CN105692768A - Method for selectively extracting heavy metals in heavy metal-ammonia complexing wastewater by virtue of chelate resin - Google Patents
Method for selectively extracting heavy metals in heavy metal-ammonia complexing wastewater by virtue of chelate resin Download PDFInfo
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- CN105692768A CN105692768A CN201610197130.8A CN201610197130A CN105692768A CN 105692768 A CN105692768 A CN 105692768A CN 201610197130 A CN201610197130 A CN 201610197130A CN 105692768 A CN105692768 A CN 105692768A
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- 229920005989 resin Polymers 0.000 title claims abstract description 257
- 239000011347 resin Substances 0.000 title claims abstract description 257
- 239000002351 wastewater Substances 0.000 title claims abstract description 73
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 70
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 43
- 230000000536 complexating effect Effects 0.000 title claims abstract description 25
- 239000013522 chelant Substances 0.000 title abstract 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 71
- 150000002500 ions Chemical class 0.000 claims abstract description 32
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 10
- 230000001172 regenerating effect Effects 0.000 claims abstract description 9
- 230000008929 regeneration Effects 0.000 claims abstract description 6
- 238000011069 regeneration method Methods 0.000 claims abstract description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 127
- 229920001429 chelating resin Polymers 0.000 claims description 65
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 48
- 230000007704 transition Effects 0.000 claims description 28
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 15
- 239000001117 sulphuric acid Substances 0.000 claims description 15
- 235000011149 sulphuric acid Nutrition 0.000 claims description 15
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 14
- 238000000605 extraction Methods 0.000 claims description 14
- 239000004471 Glycine Substances 0.000 claims description 10
- PTMHPRAIXMAOOB-UHFFFAOYSA-N phosphoramidic acid Chemical compound NP(O)(O)=O PTMHPRAIXMAOOB-UHFFFAOYSA-N 0.000 claims description 8
- 229940061584 phosphoramidic acid Drugs 0.000 claims description 8
- 230000001105 regulatory effect Effects 0.000 claims description 7
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 6
- 229910001431 copper ion Inorganic materials 0.000 claims description 5
- 229910001453 nickel ion Inorganic materials 0.000 claims description 5
- KXDHJXZQYSOELW-UHFFFAOYSA-N carbonic acid monoamide Natural products NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 claims description 3
- KJAMZCVTJDTESW-UHFFFAOYSA-N tiracizine Chemical compound C1CC2=CC=CC=C2N(C(=O)CN(C)C)C2=CC(NC(=O)OCC)=CC=C21 KJAMZCVTJDTESW-UHFFFAOYSA-N 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 2
- 150000003927 aminopyridines Chemical class 0.000 claims description 2
- 238000011049 filling Methods 0.000 claims description 2
- 239000012492 regenerant Substances 0.000 claims description 2
- 239000007788 liquid Substances 0.000 abstract description 32
- 230000035515 penetration Effects 0.000 abstract description 26
- 230000008569 process Effects 0.000 abstract description 10
- 238000004140 cleaning Methods 0.000 abstract description 7
- 238000000926 separation method Methods 0.000 abstract description 4
- 238000004065 wastewater treatment Methods 0.000 abstract description 4
- 239000003513 alkali Substances 0.000 abstract description 2
- 230000007935 neutral effect Effects 0.000 abstract description 2
- 238000004064 recycling Methods 0.000 abstract description 2
- 238000007599 discharging Methods 0.000 abstract 1
- 238000005086 pumping Methods 0.000 abstract 1
- 230000009466 transformation Effects 0.000 abstract 1
- 238000003795 desorption Methods 0.000 description 102
- 229910052759 nickel Inorganic materials 0.000 description 54
- 238000010521 absorption reaction Methods 0.000 description 53
- 239000010949 copper Substances 0.000 description 43
- 238000009713 electroplating Methods 0.000 description 37
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 34
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 29
- 229910052802 copper Inorganic materials 0.000 description 29
- 238000001179 sorption measurement Methods 0.000 description 26
- 238000012360 testing method Methods 0.000 description 25
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 24
- 238000004088 simulation Methods 0.000 description 24
- 239000000243 solution Substances 0.000 description 23
- NBFQLHGCEMEQFN-UHFFFAOYSA-N N.[Ni] Chemical compound N.[Ni] NBFQLHGCEMEQFN-UHFFFAOYSA-N 0.000 description 12
- 235000019270 ammonium chloride Nutrition 0.000 description 12
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 12
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 12
- 235000011130 ammonium sulphate Nutrition 0.000 description 12
- 229920006395 saturated elastomer Polymers 0.000 description 12
- 239000002253 acid Substances 0.000 description 9
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 8
- 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 7
- 238000005516 engineering process Methods 0.000 description 7
- 239000003456 ion exchange resin Substances 0.000 description 7
- 229920003303 ion-exchange polymer Polymers 0.000 description 7
- 238000012545 processing Methods 0.000 description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 6
- 229910017604 nitric acid Inorganic materials 0.000 description 6
- 229920000768 polyamine Polymers 0.000 description 6
- 238000010668 complexation reaction Methods 0.000 description 4
- 238000005530 etching Methods 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 238000004062 sedimentation Methods 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- QKSIFUGZHOUETI-UHFFFAOYSA-N copper;azane Chemical compound N.N.N.N.[Cu+2] QKSIFUGZHOUETI-UHFFFAOYSA-N 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 3
- 239000003463 adsorbent Substances 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- -1 cationic ion Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- PDQXSLJFPJSYBF-UHFFFAOYSA-N 2-(dithiocarboxyamino)acetic acid Chemical compound OC(=O)CNC(S)=S PDQXSLJFPJSYBF-UHFFFAOYSA-N 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000011953 bioanalysis Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000701 coagulant Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- JJLJMEJHUUYSSY-UHFFFAOYSA-L copper(II) hydroxide Inorganic materials [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000009615 deamination Effects 0.000 description 1
- 238000006481 deamination reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000010814 metallic waste Substances 0.000 description 1
- DAKZISABEDGGSV-UHFFFAOYSA-N n-(2-aminoethyl)acetamide Chemical compound CC(=O)NCCN DAKZISABEDGGSV-UHFFFAOYSA-N 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000002699 waste material 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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
-
- 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
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/04—Surfactants, used as part of a formulation or alone
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)
- Water Treatment By Sorption (AREA)
Abstract
The invention discloses a method for selectively extracting heavy metals in heavy metal-ammonia complexing wastewater by virtue of chelate resin, belonging to the fields of heavy metal wastewater treatment and recycling. The method comprises the steps of pumping heavy metal-ammonia complexing wastewater into a resin column filled with chelate resin, regenerating resin by virtue of a regenerating agent after concentration of heavy metals in effluent of the resin column reaches a penetration concentration, cleaning with clean water, and carrying out transformation on the chelate resin by virtue of a dilute alkali solution after the pH of effluent of the resin column becomes neutral, wherein obtained regeneration liquid is a recyclable high-concentration heavy metal solution, and obtained cleaning liquid is used for preparing the next batch of regenerating agents or is recycled as cleaning water in the next process; the transformed chelate resin can be recycled. According to the method, heavy metal-ammonia complexing wastewater is resourcefully treated by virtue of the chelate resin capable of selectively adsorbing and separating heavy metal ions, the selective separation of complexed heavy metals is realized in a low consumption manner, and the concentration of the effluent meets discharging standards.
Description
Technical field
The invention belongs to field of waste water treatment, specifically, relate to process and the method for resource of one heavy metal species-ammonia complexing waste water, more particularly, it relates to a kind of method utilizing chelating resin selective extraction heavy metal-ammonia complexing heavy metal in waste water。
Background technology
Ammonia is chelating agent common in field of electroplating and additive, can make coating evenly light, promote anodic solution。Alkalescence plating solution covering power containing ammonia is good, good toughness, and coating is more excellent。Such as, ammonium salt zinc-plated obtain the careful light of coating crystallization, plating solution current efficiency is high, deposition velocity is fast。It addition, also containing a large amount of ammonia in printed circuit board (PCB) (PCB) etching solution, especially in alkaline etching liquid, high strength ammonia maintains heavy metal to be existed with the dissolved coordination compound in alkaline solution, it is prevented that heavy metal precipitation, and participates in metal surface etching。In electroplating technology, heavy metals emission point is mainly electroplating cleaning and electroplating effluent forms link, along with scrapping of printed circuit board (PCB) alkaline etching liquid, also can produce alkaline high ammonia heavy metal-containing waste water。This type of waste water characteristic is: waste water is in alkalescence, and Heavy Metals is complicated, and toxicity is high。Ammonia is conventional buffer agent, and acid adjustment contact break acid requirement is big, increase handling with and go out salinity water。Therefore, this type of waste water alkalescence contact break processes great economy and high efficiency。But, general the processing method such as sedimentation method, electrochemical deposition method, membrance separation, electrolysis, solvent extraction and bioanalysis etc. are difficult to reach the effect of heavy-metal ion removal, or face process costly, the difficult problem such as complicated operation and secondary pollution。
The method processing ammonia Counter weight metal waste water at present mainly has the sedimentation method, reducing process, embrane method and ion exchange etc.。If Chinese Patent Application No. is 201310449645.9, application publication date is the open a kind of Copper ammonia complexation wastewater treatment method of in December, 2013 patent application document of 25 days, utilizes MAP method by ammonia from copper ammonia complexation ion [Cu (NH3)4]2+Middle disengaging, ammonia and copper are respectively with MgNH4PO4、Cu(OH)2Form precipitates, precipitated product through deamination, reclaim and return water treatment technology after copper, but adding of agent is required height, complicated operation by this method, and copper recovery difficult is big, and increases and salinity water。Chinese Patent Application No. is 201410491730.6, application publication date is that in December, 2014 patent application document of 24 days is open a kind of to be reclaimed containing copper ammonia complexation waste water resource and zero-emission membranous system and processing method thereof and application, application film combined treatment cuprammonium waste water is proposed, four groups of film cascades run and add operation easier, high for actual electroplating wastewater pre-processing requirements, fouling membrane is also a great problem。Reducing process is to add iron powder, ferrous sulfate etc. in waste water to be replaced by copper, but the useless yield of this method danger is big, and is difficult to heavy metal and reclaims。Chinese Patent Application No. is 201310161883.X, the patent application document that application publication date is on August 14th, 2013 discloses a kind of method and apparatus reclaiming heavy metal out of electroplating wastewater, the method comprises the following steps: electroplating wastewater is carried out ion exchange resin treatment by (1), and what make in electroplating wastewater is heavy metal ion adsorbed on ion exchange resin；(2) it is adsorbed in the heavy metal ion on ion exchange resin with regenerative agent eluting, obtains regenerated liquid；(3) adopt cyclone electrolytic cell technology electrolytic regeneration liquid, make a huge sum of money belong to and negative electrode precipitates out。But for the heavy metal under high-concentration ammonia-nitrogen in alkaline solution, heavy metal exists with cation complex form, the selectivity of ion exchange resin heavy metal is poor, it is difficult to effective by heavy metals removal, for the recovery of alkaline high ammonia density heavy metal in waste water inapplicable。It is more that chelating resin heavy metal reclaims research, if the patent No. is that the patents such as ZL200610041366.9 and ZL201010512734.X are all based on the chelating resin absorption for ionic state heavy metal, and it is not mentioned for the absorption of complexity complex state heavy metal in alkaline high ammono-system, chelating resin is different to the avtive spot of different conditions heavy metal, mechanism of action is different, and therefore performance difference is notable。The method processing ammino heavy metal wastewater thereby at present mainly concentrates on cuprammonium waste water, and the report that other heavy metals-ammonia waste water processes is less, and this respect technology is deficient, therefore needs the new technology and method processed for heavy metal-ammonia complexing waste water high-efficiency badly。Adsorption technology is owing to having the features such as simple to operate, non-secondary pollution and resource regeneration, receive much attention in recent years, and it is widely used in purification and the recycling treatment of heavy metal wastewater thereby, but in heavy metal-ammonia waste water, all ion exchange resin and part chelating resin are all difficult to heavy metal Selective Separation be removed and reclaim, because the high strength ammonia heavy metal exchange coexisted all has obvious inhibiting effect with complexation process。
Summary of the invention
1. the problem solved
Secondary pollution is there is serious for the method processing heavy metal-ammonia complexing waste water at present, processing cost is high and heavy metal cannot the effective problem such as recovery, the present invention provides a kind of method utilizing chelating resin selective extraction heavy metal-ammonia complexing heavy metal in waste water, chelating resin is as a kind of new adsorbent, its N, O and S can form stable coordination with heavy metal, heavy metal in waste water-ammino-complex can be carried out in the basic conditions selective absorption, make content of beary metal in water outlet up to standard, after resin penetrates, heavy metal carries out desorption recovery, finally with sodium hydroxide solution resin made the transition and continue to run with。
2. technical scheme
In order to solve the problems referred to above, the technical solution adopted in the present invention is as follows:
A kind of method utilizing chelating resin selective extraction heavy metal-ammonia complexing heavy metal in waste water, the steps include:
1) pH to 5-10 of heavy metal-ammonia complexing waste water is regulated；
2) by step 1) in heavy metal-ammonia complexing waste water pump into filling chelating resin resin column；
3) treat step 2) in resin column water outlet reach breakthrough concentration (GB21900-2008 table three standard limited value: nickel ion concentration reaches 0.1mg/L, copper ion concentration reaches 0.3mg/L) after, with the regenerative agent of 1-5 times of resin bed volume, chelating resin is carried out Regeneration Treatment；
4) until step 3) in after resin regeneration, with clear water, chelating resin is carried out, to be cleaned to resin column water outlet pH value close to neutrality, adopt dilute alkaline soln that chelating resin is made the transition, be alkaline by chelating resin functional group conversions。
Preferably, the content of described heavy metal-ammonia complexing heavy metal in waste water is 0.3-300mg/L, and the content of ammonia is 0.3-10.5g/L, pH is 5-10。
Preferably, described chelating resin is carbamic acid type, glycine type, phosphoramidic acid type, aminopyridine type chelating resin or many amines chelating resin。
Preferably, described heavy metal is divalent heavy metal ions, including nickel ion and copper ion。
Preferably, described step 2) in resin column Water discharge flow speed be 1-20 times of bed volume (BV/h) per hour。
Preferably, described step 3) in, the breakthrough concentration of nickel ion is 0.1mg/L, and the breakthrough concentration of copper ion is 0.3mg/L。
Preferably, described step 3) in regenerative agent be the hydrochloric acid of 5-15% (mass fraction), sulphuric acid or salpeter solution。
Preferably, described step 3) in regenerant flow rate be 0.5-5BV/h。
Preferably, described step 4) in clean water flow velocity be 1-20BV/h。
Preferably, described step 4) in dilute alkaline soln refer to the sodium hydroxide solution or potassium hydroxide solution that mass fraction is 1-10%, flow velocity is 1-10BV/h。
Wherein, step 4) in desorption liquid be callable high concentration heavy metal solution, can as the raw material of bath solution or reclaimed by electrochemical process, aqueous cleaning is used for preparing next group regenerative agent or cleaning water jacket as next group using。
In heavy metal-ammonia waste water, heavy metal exists with the ammino form of heavy metal in the basic conditions, is in dissolved state, and general coagulant sedimentation is difficult to hydroxide form precipitation, the heavy metal in heavy metal-ammonia waste water is removed (such as formula one and formula two)。
Cu2++4NH4 ++OH-=Cu (NH3)4 2++4H2O formula one
Ni2++2NH4 ++OH-=Ni (NH3)2 2++2H2O formula two
Under high-concentration ammonia-nitrogen, heavy metal forms the multidentate ligand complex that surrounded by ammonia, as nickel and copper and ammonia form complexed as shown in Figure 1。
For cationic ion exchanger resin, the functional group on resin can not identify preferably with the ammonium radical ion in positive electricity and heavy metal-ammino-complex, cause ion exchange resin can not effective as selective by heavy metals removal。And the function base such as the carboxyl on chelating resin and amino has stronger coordination ability with heavy metal, may identify which the heavy metal under high-concentration ammonia-nitrogen, reach the purpose of heavy metal under selective extraction alkalescence high-concentration ammonia-nitrogen, it also avoid in conventional treatment method substantial amounts of medicament expense needed for contact break acid adjustment with and go out the increase of salinity water。
3. beneficial effect
Compared to prior art, the invention have the benefit that
(1) present invention can remove the heavy metal existed with complex form with ammonia in electroplating wastewater effectively, it is adaptable to electroplating cleaning waste water that in electroplating industry neutral and alkali cyanideless electro-plating, heavy metal and ammonia electroplating process produce or the advanced treating of tail water；
(2) chelating resin that the present invention adopts is a kind of new adsorbent, N, O and S on chelating resin can form stable coordination with heavy metal, can efficiently, selectively extract the heavy metal in wastewater with high ammonia nitrogen concentration, avoid useless generation of endangering in the sedimentation method, and general ion exchange resin can not effectively select the defect of the heavy metal in high-concentration ammonia-nitrogen, great economy, high efficiency；
(3) present invention utilizes the coordination ability that the functional group on chelating resin is stronger with heavy metal, by the heavy metal efficient selective adsorbing separation under alkalescence high-concentration ammonia-nitrogen, can make heavy metal qualified discharge standard；
(4) present invention can adopt automatic control system to carry out wastewater treatment, saves manpower, has broad application prospects。
Accompanying drawing explanation
Fig. 1 is the structural formula of cuprammonium and nickel ammine。
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is further described below。
Embodiment 1
21mL (humid volume) glycine chelating resin is inserted resin column, (nickel initial concentration is 100mg/L to regulate simulation nickel ammonia electroplating wastewater, ammonium sulfate initial concentration is 2.5g/L) pH is 5, pumps in resin column, resin the rate of output water is 1BV/h。After adsorption penetration, the resin after absorption is carried out desorption with the hydrochloric acid that mass fraction is 5% by (Ni ion concentration is more than 0.1mg/L), and flow velocity is 0.5BV/h。Being carried out resin column to neutrality with clear water after desorption, be then pumped into the sodium hydroxide solution that mass fraction is 1%, flow velocity is 1BV/h, and resin is made the transition, and resin functionality is converted into alkalescence。After testing: resin treatment ability is 160BV, after resin absorption is saturated, desorption liquid nickel concentration is 4.6g/L, and nickel desorption rate is 99.7%。
Embodiment 2
21mL (humid volume) glycine chelating resin is inserted resin column, (nickel initial concentration is 100mg/L to regulate simulation nickel ammonia electroplating wastewater, ammonium sulfate initial concentration is 2.5g/L) pH is 8, pumps in resin column, resin the rate of output water is 10BV/h。After adsorption penetration, the resin after absorption is carried out desorption with the hydrochloric acid that mass fraction is 10% by (Ni ion concentration is more than 0.1mg/L), and flow velocity is 2BV/h。Being carried out resin column to neutrality with clear water after desorption, be then pumped into the sodium hydroxide solution that mass fraction is 4%, flow velocity is 4BV/h, and resin is made the transition, and resin functionality is converted into alkalescence。After testing: resin treatment ability reaches 250BV, after resin absorption is saturated, desorption liquid nickel concentration is 10.7g/L, and nickel desorption rate is 99.5%。
Embodiment 3
21mL (humid volume) glycine chelating resin is inserted resin column, (nickel initial concentration is 100mg/L to regulate simulation nickel ammonia electroplating wastewater, ammonium sulfate initial concentration is 2.5g/L) pH is 10, pumps in resin column, resin the rate of output water is 20BV/h。After adsorption penetration, the resin after absorption is carried out desorption with the hydrochloric acid that mass fraction is 15% by (Ni ion concentration is more than 0.1mg/L), and flow velocity is 5BV/h。Being carried out resin column to neutrality with clear water after desorption, pump into the sodium hydroxide solution that mass fraction is 10%, flow velocity is 10BV/h, and resin is made the transition, and resin functionality is converted into alkalescence。After testing: resin treatment ability reaches 180BV, after resin absorption is saturated, desorption liquid nickel concentration is 15.3g/L, and nickel desorption rate is 99.6%。
Embodiment 4
(humid volume) phosphoramidic acid chelating resin of 21mL is inserted resin column, (nickel initial concentration is 100mg/L to regulate simulation nickel ammonia electroplating wastewater, ammonium sulfate initial concentration is 2.5g/L) pH is 5, pumps in resin column, resin the rate of output water is 1BV/h。After adsorption penetration, the resin after absorption is carried out desorption with the sulphuric acid that mass fraction is 5% by (Ni ion concentration is more than 0.1mg/L), and flow velocity is 0.5BV/h。Being carried out resin column to neutrality with clear water after desorption, be then pumped into the sodium hydroxide solution that mass fraction is 1%, flow velocity is 1BV/h, and resin is made the transition, and resin functionality is converted into alkalescence。After testing: resin treatment ability reaches 90BV, after resin absorption is saturated, desorption liquid nickel concentration is 2.9g/L, and nickel desorption rate is 99.8%。
Embodiment 5
21mL (humid volume) phosphoramidic acid chelating resin is inserted resin column, (nickel initial concentration is 100mg/L to regulate simulation nickel ammonia electroplating wastewater, ammonium sulfate initial concentration is 2.5g/L) pH is 8, pumps in resin column, resin the rate of output water is 10BV/h。After adsorption penetration, the resin after absorption is carried out desorption with the sulphuric acid that mass fraction is 10% by (Ni ion concentration is more than 0.1mg/L), and flow velocity is 2BV/h。Being carried out resin column to neutrality with clear water after desorption, be then pumped into the sodium hydroxide solution that mass fraction is 4%, flow velocity is 4BV/h, and resin is made the transition, and makes resin functionality be converted into alkalescence。After testing: resin treatment ability reaches 160BV, after resin absorption is saturated, desorption liquid nickel concentration is 7.4g/L, and nickel desorption rate is 99.7%。
Embodiment 6
21mL (humid volume) phosphoramidic acid chelating resin is inserted resin column, (nickel initial concentration is 100mg/L to regulate simulation nickel ammonia electroplating wastewater, ammonium sulfate initial concentration is 2.5g/L) pH is 10, pumps in resin column, resin the rate of output water is 20BV/h。After adsorption penetration, the resin after absorption is carried out desorption with the sulphuric acid that mass fraction is 15% by (Ni ion concentration is more than 0.1mg/L), and flow velocity is 5BV/h。Being carried out resin column to neutrality with clear water after desorption, pump into the sodium hydroxide solution that mass fraction is 10%, flow velocity is 10BV/h, and resin is made the transition, and makes resin functionality be converted into alkalescence。After testing: resin treatment ability reaches 140BV, after resin absorption is saturated, desorption liquid nickel concentration is about 12.9g/L, and nickel desorption rate is 98.5%。
Embodiment 7
4mL (humid volume) glycine chelating resin is inserted resin column, (copper initial concentration is 50mg/L to regulate simulation cuprammonium electroplating wastewater, ammonium chloride initial concentration is 3.75g/L) pH is 5, pumps in resin column, resin the rate of output water is 1BV/h。After adsorption penetration, the resin after absorption is carried out desorption with the sulphuric acid that mass fraction is 5% by (Cu ion concentration is more than 0.3mg/L), and flow velocity is 0.5BV/h。Being carried out resin column to neutrality with clear water after desorption, pump into the sodium hydroxide solution that mass fraction is 1%, flow velocity is 1BV/h, and resin is made the transition, and makes resin functionality be converted into alkalescence。After testing: resin treatment ability reaches 440BV, after resin absorption penetrates, desorption liquid copper concentration is 2.1g/L, and nickel desorption rate is 93%。
Embodiment 8
4mL (humid volume) glycine chelating resin is inserted resin column, (copper initial concentration is 50mg/L to regulate simulation cuprammonium electroplating wastewater, ammonium chloride initial concentration is 3.75g/L) pH is 8, pumps in resin column, resin the rate of output water is 10BV/h。After adsorption penetration, the resin after absorption is carried out desorption with the sulphuric acid that mass fraction is 10% by (Cu ion concentration is more than 0.3mg/L), and flow velocity is 2BV/h。Being carried out resin column to neutrality with clear water after desorption, pump into the sodium hydroxide solution that mass fraction is 4%, flow velocity is 4BV/h, and resin is made the transition, and makes resin functionality be converted into alkalescence。After testing: resin treatment ability reaches 520BV, after resin absorption penetrates, desorption liquid copper concentration is 6.9g/L, and nickel desorption rate is 93.1%。
Embodiment 9
4mL (humid volume) glycine chelating resin is inserted resin column, (copper initial concentration is 50mg/L to regulate simulation cuprammonium electroplating wastewater, ammonium chloride initial concentration is 3.75g/L) pH is 10, pumps in resin column, resin the rate of output water is 20BV/h。After adsorption penetration, the resin after absorption is carried out desorption with the sulphuric acid that mass fraction is 15% by (Cu ion concentration is more than 0.3mg/L), and flow velocity is 5BV/h。Being carried out resin column to neutrality with clear water after desorption, pump into the sodium hydroxide solution that mass fraction is 10%, flow velocity is 10BV/h, and resin is made the transition, and makes resin functionality be converted into alkalescence。After testing: resin treatment ability reaches 265BV, after resin absorption penetrates, desorption liquid copper concentration is 6.2g/L, and nickel desorption rate is 98.5%。
Embodiment 10
4mL (humid volume) phosphoramidic acid chelating resin is inserted resin column, (copper initial concentration is 50mg/L to regulate simulation cuprammonium electroplating wastewater, ammonium chloride initial concentration is 3.75g/L) pH is 5, pumps in resin column, resin the rate of output water is 1BV/h。After adsorption penetration, the resin after absorption is carried out desorption with the nitric acid that mass fraction is 5% by (Cu ion concentration is more than 0.3mg/L), and flow velocity is 0.5BV/h。Being carried out resin column to neutrality with clear water after desorption, pump into the sodium hydroxide solution that mass fraction is 1%, flow velocity is 1BV/h, and resin is made the transition, and makes resin functionality be converted into alkalescence。After testing: resin treatment ability reaches 380BV, after resin absorption penetrates, desorption liquid copper concentration is 1.8g/L, and nickel desorption rate is 99.3%。
Embodiment 11
(humid volume) phosphoramidic acid chelating resin of 4mL is inserted resin column, (copper initial concentration is 50mg/L to regulate simulation cuprammonium electroplating wastewater, ammonium chloride initial concentration is 3.75g/L) pH is 8, pumps in resin column, resin the rate of output water is 10BV/h。After adsorption penetration, the resin after absorption is carried out desorption with the nitric acid that mass fraction is 10% by (Cu ion concentration is more than 0.3mg/L), and flow velocity is 2BV/h。Being carried out resin column to neutrality with clear water after desorption, pump into the sodium hydroxide solution that mass fraction is 4%, flow velocity is 4BV/h, and resin is made the transition, and makes resin functionality be converted into alkalescence。After testing: resin treatment ability reaches 350BV, after resin absorption penetrates, desorption liquid copper concentration is 4.9g/L, and nickel desorption rate is 99.1%。
Embodiment 12
4mL (humid volume) phosphoramidic acid chelating resin is inserted resin column, (copper initial concentration is 50mg/L to regulate simulation cuprammonium electroplating wastewater, ammonium chloride initial concentration is 3.75g/L) pH is 10, pumps in resin column, resin the rate of output water is 20BV/h。After adsorption penetration, the resin after absorption is carried out desorption with the nitric acid that mass fraction is 15% by (Cu ion concentration is more than 0.3mg/L), and flow velocity is 5BV/h。Being carried out resin column to neutrality with clear water after desorption, pump into the sodium hydroxide solution that mass fraction is 10%, flow velocity is 10BV/h, and resin is made the transition, and makes resin functionality be converted into alkalescence。After testing: resin treatment ability reaches 180BV, after resin absorption penetrates, desorption liquid copper concentration is 3.8g/L, and nickel desorption rate is 99.5%。
Embodiment 13
4mL (humid volume) amidocarbonic acid chelating resin is inserted resin column, (nickel initial concentration is 100mg/L to regulate simulation nickel ammonia electroplating wastewater, ammonium sulfate initial concentration is 2.5g/L) pH is 5, pumps in resin column, resin the rate of output water is 1BV/h。After adsorption penetration, the resin after absorption is carried out desorption with the sulphuric acid that mass fraction is 5% by (Ni ion concentration is more than 0.1mg/L), and flow velocity is 0.5BV/h。Being carried out resin column to neutrality with clear water after desorption, pump into the potassium hydroxide solution that mass fraction is 1%, flow velocity is 1BV/h, and resin is made the transition, and makes resin functionality be converted into alkalescence。After testing: resin treatment ability is 100BV, after resin absorption is saturated, desorption liquid nickel concentration is 3.2g/L, and nickel desorption rate is 99.3%。
Embodiment 14
4mL (humid volume) amidocarbonic acid chelating resin is inserted resin column, (nickel initial concentration is 100mg/L to regulate simulation nickel ammonia electroplating wastewater, ammonium sulfate initial concentration is 2.5g/L) pH is 8, pumps in resin column, resin the rate of output water is 10BV/h。After adsorption penetration, the resin after absorption is carried out desorption with the sulphuric acid that mass fraction is 10% by (Ni ion concentration is more than 0.1mg/L), and flow velocity is 2BV/h。Being carried out resin column to neutrality with clear water after desorption, pump into the potassium hydroxide solution that mass fraction is 4%, flow velocity is 4BV/h, and resin is made the transition, and makes resin functionality be converted into alkalescence。After testing: resin treatment ability is 180BV, after resin absorption is saturated, desorption liquid nickel concentration is 9.5g/L, and nickel desorption rate is 99.6%。
Embodiment 15
4mL (humid volume) amidocarbonic acid chelating resin is inserted resin column, (nickel initial concentration is 100mg/L to regulate simulation nickel ammonia electroplating wastewater, ammonium sulfate initial concentration is 2.5g/L) pH is 10, pumps in resin column, resin the rate of output water is 20BV/h。After adsorption penetration, the resin after absorption is carried out desorption with the sulphuric acid that mass fraction is 15% by (Ni ion concentration is more than 0.1mg/L), and flow velocity is 5BV/h。Being carried out resin column to neutrality with clear water after desorption, pump into the potassium hydroxide solution that mass fraction is 10%, flow velocity is 10BV/h, and resin is made the transition, and makes resin functionality be converted into alkalescence。After testing: resin treatment ability is 90BV, after resin absorption is saturated, desorption liquid nickel concentration is 9.7g/L, and nickel desorption rate is 98.6%。
Embodiment 16
4mL (humid volume) amidocarbonic acid chelating resin is inserted resin column, (copper initial concentration is 50mg/L to regulate simulation cuprammonium electroplating wastewater, ammonium chloride initial concentration is 3.75g/L) pH is 5, pumps in resin column, resin the rate of output water is 1BV/h。After adsorption penetration, the resin after absorption is carried out desorption with the hydrochloric acid that mass fraction is 5% by (Cu ion concentration is more than 0.3mg/L), and flow velocity is 0.5BV/h。Being carried out resin column to neutrality with clear water after desorption, pump into the potassium hydroxide solution that mass fraction is 1%, flow velocity is 1BV/h, and resin is made the transition, and makes resin functionality be converted into alkalescence。After testing: resin treatment ability reaches 360BV, after resin absorption penetrates, desorption liquid copper concentration is 1.9g/L, and nickel desorption rate is 99.2%。
Embodiment 17
4mL (humid volume) amidocarbonic acid chelating resin is inserted resin column, (copper initial concentration is 50mg/L to regulate simulation cuprammonium electroplating wastewater, ammonium chloride initial concentration is 3.75g/L) pH is 8, pumps in resin column, resin the rate of output water is 10BV/h。After adsorption penetration, the resin after absorption is carried out desorption with the hydrochloric acid that mass fraction is 10% by (Cu ion concentration is more than 0.3mg/L), and flow velocity is 2BV/h。Being carried out resin column to neutrality with clear water after desorption, pump into the potassium hydroxide solution that mass fraction is 4%, flow velocity is 4BV/h, and resin is made the transition, and makes resin functionality be converted into alkalescence。After testing: resin treatment ability reaches 420BV, after resin absorption penetrates, desorption liquid copper concentration is 6.4g/L, and nickel desorption rate is 99.2%。
Embodiment 18
4mL (humid volume) amidocarbonic acid chelating resin is inserted resin column, (copper initial concentration is 50mg/L to regulate simulation cuprammonium electroplating wastewater, ammonium chloride initial concentration is 3.75g/L) pH is 10, pumps in resin column, resin the rate of output water is 20BV/h。After adsorption penetration, the resin after absorption is carried out desorption with the hydrochloric acid that mass fraction is 15% by (Cu ion concentration is more than 0.3mg/L), and flow velocity is 5BV/h。Being carried out resin column to neutrality with clear water after desorption, pump into the potassium hydroxide solution that mass fraction is 10%, flow velocity is 10BV/h, and resin is made the transition, and makes resin functionality be converted into alkalescence。After testing: resin treatment ability reaches 230BV, after resin absorption penetrates, desorption liquid copper concentration is 5.8g/L, and nickel desorption rate is 99.0%。
Embodiment 19
(humid volume) polyamines chelating resin of 4mL is inserted resin column, and regulating simulation nickel ammonia electroplating wastewater (nickel initial concentration is 100mg/L, and ammonium sulfate initial concentration is 2.5g/L) pH is 5, pumps in resin column, and resin the rate of output water is 1BV/h。After adsorption penetration, the resin after absorption is carried out desorption with the nitric acid that mass fraction is 5% by (Ni ion concentration is more than 0.1mg/L), and flow velocity is 0.5BV/h。Being carried out resin column to neutrality with the useless clear water after processing after desorption, pump into the potassium hydroxide solution that mass fraction is 1%, flow velocity is 1BV/h, and resin is made the transition, and makes resin functionality be converted into alkalescence。After testing: resin treatment ability reaches 85BV, after resin absorption is saturated, desorption liquid nickel concentration is 2.7g/L, and nickel desorption rate is 99.1%。
Embodiment 20
(humid volume) polyamines chelating resin of 4mL is inserted resin column, and regulating simulation nickel ammonia electroplating wastewater (nickel initial concentration is 100mg/L, and ammonium sulfate initial concentration is 2.5g/L) pH is 8, pumps in resin column, and resin the rate of output water is 10BV/h。After adsorption penetration, the resin after absorption is carried out desorption with the nitric acid that mass fraction is 10% by (Ni ion concentration is more than 0.1mg/L), and flow velocity is 2BV/h。Being carried out resin column to neutrality with the useless clear water after processing after desorption, pump into the potassium hydroxide solution that mass fraction is 4%, flow velocity is 4BV/h, and resin is made the transition, and makes resin functionality be converted into alkalescence。After testing: resin treatment ability reaches 115BV, after resin absorption is saturated, desorption liquid nickel concentration is 6.2g/L, and nickel desorption rate is 99.8%。
Embodiment 21
(humid volume) polyamines chelating resin of 4mL is inserted resin column, (nickel initial concentration is 100mg/L to regulate simulation nickel ammonia electroplating wastewater, ammonium sulfate initial concentration is 2.5g/L) pH is 10, pumps in resin column, resin the rate of output water is 20BV/h。After adsorption penetration, the resin after absorption is carried out desorption with the nitric acid that mass fraction is 15% by (Ni ion concentration is more than 0.1mg/L), and flow velocity is 5BV/h。Being carried out resin column to neutrality with the useless clear water after processing after desorption, pump into the potassium hydroxide solution that mass fraction is 10%, flow velocity is 10BV/h, and resin is made the transition, and makes resin functionality be converted into alkalescence。After testing: resin treatment ability reaches 70BV, after resin absorption is saturated, desorption liquid nickel concentration is 7.5g/L, and nickel desorption rate is 99.5%。
Embodiment 22
4mL (humid volume) polyamines chelating resin is inserted resin column, and regulating simulation cuprammonium electroplating wastewater (copper initial concentration is 50mg/L, and ammonium chloride initial concentration is 3.75g/L) pH is 5, pumps in resin column, and resin the rate of output water is 1BV/h。After adsorption penetration, the resin after absorption is carried out desorption with the sulphuric acid that mass fraction is 5% by (Cu ion concentration is more than 0.3mg/L), and flow velocity is 0.5BV/h。Being carried out resin column to neutrality with clear water after desorption, pump into the potassium hydroxide solution that mass fraction is 1%, flow velocity is 1BV/h, and resin is made the transition, and makes resin functionality be converted into alkalescence。After testing: resin treatment ability reaches 250BV, after resin absorption penetrates, desorption liquid copper concentration is 1.5g/L, and nickel desorption rate is 99.6%。
Embodiment 23
4mL (humid volume) polyamines chelating resin is inserted resin column, and regulating simulation cuprammonium electroplating wastewater (copper initial concentration is 50mg/L, and ammonium chloride initial concentration is 3.75g/L) pH is 8, pumps in resin column, and resin the rate of output water is 10BV/h。After adsorption penetration, the resin after absorption is carried out desorption with the sulphuric acid that mass fraction is 10% by (Cu ion concentration is more than 0.3mg/L), and flow velocity is 2BV/h。Being carried out resin column to neutrality with clear water after desorption, pump into the potassium hydroxide solution that mass fraction is 4%, flow velocity is 4BV/h, and resin is made the transition, and makes resin functionality be converted into alkalescence。After testing: resin treatment ability reaches 320BV, after resin absorption penetrates, desorption liquid copper concentration is 4.9g/L, and nickel desorption rate is 99.7%。
Embodiment 24
4mL (humid volume) polyamines chelating resin is inserted resin column, and regulating simulation cuprammonium electroplating wastewater (copper initial concentration is 50mg/L, and ammonium chloride initial concentration is 3.75g/L) pH is 10, pumps in resin column, and resin the rate of output water is 20BV/h。After adsorption penetration, the resin after absorption is carried out desorption with the sulphuric acid that mass fraction is 15% by (Cu ion concentration is more than 0.3mg/L), and flow velocity is 5BV/h。Being carried out resin column to neutrality with clear water after desorption, pump into the potassium hydroxide solution that mass fraction is 10%, flow velocity is 10BV/h, and resin is made the transition, and makes resin functionality be converted into alkalescence。After testing: resin treatment ability reaches 180BV, after resin absorption penetrates, desorption liquid copper concentration is 4.5g/L, and nickel desorption rate is 98.9%。
Embodiment 25
(humid volume) glycine chelating resin of 4mL is inserted resin column, (nickel initial concentration is 100mg/L to pump into actual Treating Electroplate Wastewater Containing Nickel, the concentration of ammonia nitrogen is 360mg/L, the concentration of hypophosphorous acid is 200mg/L, electrical conductivity is 1324.1 μ s/cm, pH is 9.12) to resin column, resin the rate of output water is 5BV/h。After adsorption penetration, the resin after absorption is carried out desorption with the sulphuric acid that mass fraction is 12% by (Ni ion concentration is more than 0.1mg/L), and flow velocity is 1BV/h。Being carried out resin column to neutrality with clear water after desorption, pump into the sodium hydroxide solution that mass fraction is 4%, flow velocity is 1BV/h, and resin is made the transition, and makes resin functionality be converted into alkalescence, makes resin functionality be converted into alkalescence。After testing: resin treatment ability reaches 260BV, after resin absorption penetrates, desorption liquid nickel concentration is 13.2g/L, and nickel desorption rate is 95.6%。
By embodiment 1-25, each embodiment is removed and recovering state is as shown in table 1。
The result of resin treatment heavy metal-ammonia waste water in table 1 embodiment 1-25
Remarks: the glycine resin in embodiment 1-25 is the IRC-748 that Amberlite company produces; phosphoramidic-resin is the IRC-747 that Amberlite company produces; carbamic acid resin is the N-methyl in China Patent No. ZL200610041366.9 embodiment 1; N-carboxymethyl dithio amidocarbonic acid chelating resin, many polyimide resins are the N-acetylethylenediamine resin in China Patent No. ZL201010512734.X embodiment 1。
Schematically the present invention and embodiment being described above, this description does not have restricted, and data used are also one of embodiments of the present invention, and actual data set closes and is not limited thereto。So, if those of ordinary skill in the art is enlightened by it, when creating objective without departing from present aspect, design the embodiment similar to this technical scheme and embodiment without creationary, belong to protection scope of the present invention。
Claims (9)
1. the method utilizing chelating resin selective extraction heavy metal-ammonia complexing heavy metal in waste water, the steps include:
1) pH to 5-10 of heavy metal-ammonia complexing waste water is regulated；
2) by step 1) in heavy metal-ammonia complexing waste water pump into filling chelating resin resin column；
3) until step 2) in after resin column water outlet reaches breakthrough concentration, with the regenerative agent of 1-5 times of resin bed volume, chelating resin is regenerated；
4) until step 3) in after resin regeneration, with clear water, chelating resin is carried out, to be cleaned to resin column water outlet pH value close to neutrality, adopt dilute alkaline soln that chelating resin is made the transition。
2. a kind of method utilizing chelating resin selective extraction heavy metal-ammonia complexing heavy metal in waste water according to claim 1, it is characterised in that: described chelating resin is carbamic acid type, glycine type, phosphoramidic acid type, aminopyridine type chelating resin or many amines chelating resin。
3. a kind of method utilizing chelating resin selective extraction heavy metal-ammonia complexing heavy metal in waste water according to claim 1, it is characterised in that: described heavy metal is divalent heavy metal ions, including nickel ion and copper ion。
4. a kind of method utilizing chelating resin selective extraction heavy metal-ammonia complexing heavy metal in waste water according to claim 1, it is characterised in that: described step 2) in resin column Water discharge flow speed be 1-20BV/h。
5. a kind of method utilizing chelating resin selective extraction heavy metal-ammonia complexing heavy metal in waste water according to claim 3, it is characterized in that: described step 3) in, the breakthrough concentration of nickel ion is 0.1mg/L, and the breakthrough concentration of copper ion is 0.3mg/L。
6. a kind of method utilizing chelating resin selective extraction heavy metal-ammonia complexing heavy metal in waste water according to claim 1, it is characterised in that: described step 3) in regenerative agent be the hydrochloric acid of 5-15% (mass fraction), sulphuric acid or salpeter solution。
7. a kind of method utilizing chelating resin selective extraction heavy metal-ammonia complexing heavy metal in waste water according to claim 1 or 6, it is characterised in that: described step 3) in regenerant flow rate be 0.5-5BV/h。
8. a kind of method utilizing chelating resin selective extraction heavy metal-ammonia complexing heavy metal in waste water according to claim 1, it is characterised in that: described step 4) in clean water flow velocity be 1-20BV/h。
9. a kind of method utilizing chelating resin selective extraction heavy metal-ammonia complexing heavy metal in waste water according to claim 1, it is characterized in that: described step 4) in dilute alkaline soln refer to the sodium hydroxide solution or potassium hydroxide solution that mass fraction is 1-10%, flow velocity is 1-10BV/h。
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| CN112645482A (en) * | 2020-11-06 | 2021-04-13 | 江苏泉之源环境技术有限公司 | Treatment method of carboxyl complex heavy metal wastewater |
| CN117004830A (en) * | 2023-09-28 | 2023-11-07 | 上海稀固科技有限公司 | Method for recovering nickel from nickel-containing iron material liquid |
| CN117004830B (en) * | 2023-09-28 | 2023-12-08 | 上海稀固科技有限公司 | Method for recovering nickel from nickel-containing iron material liquid |
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Application publication date: 20160622 |