz filter, micro-filtration and nanofiltration, removes
Impurity in leachate is removed, then selective absorption functional membrane is used to be further processed in a manner of membrane filtration, with tap water flushing membrane,
The impurity of the non-affine absorption of film surface is washed out, is evaporated crystallization treatment and point row discharge to purifying filtered water with Low Temperature Steam
For the purified water and salt of reuse；The inventive method enter concentrated water it is reverse osmosis before the hardness ions such as heavy metal ion, calcium and magnesium,
Silicon, COD and other contaminant removals improve the operation stability of crystallizing evaporator.Adsorption function film is used in the patent
Reverse osmosis membrane or NF membrane are not amberplexes.Using reverse osmosis membrane in addition to water, other ions cannot all pass through, and nanofiltration
Though film separates monovalent anion salting liquid and high-valence anion salting liquid, either reverse osmosis membrane or NF membrane, all must
Must be work with pressure, energy consumption is big.
Chinese invention patent, application number：201210001029.2 disclose a kind of side for removing heavy metal ion in water
Method, technical principle are the exchange interactions using amberplex so that water pollutant heavy metal ion is by highly concentrated one
Side infiltrates into the low side of concentration, and the low side of concentration applies alkalinity or carbonate or vulcanization salting liquid so that heavy metal ion
It forms slightly solubility hydroxide or carbonate or sulphurizing salt is able to precipitation removal.The invention has UF membrane and chemical precipitation process
Machine links together, and realizes the film dialysis progress synchronous with precipitation removal of heavy metal.The invention is using continuous in acceptable solution
Consumption heavy metal ion reduces its concentration, to promote the infiltration of heavy metal；The chemical precipitation of formation easily blocks fenestra road, suppression
It is film-made flux.
Invention content
1. technical problems to be solved by the inivention
After cationic exchange resin adsorption of the effluent containing heavy metal ions in the prior art using load nano-oxide
Discomfort shares sour desorption, can only use salting liquid desorption and regeneration, and salt and heavy metal of the desorption liquid containing high concentration of gained are not suitable for straight
The problem of connecing with electrodeposition process or chemical precipitation method separating beavy metal and salt, the present invention provides a kind of resin adsorption desorption-diffusion and oozes
The method of analysis processing heavy metal-containing waste water.It can use diffusive dialysis method to handle desorption liquid, and heavy metal is separated, is divided
From salt can reuse in desorption liquid.
2. technical solution
To solve the above problems, technical solution provided by the invention is：
A kind of method of resin adsorption desorption-diffusion dialysis processing heavy metal-containing waste water, step are：
(A) waste water containing heavy metal ion is made into resin adsorption saturation, the discharge of the first standard water discharge of gained by resin；
(B) salting liquid is added in the resin of adsorption penetration as desorbing agent, makes resin regeneration, the salt includes sodium chloride
Or potassium chloride；
(C) the de- of diffusion dialysis device will be separately added into from the desorption liquid of step (B) containing heavy metal ion and salt and water
Attached liquid and water inlet respectively obtain water outlet with high salt and the first raffinate rich in heavy metal ion；
(D) first raffinate is handled with electrodeposition process or chemical precipitation method, obtains heavy metal accumulation object and the second raffinate,
The heavy metal accumulation object as solid waste or industrial by-product, in second raffinate heavy metal concentration be reduced to 5mg/L hereinafter, with
Through resin treatment qualified discharge, tree of the water outlet with high salt as step (B) after the merging of the waste water containing heavy metal ion in step (A)
Fat desorbing agent recycles.
Preferably, heavy metal described in step (A) includes one or more of copper, nickel, zinc, lead, chromium, manganese or cadmium.
Preferably, the skeleton of resin described in step (A) key on polystyrene divinyl benzene or polyacrylic acid, skeleton
The functional group of connection is selected from sulfonic group, phosphate, carboxylic acid group, imino group or phenolic hydroxyl group, and the nano particle loaded is selected from oxidation
The compound of one or more of iron, zirconium oxide or manganese oxide.
Preferably, step (B) is under room temperature, pH neutrallty conditions, with the rate of 0.5-2BV/h in the resin of adsorption penetration
5-10% salting liquids are added as desorbing agent, make resin regeneration.
Preferably, heavy metal ion content is less than concentration of heavy metal ion in desorption liquid in the water outlet with high salt of step (C) gained
5%.
Preferably, using the water outlet with high salt of step (D) recycling be configured to 5-10% salt content again return to step (B) as
Desorbing agent.
Preferably, it is 1-5mg/L by heavy metal ion content in the step (A), pH is the waste water of 4-8 with 1-20BV/
H rates amount to 1000-5000BV, make resin adsorption saturation, water outlet content of beary metal is less than 0.01mg/L by resin.
Preferably, the middle electrodeposition process of step (D) or chemical precipitation method handle the heavy metal accumulation object recycling heavy metal.
Preferably, the salt includes sodium chloride or potassium chloride.
Preferably, desorption rate described in step (C) is laboratory scale to industrially scalable, the desorption flow velocity and water
Velocity ratio be 1:1.12~1:1.75, the flow velocity that is desorbed is 1L/h~5000L/h, the second raffinate described in step (D)
According to 1:1000 constants are added in step (A) described heavy metal ion-containing waste water.
3. advantageous effect
Using technical solution provided by the invention, compared with prior art, have the advantages that：
(1) present invention is directed to the waste water of the low-concentration heavy metal ions containing 1-5mg/L, and weight is persistently adsorbed using resin sorbent
Metal so that concentration of heavy metal ion is less than 0.01mg/L, then is adsorbed obtained by flushed in the liquid crossed through adsorption treatment
The resin penetrated obtains high concentration heavy metal high concentration salt solutions, the suitable diffusion dialysis device separating beavy metal of reselection and salt
Solution, without using acid solution in wastewater treatment process of the invention, there is no need to the special equipment of anti-acid corrosion, without addition
Alkali neutralizes, and saves process and cost.
(2) present invention for desorption salting liquid can recovery again, significantly reduce production cost and environment
Pollution meets the energy-saving and emission-reduction industrial policy of current country, suitable for industrialization promotion.
(3) the moisture film flux of diffusive dialysis method of the prior art is very low, is not suitable for the waste water treatment industrialization of big yield
Using；The present invention creatively for handling the desorption liquid containing heavy metal ion and salt of small water, respectively obtain salting liquid and
Raffinate containing heavy metal ion；Salting liquid is recycled as desorbing agent, raffinate electrodeposition process or change containing heavy metal ion
It learns the precipitation method to handle to obtain heavy metal accumulation object, on the one hand reduces cost, reduce pollution；On the other hand, recycling can be realized
Handle heavy metal wastewater thereby.Raffinate is proportionally back in the heavy metal-containing waste water of water after processing, continues cycling through processing.
(4) present invention is using resin adsorption heavy metal wastewater thereby, after saturation, first with salting liquid to resin desorption, diffusion dialysis
Method detaches the heavy metal in desorption waste liquid and salting liquid, the advantages of combining resin adsorption and diffusive dialysis method, can realize
The recycling treatment of heavy metal wastewater thereby.
(5) present invention is using resin sorbent, using such as sodium chloride or potassium chloride salting liquid as desorbing agent, and make
With the waste water of diffusion dialysis technical tie-up processing heavy metal ion containing 1-5mg/L, the sodium chloride obtained after diffusion dialysis or chlorination
Potassium salt soln reuse can make resin desorption agent again, and entire technological process only discharges the first water outlet and as solid waste or industrial by-product
Heavy metal is recycled, wherein concentration of heavy metal ion is less than 0.01mg/L, qualified discharge, so as to fulfill heavy metal contained by the first water outlet
With the efficient resource utilization of salt, cost is saved, adapts to the needs handled on a large scale.
Specific embodiment
Fig. 1 is flow diagram of the present invention.
Specific embodiment
To further appreciate that present disclosure, with reference to accompanying drawings and embodiments, the present invention is described in detail.
The term BV used in the present invention refers to resin bed volume；The content of the present invention, percentage are being not particularly illustrated
Under the premise of, each mean weight.
Diffusion dialysis is by the use of the concentration difference of amberplex both sides solute as driving force, passes through the choosing of amberplex
Permeability is selected to realize the separation of heavy metal ion and salt in resin desorption liquid, it is heavy in diffuser casing with the increase of water flow
The concentration of metal ion and salt reduces, and the concentration of solute is constant in dialysing compartment, and the concentration difference of such film both sides solute increases, because
This, has more sodium or potassium ion to enter diffuser casing through film from dialysing compartment, so as to cause the salt rate of recovery and heavy metal slip
Increase.Sodium potassium ion and heavy metal ion can be transferred through amberplex, but sodium potassium ion by speed ratio heavy metal ion
By speed it is fast, achieve the purpose that separation in this way, in this way separation be to be determined by the property of desorption liquid anacidity with high salt
's.
Embodiment 1
A kind of method of resin adsorption desorption-diffusion dialysis processing heavy metal-containing waste water, step are：
(A) content of copper ion, pH value copper-containing wastewater as shown in Table 1 are passed through into NDA-Cu type resins with 1-20BV/h rates
Column makes resin adsorption saturation；
(B) in room temperature, under conditions of pH is 6-8, with the rate of 0.5-2BV/h in the NDA-Cu type resins of adsorption penetration
5-10% sodium chloride solutions are added as desorbing agent, make resin regeneration；
(C) will come from step (B) contains Cu2+The desorption and regeneration liquid and water of ion and sodium chloride are separately added into using NDADF1
The velocity ratio of the desorption liquid of the diffusion dialysis device of anion-exchange membrane and water inlet, control desorption flow velocity and water is 1:1.12
~1:1.75, wherein desorption flow velocity is 1L/h~5000L/h, respectively obtain the water outlet with high salt of 1 concentration of table and high-copper water outlet；
(D) it is discharged to obtain Cu with usually used electrodeposition process or chemical precipitation method processing high-copper2+Ion enrichment solution returns
It receives and utilizes, the content that the sodium chloride solution that step (C) is recycled is configured to 5-10% again returns to step (B) as desorbing agent.
The resin used in the present invention includes：NDA-Cu, NDA-Ni from Jiangsu NJU Environmental Technology Co., Ltd.,
NDA-Fe, NDA-Cr and NDA-Mn type resin；The LX- of Xi'an Sunresin New Materials Co., Ltd. can also be used
300C、LSI-296、LSC-100、LSC-500；PUROLITES950；AmberliteIRC747、AmberliteIRC748、
AmberliteIRC86；Zhejiang wins honour for D113, D851, D860, D417 of resin processing plant.
The anion-exchange membrane used in the present invention includes：NDADF1 from Jiangsu NJU Environmental Technology Co., Ltd. and
NDADF2 type anion-exchange membranes；TWDDA1, TWDDA2 of Shandong Tianwei Membrane Technology Co., Ltd. can also be used.
The parameter value of 1 scheme 1-4 of table
Embodiment 2
A kind of method of resin adsorption desorption-diffusion dialysis processing heavy metal-containing waste water, step are：
(A) nickel ion content, pH value nickel-containing waste water as shown in Table 2 are passed through into NDA-Ni type resins with 1-20BV/h rates
Column 2h makes resin adsorption saturation；
(B) in room temperature, under conditions of pH is 6-8, with the rate of 0.5-2BV/h in the NDA-Ni type resins of adsorption penetration
5-10% Klorvess Liquids are added as desorbing agent, make resin regeneration；
(C) will come from step (B) contains Ni2+The desorption and regeneration liquid and water of ion and potassium chloride are separately added into using NDADF2
The desorption liquid of the diffusion dialysis device of anion-exchange membrane and water inlet, control are desorbed flow velocity as 400-700ml/h, the stream of water
Speed is 450-850ml/h, respectively obtains the Klorvess Liquid of 2 concentration of table and containing Ni2+The raffinate of ion；
(D) with usually used electrodeposition process or chemical precipitation method processing containing Ni2+The raffinate of ion obtains Ni2+Ion is rich
Collect solution recycle, using step (C) recycle Klorvess Liquid be configured to 5-10% content again return to step (B) as
Desorbing agent.
The parameter value of 2 scheme 5-8 of table
Embodiment 3
A kind of method of resin adsorption desorption-diffusion dialysis processing heavy metal-containing waste water, step are：
(A) waste water containing heavy metal ion is made into resin adsorption saturation by resin；I.e. heavy metal ion content is 1-
5mg/L, when it is implemented, the numerical value such as 1mg/L, 5mg/L, 1.2mg/L, 2.5mg/L or 4.2mg/L can be selected；PH is 4-8
The waste water of (when it is implemented, the numerical value such as 4,5,6,7 or 8 can be selected) with 1-20BV/h (when it is implemented, can select 1,
20th, the numerical value such as 12,6 or 2) rate by resin, amount to 1000-5000BV (when it is implemented, can select 1000,1200,
3600th, the numerical value such as 4800 or 5000), make resin adsorption saturation；
Wherein, the heavy metal in the present embodiment can be one or more of copper, nickel, zinc, lead, chromium, manganese or cadmium；
The skeleton of resin functional group bonded on polystyrene divinyl benzene or polyacrylic acid, skeleton is selected from
Sulfonic group, phosphate, carboxylic acid group, imino group or phenolic hydroxyl group, the nano particle loaded are selected from iron oxide, zirconium oxide or manganese oxide
One or more of compound.
The resin is NDA-Cu, NDA-Ni, NDA-Fe, NDA-Cr and NDA-Mn type resin；Xi'an can also be used
LX-300C, LSI-296, LSC-100, LSC-500 of indigo plant dawn scientific and technological new material limited company；PUROLITES950；
AmberliteIRC747、AmberliteIRC748、AmberliteIRC86；Zhejiang win honour for resin processing plant D113, D851,
D860、D417。
(B) salting liquid is added in the resin of adsorption penetration as desorbing agent, makes resin regeneration, the salt includes sodium chloride
Or potassium chloride；
Under room temperature, pH neutrallty conditions, with the rate of 0.5-2BV/h addition 5-10% (tools in the resin of adsorption penetration
When body is implemented, the numerical value such as 5%, 10%, 6%, 7% or 8% can be selected) salting liquid as desorbing agent, makes resin regeneration, and it is described
Salt includes sodium chloride or potassium chloride.
(C) the de- of diffusion dialysis device will be separately added into from the desorption liquid of step (B) containing heavy metal ion and salt and water
Attached liquid and water inlet, desorption rate are laboratory scale to industrially scalable, and the velocity ratio of the desorption flow velocity and water is 1:
1.12~1:1.75, (when it is implemented, 1 can be selected:1.12、1:1.25、1:1.28、1:1.42、1:1.48 or 1:1.75 it waits
Numerical value), control desorption flow velocity for 1L/h~5000L/h (when it is implemented, can select 1,20,50,250,3000,3200,
4500 or 5000 grade numerical value), respectively obtain water outlet and the water outlet of heavy metal ion enrichment with high salt；
NDADF1 or NDADF2 type anion-exchange membranes are used in the diffusion dialysis device；Shandong day dimension film can also be used
TWDDA1, TWDDA2 of Technology Co., Ltd..Heavy metal ion content is less than 0.01mg/L in salting liquid obtained by step (C)；It will
The salting liquid of step (C) recycling is configured to 5-10% (when it is implemented, the number such as 5%, 10%, 6%, 7% or 8% can be selected
Value) content again return to step (B) as desorbing agent.
(D) with electrodeposition process or chemical precipitation method processing, the raffinate containing heavy metal ion obtains heavy metal accumulation object, recycles
It utilizes.
The physico-chemical structure index of anion-exchange membrane used in the embodiment of the present invention 1-3 diffusion dialysis devices is shown in Table 3, table
4。
The physico-chemical structure index of 3 two kinds of anion-exchange membranes of table
| Film properties parameter | NDADF1 types | NDADF2 types |
| Water content (%) | 24 | 26.4 |
| Exchange capacity (milliequivalent/dry film) | 1.8 | 2.0 |
| Fixed group concentration | 0.950 | 0.982 |
| Film thickness (mm) | 0.11-0.13 | 0.25-0.28 |
| Functional group | -NR3 | -NR3 |
| Film matrix | Polystyrene | Polyphenylene oxide |
The key technical indexes of 4 diffusion dialysis anion-exchange membrane of table
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail, within the scope of the technical concept of the present invention, a variety of equivalents can be carried out to technical scheme of the present invention, this
A little equivalents all belong to the scope of protection of the present invention.
Claims (10)
1. a kind of method of resin adsorption desorption-diffusion dialysis processing heavy metal-containing waste water, it is characterised in that：
(A) waste water containing heavy metal ion is made into resin adsorption saturation, the discharge of the first standard water discharge of gained by resin；
(B) salting liquid is added in the resin of adsorption penetration as desorbing agent, makes resin regeneration, the salt includes sodium chloride or chlorine
Change potassium；
(C) desorption liquid for diffusion dialysis device being separately added into from the desorption liquid of step (B) containing heavy metal ion and salt and water
With water inlet, water outlet with high salt and the first raffinate rich in heavy metal ion are respectively obtained；
(D) first raffinate is handled with electrodeposition process or chemical precipitation method, obtains heavy metal accumulation object and the second raffinate, it is described
Heavy metal accumulation object is as solid waste or industrial by-product, and heavy metal concentration is reduced to 5mg/L hereinafter, and step in second raffinate
(A) waste water containing heavy metal ion in takes off after merging through resin treatment qualified discharge, water outlet with high salt as the resin of step (B)
Attached dose of recycling.
2. the method for resin adsorption desorption according to claim 1-diffusion dialysis processing heavy metal-containing waste water, feature exist
In heavy metal described in step (A) includes one or more of copper, nickel, zinc, lead, chromium, manganese or cadmium.
3. the method for resin adsorption desorption according to claim 1-diffusion dialysis processing heavy metal-containing waste water, feature exist
In the functional group bonded on polystyrene divinyl benzene or polyacrylic acid, skeleton of the skeleton of resin described in step (A)
Selected from sulfonic group, phosphate, carboxylic acid group, imino group or phenolic hydroxyl group, the nano particle loaded is selected from iron oxide, zirconium oxide or oxygen
Change the compound of one or more of manganese.
4. according to the method for claim 1-3 any one of them resin adsorption desorption-diffusion dialysis processing heavy metal-containing waste water,
It is characterized in that, step (B) adds 5- in the resin of adsorption penetration under room temperature, pH neutrallty conditions with the rate of 0.5-2BV/h
10% salting liquid makes resin regeneration as desorbing agent.
5. the method for resin adsorption desorption according to claim 2-diffusion dialysis processing heavy metal-containing waste water, feature exist
In heavy metal ion content is less than 5% of concentration of heavy metal ion in desorption liquid in the water outlet with high salt of step (C) gained.
6. the method for resin adsorption desorption according to claim 2-diffusion dialysis processing heavy metal-containing waste water, feature exist
In the salt content that the water outlet with high salt recycling of step (D) is configured to 5-10% again returns to step (B) as desorbing agent.
7. the method for resin adsorption desorption according to claim 4-diffusion dialysis processing heavy metal-containing waste water, feature exist
In, in the step (A), by heavy metal ion content be 1-5mg/L, pH be 4-8 waste water tree is passed through with 1-20BV/h rates
Fat amounts to 1000-5000BV, makes resin adsorption saturation, and the first water outlet content of beary metal is less than 0.01mg/L.
8. the method for resin adsorption desorption-diffusion dialysis processing heavy metal-containing waste water according to claim 1 or 3, feature
It is, the middle electrodeposition process of step (D) or chemical precipitation method handle the heavy metal accumulation object recycling heavy metal.
9. the method for resin adsorption desorption according to claim 4-diffusion dialysis processing heavy metal-containing waste water, feature exist
In the salt includes sodium chloride or potassium chloride.
10. the method for resin adsorption desorption according to claim 9-diffusion dialysis processing heavy metal-containing waste water, feature exist
In the velocity ratio that flow velocity and water are desorbed described in step (C) is 1:1.12~1:1.75, it is described desorption flow velocity for 1L/h~
5000L/h, the second raffinate is according to 1 described in step (D):1000 constants, which add in, contains heavy metal ion described in step (A)
Waste water.
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| CN115072846A (en) * | 2022-07-20 | 2022-09-20 | 中国科学院赣江创新研究院 | Method for removing heavy metal ions in industrial wastewater by utilizing electric drive and modified membrane |
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| CN114804413A (en) * | 2022-04-15 | 2022-07-29 | 中国科学院生态环境研究中心 | Heavy metal wastewater treatment method, treatment system and preparation method of adsorbent thereof |
| CN115072846A (en) * | 2022-07-20 | 2022-09-20 | 中国科学院赣江创新研究院 | Method for removing heavy metal ions in industrial wastewater by utilizing electric drive and modified membrane |
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