CN103979639A - Method of reinforcement removal and selective recovery of heavy metal ions in salt-containing waste water by utilization of chelate resin - Google Patents
Method of reinforcement removal and selective recovery of heavy metal ions in salt-containing waste water by utilization of chelate resin Download PDFInfo
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- CN103979639A CN103979639A CN201410202114.4A CN201410202114A CN103979639A CN 103979639 A CN103979639 A CN 103979639A CN 201410202114 A CN201410202114 A CN 201410202114A CN 103979639 A CN103979639 A CN 103979639A
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- 229920005989 resin Polymers 0.000 title claims abstract description 79
- 239000011347 resin Substances 0.000 title claims abstract description 79
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 61
- 238000000034 method Methods 0.000 title claims abstract description 26
- 150000002500 ions Chemical class 0.000 title claims abstract description 22
- 239000002351 wastewater Substances 0.000 title claims abstract description 19
- 238000011084 recovery Methods 0.000 title claims abstract description 16
- 150000003839 salts Chemical class 0.000 title claims abstract description 10
- 239000013522 chelant Substances 0.000 title abstract 6
- 230000002787 reinforcement Effects 0.000 title abstract 2
- 238000001179 sorption measurement Methods 0.000 claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 3
- 230000008929 regeneration Effects 0.000 claims description 36
- 238000011069 regeneration method Methods 0.000 claims description 36
- 239000002699 waste material Substances 0.000 claims description 22
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 15
- 238000010521 absorption reaction Methods 0.000 claims description 12
- 239000012267 brine Substances 0.000 claims description 12
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 12
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims description 12
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 10
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 10
- 235000010344 sodium nitrate Nutrition 0.000 claims description 10
- 239000004317 sodium nitrate Substances 0.000 claims description 10
- 229940001516 sodium nitrate Drugs 0.000 claims description 10
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 9
- 238000005728 strengthening Methods 0.000 claims description 9
- 102100034156 Apical endosomal glycoprotein Human genes 0.000 claims description 6
- 101000780564 Homo sapiens Apical endosomal glycoprotein Proteins 0.000 claims description 6
- DAKZISABEDGGSV-UHFFFAOYSA-N n-(2-aminoethyl)acetamide Chemical compound CC(=O)NCCN DAKZISABEDGGSV-UHFFFAOYSA-N 0.000 claims description 6
- 150000003141 primary amines Chemical group 0.000 claims description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 5
- 235000010333 potassium nitrate Nutrition 0.000 claims description 5
- 239000004323 potassium nitrate Substances 0.000 claims description 5
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 5
- 235000011152 sodium sulphate Nutrition 0.000 claims description 5
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 4
- LBPACUJFGRCWDF-UHFFFAOYSA-L Cl[Mg]Cl.[Na] Chemical compound Cl[Mg]Cl.[Na] LBPACUJFGRCWDF-UHFFFAOYSA-L 0.000 claims description 4
- 239000001110 calcium chloride Substances 0.000 claims description 4
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 4
- 238000002203 pretreatment Methods 0.000 claims description 4
- 238000004065 wastewater treatment Methods 0.000 claims description 4
- 238000011109 contamination Methods 0.000 claims description 3
- 238000011068 loading method Methods 0.000 claims description 2
- 239000010814 metallic waste Substances 0.000 abstract description 5
- 239000012535 impurity Substances 0.000 abstract description 2
- 238000004140 cleaning Methods 0.000 abstract 1
- 230000007935 neutral effect Effects 0.000 abstract 1
- 238000011112 process operation Methods 0.000 abstract 1
- 238000005086 pumping Methods 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 239000012492 regenerant Substances 0.000 abstract 1
- 230000001172 regenerating effect Effects 0.000 abstract 1
- 238000003795 desorption Methods 0.000 description 34
- 239000007788 liquid Substances 0.000 description 13
- 239000011521 glass Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 5
- 239000010865 sewage Substances 0.000 description 5
- 239000003513 alkali Substances 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000002689 soil Substances 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium Chemical compound [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000011790 ferrous sulphate Substances 0.000 description 2
- 235000003891 ferrous sulphate Nutrition 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 239000002341 toxic gas 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
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 229920001429 chelating resin Polymers 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000701 coagulant Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- -1 have broad spectrum Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 238000013332 literature search Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 210000004243 sweat Anatomy 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Landscapes
- Treatment Of Water By Ion Exchange (AREA)
- Removal Of Specific Substances (AREA)
- Water Treatment By Sorption (AREA)
Abstract
The invention discloses a method of reinforcement removal and selective recovery of heavy metal ions in salt-containing waste water by utilization of chelate resin, and belongs to the field of resourcelization and innocent treatment of heavy metal waste water. The method includes steps as follows: (1) pretreating salt-containing heavy metal waste water to be treated so as to remove suspended impurities, and pumping the pretreated heavy metal waste water into an adsorption column filled with the chelate resin; and (2) regenerating the chelate resin in the step (1) with a regenerant when the adsorption in the step (1) is saturated, cleaning the regenerated chelate resin with clean water until the resin is neutral and repeatedly using the chelate resin. The method can be used for treating various types of salt-containing heavy metal waste water, and has characteristics of broad range, low cost of raw materials and simple process operation.
Description
Technical field
The invention belongs to brine waste process field, specifically, relate to a kind of method of utilizing heavy metal ion in resin strengthening removal and selective recovery brine waste, more particularly, to utilize resin efficiently to remove the heavy metal ion in waste water under saliferous condition, avoid the detrimentally affect of salt pair removal of heavy metal ions generation that coexists simultaneously, thereby meet the method for the processing requirements of heavy metal in waste water.
Background technology
If heavy metal wastewater thereby does not carry out resource utilization, innoxious control, not only can cause environmental hazard, and can produce the wasting of resources.Saliferous heavy metal wastewater thereby generally derives from the production processes such as electronics plating, mining, smelting, wherein, representative heavy metal ion copper, lead, nickel isoconcentration Chang Gaoda 100-150mg/L, the salts such as coexistent a large amount of alkali (soil) metal, have increased pollution intractability.Conventional water technology (as neutralization precipitation method, chemical precipitation method, electrochemical process, coagulant sedimentation and biological restoration etc.) often has poor removal effect, reagent consumption is large, working cost is high, operation operation is difficult, the secondary pollution deficiency such as heavily.The requirement of going with the stream, the heavy metal deep purifying treatment technologies such as ion-exchange, membrane sepn are developed rapidly.But alkali (soil) metal is being brought into play site direct competitive effect significantly in strong, weakly acidic cation-exchange resin and heavy metal ion mechanism because coexist, obviously reduced the exchange capacity of heavy metal, cause treatment effect bad, seriously limited the application of ion exchange method; And NF/RO membrane separation technique has been held back alkali (soil) metal in heavy-metal ion removal, reduced membrane module service efficiency and effect, increased construction investment cost.To sum up, in the alkali that coexists (soil) the metal environment of high density relatively, all there is the open defects such as micro heavy ion selectivity is poor, clearance is low in ion-exchange, membrane sepn, and the negative effect of inorganic salt is remarkable.
In literature search report, find that the method for processing heavy metal has a lot, Chinese Patent Application No. for example: 201310661201.1, in open day on March 19th, 2014, disclose a kind of method of removing heavy metal in industrial sewage, and it is first adjusted to 7-8 by the pH value of industrial sewage; Then add sodium sulphite, regulating pH value is 9-10, makes sulfonium ion react the precipitation that generates sulfide with most of heavy metal ion, and can effectively prevent the generation of toxic gas hydrogen sulfide; Then under agitation add ferrous sulfate, with the precipitation of sulfonium ion generation Iron sulfuret, the pollution causing to remove unnecessary sulfonium ion; Utilizing the slightly acidic of ferrous sulfate that the pH value of industrial sewage is recalled to neutrality, also avoided can producing with acid for adjusting pH value the pollution of hydrogen sulfide toxic gas simultaneously; After press filtration, discharge.This is removed, and the method technical process of heavy metal in industrial sewage is simple, highly versatile, can meet the needs of all types of industries sewage removal heavy metal.But cannot be suitable for the processing of saliferous heavy metal wastewater thereby.
In existing document, do not see the method for heavy metal selective removal in suitable brine waste high efficiente callback, that as can be seen here, develops efficient highly selective, the low residual volume of low consumption is suitable for that saliferous heavy metal wastewater thereby is innoxious, recycling processing method has very large realistic meaning and using value.
Summary of the invention
1. the technical problem that will solve
In order to solve prior art, cannot efficient low-consume carry out that the degree of depth is innoxious, the problem of recycling treatment saliferous heavy metal wastewater thereby, the invention provides a kind of method of utilizing heavy metal ion in resin strengthening removal and selective recovery brine waste, employing this method is processed, can realize efficient removal the recovery of heavy metal under saline environment, and can not bring other impurity into, realize harmless treatment, the resource utilization of poisonous and harmful heavy metallic in waste water and control.
2. technical scheme
In order to overcome the above problems, concrete technical scheme of the present invention is as follows:
A method of utilizing heavy metal ion in resin strengthening removal and selective recovery brine waste, the steps include:
(1) heavy metal wastewater thereby of pending saliferous is carried out to pre-treatment, pre-treatment is to remove suspended contamination, then pretreated heavy metal wastewater thereby is pumped into the adsorption column of loading resin, regulate and control adsorption temp and flow velocity, wherein adsorption temp is 5-45 ℃, absorption flow velocity is 1-30BV/h, until adsorption equilibrium; Described resin is disclosed resin in the disclosed couple of primary amine groups resin EDTB or Chinese Patent Application No. 201310108031.4 in disclosed acetylethylenediamine resin or Chinese Patent Application No. 201310028758.1 in China Patent No. 201010512734.X;
(2) step (1) adsorb saturated after, with regenerator, the resin in step (1) is regenerated, the resin after regeneration is washed till neutrality with clear water, then reuses.
Preferably, salt in described step (1) in the heavy metal wastewater thereby of pending saliferous is inorganic salt, these inorganic salt are a kind of in SODIUMNITRATE, saltpetre, nitrocalcite, magnesium nitrate, sodium-chlor, magnesium chloride, calcium chloride and sodium sulfate or arbitrary combination, the mass percent of saliferous is no more than 13.6%, front 100BV solution weight metal ion clearance reaches 80.7%-100%, and removal of heavy metal ions rate raises and increases with salts contg.
Preferably, temperature when resin is regenerated in described step (2) is 5-50 ℃, and regeneration velocity is 1-10BV/h.
Preferably, in described step (2), regenerator used be massfraction be 2-15% contain HCl and/or HNO
3solution, contains NaCl and/or NaNO in regenerator
3, their total mass mark is less than or equal to 13.6%, and the heavy metal rate of recovery of front 6BV desorption liquid reaches 66.6%-99.4%, and the heavy metal rate of recovery raises and increases with salts contg.
The application of disclosed resin in the heavy metal containing wastewater treatment of saliferous in the disclosed couple of primary amine groups resin EDTB or Chinese Patent Application No. 201310108031.4 in disclosed acetylethylenediamine resin or Chinese Patent Application No. 201310028758.1 in China Patent No. 201010512734.XN.
Preferably, the processing of the above-mentioned heavy metal wastewater thereby that is applied to contain inorganic salt, wherein inorganic salt are a kind of in SODIUMNITRATE, saltpetre, nitrocalcite, magnesium nitrate, sodium-chlor, magnesium chloride, calcium chloride and sodium sulfate or arbitrary combination, and the mass percent of saliferous is no more than 13.6%.
Resin can be used clearance (Removal Rate) R to the removal effect of heavy metal in brine waste
1represent, regeneration effect can be used the rate of recovery (Reuse Rate) R
2represent, specific formula for calculation is as follows:
Wherein Ce represents to adsorb the water concentration that of rear heavy metal ion, and Co represents to adsorb the influent concentration of metal ion in front initial soln, and Ct represents the concentration of metal ion in regeneration soln; V
1express volume of water, V
2represent water inlet volume, V
3represent desorption volume.R
1be worth greatlyr, resin is higher to the clearance of heavy metal ion, and removal effect is better; R
2be worth greatlyr, resin is higher to the rate of recovery of heavy metal ion, and resource utilization effect is better.
3. beneficial effect
Than prior art, beneficial effect of the present invention is:
(1) the invention discloses a kind of method of utilizing heavy metal ion in resin strengthening removal and selective recovery brine waste, this method can be used for processing all kinds of saliferous heavy metal waste liquids, have broad spectrum, and material therefor is with low cost, technological operation is simple;
(2) the present invention is by selecting specific resin and adjusting to control adsorption temp and flow velocity, can realize the efficient removal of heavy metal, can meet heavy metal " zero release " requirement, solved a saliferous heavy metal containing wastewater treatment difficult problem, widen the range of application of resin, can realize heavy metal contamination harmless treatment;
(3) the present invention adopt massfraction be 2-15% contain HCl and/or HNO
3solution carries out desorption as regenerator, and desorption liquid is high density heavy metal solution, has good economic worth, can realize the concentrated also resource utilization of purifying of heavy metal resources and reclaim;
(4) the present invention is simple to operate, after processing, without residue, produces, and environmental friendliness, is having broad application prospects aspect the improvement of saliferous heavy metal wastewater thereby.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in detail.
Embodiment 1
By containing massfraction, be cupric (10mg/L) waste liquid of 0.001% SODIUMNITRATE under the absorption flow velocity of 30BV/h by the glass adsorption column (Ф 10 * 240mm) of 4mL Resin A is housed, adsorption temp is controlled at 5 ℃, collects water outlet.The HNO that is 10% with massfraction
3solution carries out desorption and regeneration to the resin after adsorbing, and desorption and regeneration temperature is 5 ℃, and flow velocity is 2BV/h.Resin after desorption and regeneration is washed till neutrality with clear water, reusable.
Embodiment 2
By containing massfraction, be 1.8% SODIUMNITRATE cupric (10mg/L) waste liquid under the absorption flow velocity of 30BV/h by the glass adsorption column (Ф 10 * 240mm) of 4mL Resin A is housed, adsorption temp is controlled at 5 ℃, collects water outlet.The HNO that is 10% with massfraction
3with the mixing solutions of 5% SODIUMNITRATE, the resin after adsorbing is carried out to desorption and regeneration, desorption and regeneration temperature is 5 ℃, and flow velocity is 2BV/h.Resin after desorption and regeneration is washed till neutrality with clear water, reusable.
Embodiment 3
By containing massfraction, be cupric (10mg/L) waste liquid of 13.6% SODIUMNITRATE under the absorption flow velocity of 30BV/h by the glass adsorption column (Ф 10 * 240mm) of 4mL Resin A is housed, adsorption temp is controlled at 5 ℃, collects water outlet.The HNO that is 10% with weight percent
3with the mixing solutions of 13.6% SODIUMNITRATE, the resin after adsorbing is carried out to desorption and regeneration, desorption and regeneration temperature is 5 ℃, and flow velocity is 2BV/h.Resin after desorption and regeneration is washed till neutrality with clear water, reusable.
Embodiment 4
By containing massfraction, be cupric (10mg/L) waste liquid of 0.001% SODIUMNITRATE under the absorption flow velocity of 15BV/h by the glass adsorption column (Ф 10 * 240mm) of 4mL resin B is housed, adsorption temp is controlled at 25 ℃, collects water outlet.With massfraction, be that 10%HCl solution carries out desorption and regeneration to the resin after adsorbing, desorption and regeneration temperature is 30 ℃, and flow velocity is 4BV/h.Resin after desorption and regeneration is washed till neutrality with clear water, reusable.
Embodiment 5
By containing massfraction, be cupric (50mg/L) waste liquid of 1.8% sodium sulfate under the absorption flow velocity of 15BV/h by the glass adsorption column (Ф 10 * 240mm) of 4mL resin B is housed, adsorption temp is controlled at 25 ℃, collects water outlet.The HCl that is 10% with massfraction and 5% sodium chloride solution carry out desorption and regeneration to the resin after adsorbing, and desorption and regeneration temperature is 30 ℃, and flow velocity is 4BV/h.Resin after desorption and regeneration is washed till neutrality with clear water, reusable.
Embodiment 6
By containing massfraction, be cupric (100mg/L) waste liquid of 13.6% sodium-chlor under the absorption flow velocity of 15BV/h by the glass adsorption column (Ф 10 * 240mm) of 4mL resin B is housed, adsorption temp is controlled at 25 ℃, collects water outlet.The solution of the HCl that is 15% with weight percent carries out desorption and regeneration to the resin after adsorbing, and desorption and regeneration temperature is 30 ℃, and flow velocity is 4BV/h.Resin after desorption and regeneration is washed till neutrality with clear water, reusable.
Embodiment 7
By containing massfraction, be nickeliferous (50mg/L) waste liquid of 6.8% saltpetre under the absorption flow velocity of 5BV/h by the glass adsorption column (Ф 10 * 240mm) of 4mL resin C is housed, adsorption temp is controlled at 45 ℃, collects water outlet.The HCl solution that is 15% with massfraction carries out desorption and regeneration to the resin after adsorbing, and desorption and regeneration temperature is 50 ℃, and flow velocity is 5BV/h.Resin after desorption and regeneration is washed till neutrality with clear water, reusable.
Embodiment 8
By sweat massfraction be cupric (50mg/L) waste liquid of 1.8% nitrocalcite under the absorption flow velocity of 1BV/h by the glass adsorption column (Ф 10 * 240mm) of 4mL resin C is housed, adsorption temp is controlled at 45 ℃, collects water outlet.With massfraction, than the HCl solution that is 2%, the resin after adsorbing is carried out to desorption and regeneration, desorption and regeneration temperature is 50 ℃, and flow velocity is 5BV/h.Resin after desorption and regeneration is washed till neutrality with clear water, reusable.
Embodiment 9
By containing massfraction, be 1.8% magnesium nitrate containing zinc (50mg/L) waste liquid under the absorption flow velocity of 5BV/h by the glass adsorption column (Ф 10 * 240mm) of 4mL resin C is housed, adsorption temp is controlled at 45 ℃, collects water outlet.The HCl solution that is 15% with massfraction carries out desorption and regeneration to the resin after adsorbing, and desorption and regeneration temperature is 50 ℃, and flow velocity is 10BV/h.Resin after desorption and regeneration is washed till neutrality with clear water, reusable.
Embodiment 10
By containing massfraction, be cupric (50mg/L) waste liquid of 1.8% nitrocalcite under the absorption flow velocity of 10BV/h respectively by 4mL Resin A mberlite IRC-747 is housed, Amberlite IRC-748,001 glass adsorption column (Ф 10 * 240mm), adsorption temp is controlled at 30 ℃, collects water outlet.The HCl solution that is 15% with massfraction carries out desorption and regeneration to the resin after adsorbing, and desorption and regeneration temperature is 30 ℃, and flow velocity is 5BV/h.Resin after desorption and regeneration is washed till neutrality with clear water, reusable.
By embodiment 1-10, it is as shown in table 1 that each example is removed result.
Table 1 removal situation
Resin A in embodiment 1-10 refers to the acetylethylenediamine resin in the disclosed embodiments 1 in China Patent No. 201010512734.X (wherein embodiment 1,2 and 3 resin that the embodiment 1,2 and 3 in corresponding 201010512734.X obtains respectively); Resin B is the disclosed couple of primary amine groups resin EDTB in Chinese Patent Application No. 201310028758.1 (wherein embodiment 4,5 and 6 resin that the embodiment 1,3 and 5 in corresponding 201010512734.X obtains respectively); Resin C is disclosed resin in Chinese Patent Application No. 201310108031.4 (wherein embodiment 7,8 and 9 resin that the embodiment 2,3 and 6 in corresponding 201010512734.X obtains respectively).
Below schematically the present invention and embodiment thereof are described, it is also one of preferred forms of the present invention that this description does not have restricted, used data, and actual data set merging is not limited to this.So, if those of ordinary skill in the art is enlightened by it, in the situation that not departing from the invention aim, without the creationary embodiment similar to this technical scheme and the embodiment of designing, all should belong to protection scope of the present invention.
Claims (6)
1. a method of utilizing heavy metal ion in resin strengthening removal and selective recovery brine waste, the steps include:
(1) heavy metal wastewater thereby of pending saliferous is carried out to pre-treatment, pre-treatment is to remove suspended contamination, then pretreated heavy metal wastewater thereby is pumped into the adsorption column of loading resin, regulate and control adsorption temp and flow velocity, wherein adsorption temp is 5-45 ℃, absorption flow velocity is 1-30BV/h, until adsorption equilibrium; Described resin is disclosed resin in the disclosed couple of primary amine groups resin EDTB or Chinese Patent Application No. 201310108031.4 in disclosed acetylethylenediamine resin or Chinese Patent Application No. 201310028758.1 in China Patent No. 201010512734.X;
(2) step (1) adsorb saturated after, with regenerator, the resin in step (1) is regenerated, the resin after regeneration is washed till neutrality with clear water, then reuses.
According to claim 1 a kind of utilize resin strengthening remove and selective recovery brine waste in the method for heavy metal ion, it is characterized in that, salt in described step (1) in the heavy metal wastewater thereby of pending saliferous is inorganic salt, these inorganic salt are a kind of in SODIUMNITRATE, saltpetre, nitrocalcite, magnesium nitrate, sodium-chlor, magnesium chloride, calcium chloride and sodium sulfate or arbitrary combination, and the mass percent of saliferous is no more than 13.6%.
According to claim 1 a kind of utilize resin strengthening remove and selective recovery brine waste in the method for heavy metal ion, it is characterized in that, temperature when resin is regenerated in described step (2) is 5-50 ℃, and regeneration velocity is 1-10BV/h.
According to according to a kind of described in any one in claim 1-3, utilize resin strengthening remove and selective recovery brine waste in the method for heavy metal ion, it is characterized in that, in described step (2), regenerator used be massfraction be 2-15% contain HCl and/or HNO
3solution.
5. the application of disclosed resin in the heavy metal containing wastewater treatment of saliferous in the disclosed couple of primary amine groups resin EDTB or Chinese Patent Application No. 201310108031.4 in disclosed acetylethylenediamine resin or Chinese Patent Application No. 201310028758.1 in China Patent No. 201010512734.XN.
6. according to the application of disclosed resin in the heavy metal containing wastewater treatment of saliferous in the disclosed couple of primary amine groups resin EDTB in disclosed acetylethylenediamine resin or Chinese Patent Application No. 201310028758.1 in the China Patent No. 201010512734.XN described in claims 5 or Chinese Patent Application No. 201310108031.4, it is characterized in that, the processing of the heavy metal wastewater thereby that it is applied to contain inorganic salt, wherein inorganic salt are SODIUMNITRATE, saltpetre, nitrocalcite, magnesium nitrate, sodium-chlor, magnesium chloride, a kind of or arbitrary combination in calcium chloride and sodium sulfate, the mass percent of saliferous is no more than 13.6%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410202114.4A CN103979639A (en) | 2014-05-13 | 2014-05-13 | Method of reinforcement removal and selective recovery of heavy metal ions in salt-containing waste water by utilization of chelate resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
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| CN105174556A (en) * | 2015-10-16 | 2015-12-23 | 南京大学 | High-acidity high-iron heavy metal wastewater quality-divided resource recycling method |
| CN105692768A (en) * | 2016-03-31 | 2016-06-22 | 南京大学 | Method for selectively extracting heavy metals in heavy metal-ammonia complexing wastewater by virtue of chelate resin |
| CN107417007A (en) * | 2017-07-20 | 2017-12-01 | 上海立科化学科技有限公司 | A kind of resin method recovery process for electroplating spent acid and diluted acid waste water |
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| CN105174556A (en) * | 2015-10-16 | 2015-12-23 | 南京大学 | High-acidity high-iron heavy metal wastewater quality-divided resource recycling method |
| CN105174556B (en) * | 2015-10-16 | 2017-10-24 | 南京大学 | A kind of method of peracid high ferro heavy metal wastewater thereby sub-prime resource reclaim |
| CN105692768A (en) * | 2016-03-31 | 2016-06-22 | 南京大学 | Method for selectively extracting heavy metals in heavy metal-ammonia complexing wastewater by virtue of chelate resin |
| CN107417007A (en) * | 2017-07-20 | 2017-12-01 | 上海立科化学科技有限公司 | A kind of resin method recovery process for electroplating spent acid and diluted acid waste water |
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