CN115072899B - Method for removing and recycling copper ions in high-salt water by using tetraethylenepentamine functional resin - Google Patents
Method for removing and recycling copper ions in high-salt water by using tetraethylenepentamine functional resin Download PDFInfo
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- CN115072899B CN115072899B CN202210739857.XA CN202210739857A CN115072899B CN 115072899 B CN115072899 B CN 115072899B CN 202210739857 A CN202210739857 A CN 202210739857A CN 115072899 B CN115072899 B CN 115072899B
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- tetraethylenepentamine
- functional resin
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- copper ions
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- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 229910001431 copper ion Inorganic materials 0.000 title claims abstract description 86
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 229920005989 resin Polymers 0.000 title claims abstract description 77
- 239000011347 resin Substances 0.000 title claims abstract description 77
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 238000000034 method Methods 0.000 title claims abstract description 52
- 238000004064 recycling Methods 0.000 title claims abstract description 11
- 239000010949 copper Substances 0.000 claims abstract description 28
- 238000001179 sorption measurement Methods 0.000 claims abstract description 23
- 239000000706 filtrate Substances 0.000 claims abstract description 22
- 238000003795 desorption Methods 0.000 claims abstract description 19
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052802 copper Inorganic materials 0.000 claims abstract description 18
- 238000001914 filtration Methods 0.000 claims abstract description 11
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 9
- 229920003053 polystyrene-divinylbenzene Polymers 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 33
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 239000007788 liquid Substances 0.000 claims description 20
- 235000019441 ethanol Nutrition 0.000 claims description 18
- 150000003839 salts Chemical class 0.000 claims description 17
- 239000011780 sodium chloride Substances 0.000 claims description 11
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 8
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 8
- 239000012498 ultrapure water Substances 0.000 claims description 8
- 238000004140 cleaning Methods 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical group O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- 230000008961 swelling Effects 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 125000000524 functional group Chemical group 0.000 claims description 5
- 229920005990 polystyrene resin Polymers 0.000 claims description 5
- 159000000007 calcium salts Chemical class 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 159000000003 magnesium salts Chemical class 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 4
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 4
- 159000000000 sodium salts Chemical class 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- 238000000944 Soxhlet extraction Methods 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 239000007832 Na2SO4 Substances 0.000 claims description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- 230000001172 regenerating effect Effects 0.000 claims description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims 1
- 230000008929 regeneration Effects 0.000 abstract description 9
- 238000011069 regeneration method Methods 0.000 abstract description 9
- 239000000126 substance Substances 0.000 abstract description 6
- 239000008213 purified water Substances 0.000 abstract 1
- 239000006228 supernatant Substances 0.000 description 16
- 239000000243 solution Substances 0.000 description 9
- 239000002351 wastewater Substances 0.000 description 7
- 229910001385 heavy metal Inorganic materials 0.000 description 5
- 125000003277 amino group Chemical group 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000003344 environmental pollutant Substances 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 231100000719 pollutant Toxicity 0.000 description 4
- 150000001450 anions Chemical class 0.000 description 3
- 125000000542 sulfonic acid group Chemical group 0.000 description 3
- 238000007792 addition Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000012267 brine Substances 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 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
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 206010067125 Liver injury Diseases 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000000805 composite resin Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- -1 hydrogen ions Chemical class 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 238000013332 literature search Methods 0.000 description 1
- 230000003908 liver function Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 208000030159 metabolic disease Diseases 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
Classifications
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- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
-
- 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
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
-
- 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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Treatment Of Water By Ion Exchange (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a method for removing and recycling copper ions in a high-salt water body by using tetraethylenepentamine functional resin, which comprises the following steps: adjusting the pH of the copper-containing water body and then filtering; the filtrate is passed through an adsorption tower or a fluidized bed filled with tetraethylenepentamine functional resin to obtain a deeply purified water body; the skeleton of the tetraethylenepentamine functional resin is polystyrene-divinylbenzene, and the skeleton is grafted with the tetraethylenepentamine functional group; and when the adsorption leakage point is reached, the desorption agent is used for desorption and regeneration. According to the method, the tetraethylenepentamine functional resin is adopted to treat copper ions in the high-salt water body, and when the pH value of the water body is 2.5-10.0 and high concentration Cl‑、HPO4 2‑、SO4 2‑、NO3 ‑、Ca2+、Mg2+、K+ and other competing substances coexist, the copper content of the effluent can be reduced from less than 150 mg/L to below 0.01 mg/L (calculated by Cu).
Description
Technical Field
The invention relates to the technical field of sewage treatment and harmless treatment, in particular to a method for removing and recycling copper ions in a high-salt water body by using tetraethylenepentamine functional resin, and specifically relates to a method for rapidly removing copper ions in a water body containing various anions and cations by using the tetraethylenepentamine functional resin material.
Background
Copper ions are one of common heavy metal pollutants in water bodies and widely exist in nonferrous metal ore mining and selecting industry, heavy nonferrous metal smelting industry, lead storage battery manufacturing industry, electroplating industry, chemical raw material and chemical product manufacturing industry and leather tanning processing industry. Among the above-mentioned processing industry waste water components, inorganic salt concentration is generally higher, taking nonferrous metal mine waste water as an example: the main pollutants comprise toxic and harmful substances (various heavy metal ions and various organic and inorganic medicaments), strong acid, strong alkali and oil substances, and the toxic and harmful substances can pollute surface water and underground water. The addition of the inorganic agent causes large salt load, so that nitrate, sulfate and chloride exist in the wastewater, and the wastewater discharged by the nonferrous metal mine is usually acidic, which is not beneficial to the removal of heavy metal ions. Although copper ions have the characteristics of difficult degradation, easy enrichment and the like, the copper ions not only can poison plants, but also can inhibit the growth of microorganisms and animals, and can further cause threat to human health, such as aggregation in human bodies, cause metabolic disorder of human bodies and seriously damage liver functions. However, copper is expected to find wide application in the electronics industry, energy and petrochemical industry, transportation industry, mechanical and metallurgical industry, light industry, and emerging industries and high tech fields, which suggest that copper ion recycling is of economic value.
Copper ions are generally removed by conventional and emerging techniques. Among them, the conventional techniques include chemical precipitation, ion exchange, neutralization, filtration, coagulation, adsorption, etc.; emerging technologies include membrane technology, electrochemistry, and the like. However, these processes require additional additions of chemicals for secondary treatment, which increases the cost of the technology and the salt content of the brine copper wastewater tends to clog the filters, which all present challenges to the practical application of such technologies in brine bodies. In general, adsorption is considered to be simpler and more economical. The general adsorption material has the defects of poor mechanical strength, low selective adsorption performance and the like, and the resin has the advantages of good hydrodynamic property, large specific surface area, high mechanical strength, reproducibility and the like which are prioritized. Ion exchange resins are currently widely applied to deep treatment of heavy metal pollutants, and the purpose of removing the pollutants is achieved through electrostatic attraction, and common functional groups include sulfonic acid groups, carboxylic acid groups and the like. The cation exchange resin commonly used in copper-containing water at present is sulfonic acid group resin. However, copper-containing high-salt wastewater has a serious requirement for practical application of sulfonic acid group resins. For example, when the salt concentration in the system is significantly higher than that of copper ions, cations compete with copper ions for adsorption sites, resulting in a significant decrease in removal efficiency, which is manifested by low selectivity for heavy metal ions.
Therefore, the development of a method for removing and recycling copper ions in high-salinity water has application value and practical significance.
According to the invention, the functional group-tetraethylenepentamine is grafted on the chloromethylated polystyrene resin skeleton, so that the tetraethylenepentamine functional resin can be obtained. On the one hand, the existence of salts in the high-salt copper-containing water body does not influence the removal of copper ions, and the high-selectivity removal is truly realized. On the other hand, the high-efficiency removal can be kept in a wider pH range (2.5-10). At present, literature search shows that no method for removing copper ions by adopting tetraethylenepentamine functional resin in high-salt wastewater environment is reported.
Disclosure of Invention
Aiming at the technical problems in the prior art, the invention aims to provide a method for removing and recycling copper ions in high-salt water by using tetraethylenepentamine functional resin, which realizes the efficient removal of copper ions in high-salt water and overcomes the problems that the traditional copper ion treatment method is greatly influenced by high salt and has narrow pH application range. Meanwhile, the tetraethylenepentamine functional resin after reaction can be regenerated by acid liquor and recycled.
The invention adopts the following technical scheme to solve the problems, and the method for removing and recycling copper ions in high-salt water by using tetraethylenepentamine functional resin comprises the following steps:
(1) Adjusting the pH value of the high-salt copper-containing water body, and filtering to obtain filtrate;
(2) Passing the filtrate obtained in the step (1) through an adsorption tower or a fluidized bed filled with tetraethylenepentamine functional resin to enable the high-salt copper-containing water body to fully contact with the tetraethylenepentamine functional resin material, so as to obtain a water body after deep purification;
The skeleton of the tetraethylenepentamine functional resin is polystyrene-divinylbenzene, and the skeleton is grafted with the tetraethylenepentamine functional group;
(3) Stopping operation after reaching the leakage point, and desorbing and regenerating the tetraethylenepentamine functional resin by adopting a desorbing agent; then, ethanol and ultrapure water are used for cleaning alternately until the pH of the effluent liquid is neutral;
the tetraethylenepentamine functional resin adopted by the invention is prepared by grafting tetraethylenepentamine groups on the skeleton of polystyrene-divinylbenzene. Copper ions are removed by chelation of amine groups with copper ions. When a large amount of inorganic salts coexist, anions shield the positive charge of the protonated amine groups through electrostatic attraction, so that more available adsorption sites are exposed, and therefore, the high adsorption capacity and the rapid adsorption rate can be still maintained in a high-salt water body, and the influence of hydrogen ions in an acidic solution is reduced.
Further, in the step (1), the pH value is 2.5-10; and in terms of Cu, the mass concentration of copper ions in the water body is below 150 mg/L, the mass concentration of salt in the water body is below 30%, and the salt is at least one of sodium salt, potassium salt, calcium salt and magnesium salt. The sodium salt comprises at least one of NaCl and NaNO 3、Na2SO4、NaH2PO4, and the potassium salt, the calcium salt and the magnesium salt are nitrate.
Further, in the step (2), the temperature of the filtrate passing through the adsorption tower is 5-40 ℃, and the flow rate of the filtrate is not more than 5 resin bed volumes per hour.
Further, in the step (2), the preparation method of the tetraethylenepentamine functional resin comprises the following steps: swelling chloromethylated polystyrene resin with 1, 2-dichloroethane for 10-15 h, filtering out swelling agent 1, 2-dichloroethane, adding into mixed solution of tetraethylenepentamine and lower alcohol according to the solid-to-liquid ratio of 1g to 50-70 ml, carrying out functional group grafting reaction for 24-30 h under the constant temperature oil bath condition of 60-120 ℃, filtering out the mixed solution, carrying out Soxhlet extraction with lower alcohol to remove residual tetraethylenepentamine and 1, 2-dichloroethane, drying, and obtaining the resin with the skeleton grafted with the tetraethylenepentamine groups, and marking the resin as the tetraethylenepentamine functional resin. After the preparation is finished, the tetraethylene pentamine functional resin is prepared by alternately cleaning the tetraethylene pentamine functional resin with absolute ethyl alcohol and ultrapure water for a plurality of times and vacuum drying. Wherein the lower alcohol is ethanol; the volume ratio of tetraethylenepentamine to lower alcohol in the mixed solution is 1-4: 1, a step of; the particle size of the tetraethylenepentamine functional resin is 0.2-1.0 mm, preferably 0.6-0.9 mm.
Further, in the step (3), the mass concentration of the discharged copper ions is more than 0.01 mg/L (calculated by Cu).
Further, in the step (3), the desorption agent is nitric acid or hydrochloric acid solution with the mass percent concentration of 2-15%; when the acid liquor passes through the tetraethylenepentamine functional resin, desorption is carried out at the temperature of 10-40 ℃ at the flow rate of 1-5 resin bed volumes per hour, and when the copper ion concentration in desorption effluent is less than 0.01 mg/L, the desorption is finished.
Further, in the steps (2) and (3), the operation mode of single-tower adsorption-single-tower desorption or multi-tower serial adsorption-single-tower desorption is adopted.
Compared with the prior art, the invention has the following beneficial effects:
(1) The method adopts the tetraethylenepentamine functional resin to remove and recycle copper ions in the high-salt water body, and the tetraethylenepentamine functional resin material can realize hundred percent adsorption in the high-salt copper-containing water body; experiments show that the high-efficiency interception of copper ions can be realized when the pH value of the water body is 2.5-10.0.
(2) The tetraethylenepentamine functional resin adopted by the method can be regenerated by acid liquor after reaction, and can be recycled, so that the treatment cost is reduced.
(3) The tetraethylenepentamine functional resin adopted by the method truly realizes high-selectivity removal in the high-salt copper-containing water body, can keep high-efficiency removal within a wider pH range (2.5-10), improves the adsorption capacity, accelerates the reaction rate, and avoids the influence of the salt-containing water body and the pH on materials.
(4) The tetraethylenepentamine functional resin adopted by the method has simple preparation method. The preparation method is characterized in that the preparation method is realized by grafting a functional group (tetraethylenepentamine) on chloromethylated polystyrene resin through a one-step method.
Detailed Description
The above-described matters of the present invention will be described in further detail by way of examples, but it should not be construed that the scope of the above-described subject matter of the present invention is limited to the following examples, and all techniques realized based on the above-described matters of the present invention are within the scope of the present invention.
The tetraethylenepentamine functional resin involved in the following examples is prepared by the following specific method:
Swelling chloromethylated polystyrene resin with 1, 2-dichloroethane for 12h, filtering out swelling agent 1, 2-dichloroethane, adding into mixed solution of tetraethylenepentamine and lower alcohol in a solid-to-liquid ratio of 1 g: 60ml, carrying out functional group grafting reaction for 25h under the constant temperature oil bath condition of 90 ℃, filtering out the mixed solution, carrying out Soxhlet extraction with lower alcohol to remove residual tetraethylenepentamine and 1, 2-dichloroethane, drying to obtain resin with a skeleton grafted with tetraethylenepentamine groups, and marking the resin as the tetraethylenepentamine functional resin. After the preparation is finished, the tetraethylene pentamine functional resin is prepared by alternately cleaning the tetraethylene pentamine functional resin with absolute ethyl alcohol and ultrapure water for a plurality of times and vacuum drying.
Wherein the lower alcohol is ethanol; the volume ratio of tetraethylenepentamine to lower alcohol in the mixed solution is 2.5: 1, a step of; the grain diameter of the tetraethylenepentamine functional resin is 0.6-0.9 mm.
Example 1
A method for removing and recycling copper ions in high-salt water by using tetraethylenepentamine functional resin comprises the following specific steps:
(1) The copper ion concentration in the copper ion solution containing salt is 1 mM (64 mg/L) and the mass concentration of salt is 30% (NaCl), the pH value is regulated to be 5.5+/-0.2, then the solution is filtered, and then tetraethylenepentamine functional resin (the input amount of the tetraethylenepentamine functional resin in the filtrate is 1 g/L) is added into the filtrate, and the mixture is put into a shaking table at a constant temperature of 25 ℃ for shaking 24 h.
(2) After the reaction, the copper ion concentration was measured by taking the supernatant of the solution, and after the measurement, all copper ions were removed after the reaction.
(3) And (3) carrying out solid-liquid separation on the adsorption saturated composite material and the solution, cleaning for 5-8 times by using ultrapure water, adding 2% nitric acid solution by mass percent for regeneration, and putting the mixture into a constant-temperature shaking table to oscillate at 25 ℃ and 180 rpm for 48 h.
(4) The regenerated resin was washed with ultrapure water until no copper ions were detected in the solution, the pH of the solution was near neutral, and the material was dried under vacuum at room temperature after solid-liquid separation. Repeating the steps (1), (2) and (3) after drying, wherein the experimental and detection results are basically consistent with the above results. Therefore, the tetraethylenepentamine functional resin is determined to be better regenerated, and the regenerated tetraethylenepentamine functional resin can be reused after reaction.
Example 2
The copper ions in the water body were treated in the same manner as in example 1, except that: in step (1), the initial concentration of copper ions was controlled at 2.0 mM (128 mg/L). The experimental results are: copper ions in the supernatant liquid are completely removed after the reaction.
Example 3
The same method as in example 1 is adopted to remove and recycle copper ions in water, and the difference is that: in the step (1), the pH of the filtrate is controlled to be 10.0+/-0.2. The experimental results are: copper ions in the supernatant liquid are completely removed after the reaction.
Example 4
The same method as in example 1 is adopted to remove and recycle copper ions in water, and the difference is that: in the step (1), the pH of the filtrate is controlled to be 9.0+/-0.2. The experimental results are: copper ions in the supernatant liquid are completely removed after the reaction.
Example 5
The same method as in example 1 is adopted to remove and recycle copper ions in water, and the difference is that: in the step (1), the pH of the filtrate is controlled to be 8.0+/-0.2. The experimental results are: copper ions in the supernatant liquid are completely removed after the reaction.
Example 6
The same method as in example 1 is adopted to remove and recycle copper ions in water, and the difference is that: in the step (1), the pH of the filtrate is controlled to 7.0.+ -. 0.2. The experimental results are: copper ions in the supernatant liquid are completely removed after the reaction.
Example 7
The same method as in example 1 is adopted to remove and recycle copper ions in water, and the difference is that: in the step (1), the pH of the filtrate is controlled to be 6.0+/-0.2. The experimental results are: copper ions in the supernatant liquid are completely removed after the reaction.
Example 8
The same method as in example 1 is adopted to remove and recycle copper ions in water, and the difference is that: in the step (1), the pH of the filtrate is controlled to be 5.0+/-0.2. The experimental results are: copper ions in the supernatant liquid are completely removed after the reaction.
Example 9
The same method as in example 1 is adopted to remove and recycle copper ions in water, and the difference is that: in the step (1), the pH of the filtrate is controlled to be 4.0+/-0.2. The experimental results are: copper ions in the supernatant liquid are completely removed after the reaction.
Example 10
The same method as in example 1 is adopted to remove and recycle copper ions in water, and the difference is that: in the step (1), the pH of the filtrate is controlled to be 3.0+/-0.2. The experimental results are: the removal rate of copper ions in the supernatant after the reaction is more than 90 percent.
Example 11
The same method as in example 1 is adopted to remove and recycle copper ions in water, and the difference is that: in the step (1), the pH of the filtrate is controlled to be 2.5+/-0.2. The experimental results are: the removal rate of copper ions in the supernatant after the reaction is more than 80 percent.
Example 12
The same method as in example 1 is adopted to remove and recycle copper ions in water, and the difference is that: in the step (1), the NaCl content is controlled to be 20 percent. The experimental results are: copper ions in the supernatant liquid are completely removed after the reaction.
Example 13
The same method as in example 1 is adopted to remove and recycle copper ions in water, and the difference is that: in the step (1), the NaCl content is controlled to be 10 percent. The experimental results are: copper ions in the supernatant liquid are completely removed after the reaction.
Example 14
The same method as in example 1 is adopted to remove and recycle copper ions in water, and the difference is that: in the step (1), the NaCl content is controlled to be 5 percent. The experimental results are: copper ions in the supernatant liquid are completely removed after the reaction.
Example 15
The same method as in example 1 is adopted to remove and recycle copper ions in water, and the difference is that: in the step (1), naCl is replaced by Na 2SO4 with the same mass concentration. The experimental results are: the copper ion removal rate in the supernatant after the reaction was 90%.
Example 16
The same method as in example 1 is adopted to remove and recycle copper ions in water, and the difference is that: in the step (1), naCl is replaced by NaNO 3 with the same mass concentration. The experimental results are: the removal rate of copper ions in the supernatant after the reaction is more than 80 percent.
Example 17
A method for removing and recycling copper ions in high-salt water by using tetraethylenepentamine functional resin comprises the following specific steps:
(1) Adjusting the pH value of the high-salt copper-containing water body (the concentration of Cu is 1 mmol/L and the NaCl content is 30%) to 5.5, and filtering to obtain filtrate;
(2) Loading 130 mL (about 65 g) tetraethylenepentamine functional resin into a jacketed glass adsorption column (phi 32 multiplied by 360 mm), and allowing the filtrate obtained in the step (1) to pass through the adsorption column containing the bed layer of the tetraethylenepentamine functional resin from bottom to top at the temperature of 25+/-5 ℃ at the flow rate of 1 BV/h, wherein the concentration of effluent Cu is reduced to below 0.01 mg/L, and the treatment capacity of the effluent Cu reaches about 800 BV (the concentration of the effluent Cu is increased to above 0.01 mg/L and is recorded as reaching the leakage point);
(3) Stopping operation when reaching the leakage point (the Cu concentration of the effluent is more than 0.01 mg/L), firstly carrying out desorption regeneration by using 1L nitric acid solution (the mass percent concentration of nitric acid is 2%) at the temperature of 25+/-5 ℃ from bottom to top through a resin bed layer at the flow rate of 1 BV/h, and ending the desorption when the Cu ion concentration of the effluent desorption liquid is less than 0.01 mg/L. And then alternately cleaning with ethanol and ultrapure water until the pH of the effluent is neutral, wherein the regeneration rate of the tetraethylenepentamine functional resin composite material is more than 90%, namely the treatment capacity of the leakage point is more than 720 BV when the steps (1) - (2) are repeated for treating the tetraethylenepentamine functional resin after the first regeneration.
Example 18
The same method as in example 17 is adopted to remove and recycle copper ions in water, and the difference is that: in the step (2), the temperature is set to 10+/-5 ℃. The experimental results are: the throughput to the leak is about 760 BV.
Example 19
The same method as in example 17 is adopted to remove and recycle copper ions in water, and the difference is that: in the step (2), the temperature is set to 40+ -5 ℃. The experimental results are: the throughput to the leak is about 900 BV.
Example 20
The same method as in example 17 is adopted to remove and recycle copper ions in water, and the difference is that: in step (1), the initial copper concentration was 0.5 mM. The experimental results are: the throughput to the leak is about 1000 BV.
Example 21
The same method as in example 17 is adopted to remove and recycle copper ions in water, and the difference is that: in the step (3), desorption regeneration is carried out by using hydrochloric acid desorption liquid with the mass fraction of 2 percent. The experimental results are: and (3) when the steps (1) - (2) are repeated for treatment of the tetraethylenepentamine functional resin after the first regeneration, the treatment capacity of the leakage point is reduced to about 700 BV.
Example 22
The same method as in example 17 is adopted to remove and recycle copper ions in water, and the difference is that: in the step (3), the mass percentage concentration of the nitric acid is 1%, and desorption regeneration is carried out. The experimental results are: and (3) when the steps (1) - (2) are repeated for treatment of the tetraethylenepentamine functional resin after the first regeneration, the treatment capacity of the leakage point is reduced to about 610 BV.
Example 23
The same method as in example 17 is adopted to remove and recycle copper ions in water, and the difference is that: in the step (1), naCl used in the copper-containing water body is replaced by NaH 2PO4 with the same mass concentration. The experimental results are: the throughput to the leak point is reduced to about 790 BV.
Example 24
The same method as in example 17 is adopted to remove and recycle copper ions in water, and the difference is that: in the step (1), naCl used in the copper-containing water body is replaced by Mg (NO 3)2. The experimental result is that the treatment capacity reaching the leakage point is reduced to about 770 BV.
Example 25
The same method as in example 17 is adopted to remove and recycle copper ions in water, and the difference is that: in the step (1), the NaCl content is controlled to be 5 percent. The experimental results are: the throughput to the leak is about 750 BV.
Example 26
The same method as in example 17 is adopted to remove and recycle copper ions in water, and the difference is that: in the step (1), the NaCl content is controlled to be 10 percent. The experimental results are: the throughput to the leak is about 770 BV.
Example 27
The same method as in example 17 is adopted to remove and recycle copper ions in water, and the difference is that: in the step (1), the NaCl content is controlled to be 20 percent. The experimental results are: the throughput to the leak is about 780 BV. The higher the NaCl content, the greater the throughput to the leak point. The electrostatic shielding effect of the tetraethylenepentamine functional resin is that anions are used for neutralizing protonated amine groups, so that repulsive force between the protonated amine groups and copper ions is weakened, more adsorption sites are exposed, and the adsorption of copper ions is promoted.
What has been described in this specification is merely an enumeration of possible forms of implementation for the inventive concept and may not be considered limiting of the scope of the present invention to the specific forms set forth in the examples.
Claims (6)
1. A method for removing and recycling copper ions in high-salt water by using tetraethylenepentamine functional resin is characterized by comprising the following steps:
(1) Adjusting the pH of the high-salt copper-containing water body, and filtering to obtain filtrate;
(2) Passing the filtrate obtained in the step (1) through an adsorption tower or a fluidized bed filled with tetraethylenepentamine functional resin to enable the high-salt copper-containing water body to fully contact with the tetraethylenepentamine functional resin material, so as to obtain a water body after deep purification;
The skeleton of the tetraethylenepentamine functional resin is polystyrene-divinylbenzene, and the skeleton is grafted with the tetraethylenepentamine functional group;
(3) Stopping operation after the treated water body reaches an adsorption leakage point, desorbing and regenerating the tetraethylenepentamine functional resin by using a desorbing agent, and then alternately cleaning by using ethanol and ultrapure water until the pH value of effluent liquid is neutral;
The pH value of the high-salt copper-containing water body after adjustment is 2.5-10;
The mass concentration of copper ions in the water body is less than 150 mg/L, the mass concentration of salt in the water body is below 30%, the salt is at least one of sodium salt, potassium salt, calcium salt and magnesium salt, the sodium salt comprises at least one of NaCl and NaNO 3、Na2SO4、NaH2PO4, and the potassium salt, the calcium salt and the magnesium salt are nitrate;
in the step (3), the desorbing agent is a nitric acid or hydrochloric acid aqueous solution with the mass percentage concentration of 2% -15%; when the acid liquor passes through the tetraethylenepentamine functional resin, desorption is carried out at the temperature of 10-40 ℃ at the flow rate of 1-5 resin bed volumes per hour, and when the concentration of copper ions in desorption effluent is less than 0.01 mg/L, the desorption is finished;
The preparation method of the tetraethylenepentamine functional resin comprises the following steps:
Swelling chloromethylated polystyrene resin with 1, 2-dichloroethane for 10-15 h, filtering out swelling agent 1, 2-dichloroethane, adding into mixed solution of tetraethylenepentamine and lower alcohol according to the solid-to-liquid ratio of 1g to 50-70 ml, carrying out functional group grafting reaction for 24-30 h under the constant temperature oil bath condition of 60-120 ℃, filtering out the mixed solution, carrying out Soxhlet extraction with lower alcohol to remove residual tetraethylenepentamine and 1, 2-dichloroethane, drying to obtain resin with skeleton grafted with tetraethylenepentamine groups, marking the resin as tetraethylenepentamine functional resin, alternately cleaning for a plurality of times with absolute ethyl alcohol and ultrapure water after preparation, and carrying out vacuum drying to obtain the tetraethylenepentamine functional resin; wherein the lower alcohol is ethanol; the volume ratio of tetraethylenepentamine to lower alcohol in the mixed solution is 1-4: 1.
2. The method for removing and recovering copper ions from a high salt water body by using a tetraethylenepentamine functional resin according to claim 1, wherein in the step (2), the temperature of the filtrate passing through an adsorption tower is 5-40 ℃, and the flow rate of the filtrate is not more than 5 resin bed volumes per hour.
3. The method for removing and recovering copper ions from a high salt water using a tetraethylenepentamine functional resin according to claim 1, wherein in the step (3), the adsorption leakage point is a mass concentration of the copper ions (calculated as Cu) of > 0.01 mg/L.
4. The method for removing and recovering copper ions from high-salt water by using tetraethylenepentamine functional resin according to claim 1, wherein the operation mode of single-tower adsorption-single-tower desorption or multi-tower serial adsorption-single-tower desorption is adopted in the steps (2) and (3).
5. The method for removing and recovering copper ions from a high salt water body by using a tetraethylenepentamine functional resin according to claim 1, wherein the particle size of the tetraethylenepentamine functional resin is 0.2-1.0 mm.
6. The method for removing and recovering copper ions from a high salt water using a tetraethylenepentamine functional resin according to claim 5, wherein the particle size of the tetraethylenepentamine functional resin is 0.6-0.9 mm.
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