CN110078280B - Method for synchronously removing low-concentration citric acid complex copper and hexavalent chromium in wastewater and application thereof - Google Patents
Method for synchronously removing low-concentration citric acid complex copper and hexavalent chromium in wastewater and application thereof Download PDFInfo
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- CN110078280B CN110078280B CN201910440683.5A CN201910440683A CN110078280B CN 110078280 B CN110078280 B CN 110078280B CN 201910440683 A CN201910440683 A CN 201910440683A CN 110078280 B CN110078280 B CN 110078280B
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- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 title claims abstract description 139
- 239000010949 copper Substances 0.000 title claims abstract description 98
- 239000002351 wastewater Substances 0.000 title claims abstract description 74
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 69
- 238000000034 method Methods 0.000 title claims abstract description 54
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 239000011651 chromium Substances 0.000 claims abstract description 57
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims abstract description 44
- 230000009467 reduction Effects 0.000 claims abstract description 20
- 239000003513 alkali Substances 0.000 claims abstract description 17
- 229910001431 copper ion Inorganic materials 0.000 claims abstract description 15
- 238000001556 precipitation Methods 0.000 claims abstract description 15
- 230000000694 effects Effects 0.000 claims abstract description 9
- 230000009471 action Effects 0.000 claims abstract description 8
- 229910001430 chromium ion Inorganic materials 0.000 claims abstract description 7
- LCTONWCANYUPML-UHFFFAOYSA-N Pyruvic acid Chemical compound CC(=O)C(O)=O LCTONWCANYUPML-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229940107700 pyruvic acid Drugs 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000013110 organic ligand Substances 0.000 claims description 8
- 239000006228 supernatant Substances 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 5
- 239000003446 ligand Substances 0.000 claims description 5
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 claims description 4
- 230000007246 mechanism Effects 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 238000012546 transfer Methods 0.000 claims description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 229910001882 dioxygen Inorganic materials 0.000 claims description 2
- 238000007323 disproportionation reaction Methods 0.000 claims description 2
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 claims 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 abstract description 24
- 229910002476 CuII Inorganic materials 0.000 abstract description 24
- 229910052804 chromium Inorganic materials 0.000 abstract description 20
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 150000002739 metals Chemical class 0.000 abstract description 3
- 238000006722 reduction reaction Methods 0.000 description 20
- 150000003254 radicals Chemical class 0.000 description 16
- 239000000243 solution Substances 0.000 description 15
- 208000028659 discharge Diseases 0.000 description 13
- 125000000129 anionic group Chemical group 0.000 description 10
- 229920002401 polyacrylamide Polymers 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 150000004699 copper complex Chemical class 0.000 description 8
- 229910001385 heavy metal Inorganic materials 0.000 description 8
- 229910001868 water Inorganic materials 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 238000004435 EPR spectroscopy Methods 0.000 description 5
- 239000003638 chemical reducing agent Substances 0.000 description 5
- 230000000536 complexating effect Effects 0.000 description 5
- QKSIFUGZHOUETI-UHFFFAOYSA-N copper;azane Chemical compound N.N.N.N.[Cu+2] QKSIFUGZHOUETI-UHFFFAOYSA-N 0.000 description 5
- 239000012528 membrane Substances 0.000 description 5
- 238000005342 ion exchange Methods 0.000 description 4
- 230000001699 photocatalysis Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000010453 quartz Substances 0.000 description 4
- 230000001603 reducing effect Effects 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 238000004065 wastewater treatment Methods 0.000 description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 238000009713 electroplating Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- 238000013032 photocatalytic reaction Methods 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000009388 chemical precipitation Methods 0.000 description 2
- 239000008139 complexing agent Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000002848 electrochemical method Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- -1 metallurgy Substances 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010408 sweeping Methods 0.000 description 2
- 230000001360 synchronised effect Effects 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- VCUVETGKTILCLC-UHFFFAOYSA-N 5,5-dimethyl-1-pyrroline N-oxide Chemical compound CC1(C)CCC=[N+]1[O-] VCUVETGKTILCLC-UHFFFAOYSA-N 0.000 description 1
- 240000000146 Agaricus augustus Species 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 239000012028 Fenton's reagent Substances 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000003321 atomic absorption spectrophotometry Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical group C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- VQWFNAGFNGABOH-UHFFFAOYSA-K chromium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Cr+3] VQWFNAGFNGABOH-UHFFFAOYSA-K 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 description 1
- 239000013078 crystal Substances 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
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 238000011835 investigation 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
- 239000007788 liquid Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100001234 toxic pollutant Toxicity 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Images
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
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
Abstract
The invention provides a method for synchronously removing low-concentration citric acid complex copper and hexavalent chromium in wastewater and application thereof, wherein the method comprises the following steps: treating wastewater containing citric acid complex copper and hexavalent chromium by ultraviolet irradiation, adding alkali for precipitation, and separating. Compared with the prior art, the invention has the advantages that the UV/CuII(Cit), pyruvic acid and CO are finally formed2 ·‑Free radicals, which realize efficient reduction of Cr (VI), so that chromium ions mainly exist in the form of Cr (III) in the solution; for CuII(Cit) copper ion, UV/Cu on the one handII(Cit) the breaking action of HO & free radicals generated in the system; on the other hand, Cu is generated under the condition of UV radiationIIThe generated LMCT effect in the (Cit) structure and the final alkali precipitation can realize the Cu2+And cr (iii) are removed efficiently. The invention realizes the simultaneous removal of the copper and chromium double metals, and has simple method and low cost.
Description
Technical Field
The invention belongs to the field of heavy metal wastewater treatment, and particularly relates to a method for synchronously removing low-concentration citric acid complex copper and hexavalent chromium in wastewater and application thereof.
Background
Heavy metal wastewater is one of industrial wastewater with the most serious environmental pollution and the most harm to human beings, and the treatment of heavy metal wastewater mainly comprises a chemical precipitation method, an adsorption method, an ion exchange method, an electrochemical method, heavy metal capture, membrane separation and the like at present, but the treatment process generally has the disadvantages of large investment, high operation cost and the likeThe operation is complicated and the like. The chemical precipitation method with the most common application range also has the problems of large dosage of medicament, low efficiency, large sludge generation amount and the like. The copper complexing wastewater mainly comes from the production industries of electroplating, circuit boards, pigments and the like, and common complexing agents comprise: NH (NH)3EDTA, ethylenediamine, tartaric acid, citric acid and the like, which coordinate with copper ions to form a very stable soluble complex, become the main pollutants of the copper complexing wastewater. Compared with free copper ions, the removal difficulty of complex copper ions is high, and the satisfactory treatment effect is difficult to obtain by a common neutralization and precipitation method. The current main treatment technology for the complexing copper wastewater is mainly divided into the following steps of breaking and not breaking:
1. breaking the complex to separate the copper from the complex state, and removing the copper, such as: (a) sulfide precipitation method: adding S to the copper complex wastewater2-(usually Na)2S, complexing Cu in the copper wastewater2+Precipitate to form CuS (K) with small solubility productSP＝6.3×10-36) Precipitation, thereby removing copper, the main problem being S2-Is difficult to control accurately, and once S is added2-Excessive odor can be generated, and secondary pollution is caused; (b) oxidation method, etc.; the strong oxidizing agent oxidatively decomposes the copper-complexed ligand, releasing the copper from the complexed state to the free state, which is then converted to Cu (OH) by addition of a base2Precipitating and removing. The commonly used oxidants include NaClO, Fenton reagent and the like, and the method is mainly applied to complexing agents with organic ligands, such as Cu-EDTA and the like. Recently, an electrocatalysis method is adopted to treat the copper ammonia complex wastewater, a chlorine-separating electrode is taken as an anode, a titanium mesh is taken as a cathode, the copper ammonia complex wastewater is introduced, the copper ammonia complex wastewater is subjected to electrolytic catalysis treatment, and the treated wastewater is directly discharged or enters subsequent treatment (application number: 201510573996. X); (c) the reduction method is a copper removal treatment method for reducing copper ions in copper complex wastewater to separate out copper by using a reducing agent, and the commonly used reducing agent comprises iron powder, hydrazine hydrate, sulfite and sodium hydrosulfite (Na)2S2O4) (application No.: 201510496787.X), and the like; (d) substitution method: the principle of copper removal by the ferrous sulfate method is based on Cu (NH)3)4 2+And EDTA-Cu2+With EDTA-Fe3+Difference in stability constant (. beta.) ofEDTA-Fe 3+＝1.70×1024,βEDTA-Cu 2+＝5.01×1018,βCu(NH3)2+＝2.09×1013，EDTA-Fe3+Has the largest stability constant, so that Fe is added into the copper complex wastewater3+Can promote EDTA-Fe3+To bond Cu2+And displacing to convert the copper from the complex state to the free state. Patent application No. (201410264651.1) adds ferric salt to the complexing waste water of target heavy metal first and takes place the replacement reaction, carries out ultraviolet irradiation and handles in order to destroy the complex in the waste water, adjusts the pH value of waste water and makes target heavy metal and iron deposit, later accomplishes the processing procedure of waste water through solid-liquid separation.
2. The complex copper and the ionic copper are directly removed simultaneously without breaking the complex, such as an adsorption method, an electrochemical method, heavy metal trapping, an adsorption method, an ion exchange method and the like. In recent years, a copper ammonia complex wastewater treatment method (application number: 201310449645.9) has been newly developed, and ammonia nitrogen is treated from copper ammonia complex ions [ Cu (NH) by using a MAP method3)4]2+The copper and the ammonia are separated, so that the copper and the ammonia are broken into complex, the copper becomes free copper ions, and the ammonia are MgNH4Precipitate in the form of PO4, copper in Cu (OH)2Form precipitation, deamination of the precipitated product, recovery of copper and return to the water treatment process.
Chromium element is listed as one of the most toxic pollutants by the United States Environmental Protection Agency (USEPA), and chromium in chromium-containing wastewater mainly comes from industries such as electroplating, tanning, chemical engineering, pigment, metallurgy, refractory materials and the like, and exists in the form of trivalent and hexavalent compounds. Hexavalent chromium is more biologically toxic than trivalent chromium due to its high solubility. At present, hexavalent chromium wastewater is mainly subjected to a chemical reduction method, which mainly comprises a medicament reduction method, a ferrite method, an iron scrap iron powder reduction method and the like. The basic principle is that hexavalent chromium is reduced into trivalent chromium by using a chemical reducing agent under an acidic condition, then chromium hydroxide precipitate is generated by using alkali precipitation to remove the trivalent chromium, and in addition, Cr (VI) can be separated from a water body by adopting methods such as ion exchange, activated carbon adsorption, reverse osmosis and the like under the condition of not changing the form of Cr (VI). Among them, the chemical reduction method, the ion exchange method, the electrolytic reduction method, and the like are widely used.
In summary, the complex copper and hexavalent chromium wastewater treatment technologies have characteristics, and in the actual wastewater treatment process, a reasonable treatment process should be selected according to the water quality characteristics (including other pollutant conditions) of the wastewater and the specific conditions of the production unit, and the economic and technical factors are comprehensively considered. Aiming at the harmfulness of the copper and hexavalent chromium complex wastewater, a more efficient and clean treatment method should be researched, which helps to solve the defects of high treatment cost, low efficiency, complex operation and the like of the heavy metal wastewater so as to promote the improvement of the treatment technical level of the copper and hexavalent chromium complex wastewater.
Disclosure of Invention
The invention aims to provide a method for synchronously removing low-concentration citric acid complex copper and hexavalent chromium in wastewater, which can realize the synchronous removal of copper and chromium double metals by treating the wastewater containing the citric acid complex copper and the hexavalent chromium by using ultraviolet radiation.
The invention aims to provide application of a method for synchronously removing low-concentration citric acid complex copper and hexavalent chromium in wastewater, and the method is used for treating the wastewater containing the citric acid complex copper or the wastewater containing the hexavalent chromium.
The specific technical scheme of the invention is as follows:
a method for synchronously removing low-concentration citric acid complex copper and hexavalent chromium in wastewater comprises the following steps:
treating wastewater containing citric acid complex copper and hexavalent chromium by ultraviolet irradiation, adding alkali for precipitation, and separating.
Further, the ultraviolet irradiation treatment time is 60-100 min.
Furthermore, the concentration of the citric acid complex copper in the wastewater is 10-30 mg/L, and the concentration of the hexavalent chromium is 8-16 mg/L.
The alkali precipitation refers to the addition of alkali to adjust the pH value to 10.0.
Further, after adding alkali, standing for 1h, centrifuging at a rotation speed of 5000r/min for 5min, and filtering with a 0.45 μm filter membrane to obtain a supernatant.
The invention provides an application of a method for synchronously removing low-concentration citric acid complex copper and hexavalent chromium in wastewater, which is used for treating wastewater containing citric acid complex copper, and the specific treatment method comprises the following steps:
adding hexavalent chromium into the wastewater of the citric acid complex copper to be treated, then irradiating by ultraviolet light, adding an anionic polyacrylamide solution into the wastewater after adding alkali, standing, and separating to obtain the product.
The wastewater containing the citric acid complex copper is mainly from cleaning wastewater generated in the electroplating industry
In the wastewater of the citric acid complex copper to be treated, the concentration of the citric acid complex copper is 10-30 mg/L.
Adding hexavalent chromium into the wastewater, wherein the concentration of the hexavalent chromium in the wastewater is 8-16 mg/L.
Furthermore, the dosage of the anionic polyacrylamide solution is that 0.5-5ml of the anionic polyacrylamide solution is added into every 1L of wastewater. The mass concentration of the anionic polyacrylamide solution was 0.1%.
The standing refers to standing for 2 hours.
The invention provides an application of a method for synchronously removing low-concentration citric acid complex copper and hexavalent chromium in wastewater, which is used for treating wastewater containing hexavalent chromium, and the specific treatment method comprises the following steps:
adding citric acid complex copper into hexavalent chromium wastewater to be treated, irradiating by ultraviolet light, adding an anionic polyacrylamide solution into the wastewater after adding alkali, standing, and separating.
The concentration of hexavalent chromium in the wastewater is 8-16 mg/L.
After the citric acid complex copper is added, the concentration of the citric acid complex copper in the wastewater is 10-30 mg/L.
Furthermore, the dosage of the anionic polyacrylamide solution is that 0.5-5ml of the anionic polyacrylamide solution is added into every 1L of wastewater. The mass concentration of the anionic polyacrylamide solution was 0.1%.
The standing refers to standing for 2 hours.
The mechanism for simultaneously removing the copper and chromium bimetallic is as follows: if only in UV/H3cit and UV/Na3Cit system, H2O and O2Generating hydroxyl radical HO. under the irradiation of ultraviolet light, and generating hydroxyl radical in UV/CuII(Cit), charge transfer (LMCT) can occur between the organic ligand in the complex copper structure and Cu (II), so that not only can corresponding ligand free radicals be generated, but also Cu (II) can be reduced to Cu (I), and due to instability of the ligand free radicals, O can be generated by further reaction with molecular oxygen in water2 ·-/HO2 ·-And citric acid molecule, under the action of disproportionation reaction2 ·-/HO2 ·-Final conversion to H2O2In Cu (I) and H2O2The generation of HO & free radicals can be accelerated based on Fenton-like reaction in the coexisting system. Further the hydroxyl radical HO, through attack of-OH in citric acid, generates oxygen free radicals, the carboxyl group connected with oxygen is broken, and pyruvic acid and CO are formed2 ·-Free radicals to realize efficient reduction of Cr (VI), so that Cr ions mainly exist in the form of Cr (III) in the solution, and for CuII(Cit) copper ion, UV/Cu on the one handII(Cit) the breaking action of HO & free radicals generated in the system; on the other hand, Cu is generated under the condition of UV radiationII(Cit) LMCT effects occurring in the structure. Under the combined action of the two actions, not only is complex copper ions liberated to form Cu2+Can be removed together with Cr (III) by alkali precipitation, and allows H to be removed3The cit organic ligand is effectively converted and decomposed, and Cr (III) and H are avoided3The further reaction of the cit organic ligand to form a stable complex, and the simple precipitation with alkali to realize Cu2+And cr (iii) are removed efficiently. The basic reaction mechanism of the present invention is shown in FIG. 6. High concentration of CuII(Cit) UV/CuII(Cit) has a strong reducing effect on Cr (VI) because of CuIIThe increase of the concentration of (Cit) increases the capability of generating HO & in the system, and simultaneously increases the concentration of citric acid molecules in the system, so that HO & is easier to capture, and more CO is generated2 ·-Thus increasing CuII(Cit) concentrations can enhance cr (vi) reduction efficiency. With CuII(Cit) increasing concentration, H3The concentration of Cit organic ligand is also increasing at the same time, with the possibility of Cu2+And Cr3+Re-complexing of (a) is detrimental to the total copper removal.
Compared with the prior art, the method can simultaneously remove the copper and chromium double metals, is simple and low in cost, can treat the wastewater containing hexavalent chromium or the copper complex containing citric acid by using the method, treats the copper complex wastewater containing citric acid by adding the hexavalent chromium into the copper complex wastewater containing citric acid, or treats the hexavalent chromium by adding the copper complex containing citric acid into the copper complex wastewater, has high removal efficiency, realizes synchronous removal, is simple, and does not cause secondary pollution.
Drawings
FIG. 1 comparison of different systems for reducing Cr (VI);
FIG. 2 different CuII(Cit) effect of concentration on cr (vi) reduction;
FIG. 3 different CuII(Cit) effect of dosing on total chromium residual concentration;
FIG. 4 shows Cu of differentII(Cit) effect of dosing on total copper residual concentration;
FIG. 5 is ESR characterization patterns under different systems;
FIG. 6 Cu under UV radiation according to the inventionII(cit) a mechanism for simultaneous decomplexing and Cr (VI) reduction;
FIG. 7 reduction ratio of Cr (VI);
FIG. 8 shows the total chromium concentration in the effluent;
FIG. 9 shows the total copper concentration of the effluent.
Detailed Description
Example 1
Configuration of simulated wastewater:
(1) preparing 500mg/L citric acid complex copper (Cu)II(cit)) stock solutions: 0.4883g of copper sulfate pentahydrate crystal and 0.5736g of trisodium citrate dihydrate are weighed, the molar ratio of the two substances is 1:1, the two substances are completely dissolved by deionized water after being mixed, and the mixture is transferred into a 250mL volumetric flask refrigerator for refrigeration and standby.
(2) Simulating wastewater containing Cr (VI): weighing potassium dichromate (K) dried at 120 deg.C for 2 hr2Cr2O7)0.2829g, dissolved completely by deionized water, and then transferred into a 250mL volumetric flask to prepare Cr (VI) concentrateThe simulated wastewater with the degree of 400mg/L contains Cr (VI).
A method for synchronously removing low-concentration citric acid complex copper and hexavalent chromium in wastewater comprises the following steps:
a quartz round-bottom test tube is used as a reaction container, reagents with different volumes and known concentrations are put into the reaction test tube, and then deionized water is used for constant volume, so that the total volume of a reaction solution is 50 mL. The reaction was carried out in a photocatalytic reaction apparatus (PL-02, Princes technologies, Beijing) using a high pressure mercury lamp with an electric power of 500W. Before the reaction starts, the UV light source is firstly started and preheated for 30min to ensure the light intensity to be stable in the reaction process, then the reaction test tube is placed into a light reaction instrument, the ultraviolet light source is started to carry out the photocatalytic reaction, and the sample is sampled and analyzed in a set time period.
Initial Cr (VI) concentration of 8mg/L, CuII(Cit) concentration was 20mg/L without initial pH adjustment. The reaction is carried out in a photocatalytic reactor (PL-02, Beijing Prinleis science and technology limited), a reaction test tube is placed in the photocatalytic reactor, a high-pressure mercury lamp irradiates simulated wastewater, after the reaction is finished, a water sample is properly diluted by deionized water, the pH value is adjusted to 10.0 by adding sodium hydroxide (0.1M), after the reaction is kept stand for 1h, the reaction product is centrifuged for 5min at the rotating speed of 5000r/min, and then a filter membrane with the diameter of 0.45 mu M is used for filtering to obtain a supernatant. When the irradiation reaction of the high-pressure mercury lamp is carried out for 20min, the reduction efficiency of Cr (VI) is 100 percent; after the reaction is carried out for 100min, no chromium element and copper ion residue is detected in the effluent, which indicates that the removal rate of chromium ions and copper ions can reach 100 percent, and the maximum allowable discharge concentration of the total chromium in the integrated wastewater discharge standard (GB 8978-1996) and the maximum allowable discharge concentration of the total copper in the primary discharge standard are 1.5mg/L and 0.5 mg/L.
Wherein, hexavalent chromium is measured by a diphenyl carbonyl dihydrazide spectrophotometry (GB 7466-1987); and (3) measuring the total chromium and total copper concentration: properly diluting a water sample with deionized water, adding sodium hydroxide (0.1M) to adjust the pH value to 10.0, standing for 1h, centrifuging for 5min at the rotation speed of 5000r/min, filtering with a 0.45-micrometer filter membrane to obtain a supernatant, and respectively measuring the concentrations of chromium and copper elements in the supernatant by adopting a flame atomic absorption spectrophotometry (TU-900, common in Beijing Pukoku (TM)).
Comparative example: under the condition that the initial concentration of Cr (VI) is 20mg/L, comparing citric acid, sodium citrate and citric acid complex copper respectively, namely: UV/H3Cit、UV/Na3Cit、UV/CuII(Cit) reduction effect of three systems on cr (vi):
wherein H3cit、Na3Cit and CuII(Cit) initial concentration was 0.312mM (as citrate) and UV treatment parameters were the same as for citrate
Example 1, the results of the test are shown in FIG. 1. As can be seen from the figure, the three systems have different degrees of reduction on Cr (VI), and when the reaction time is 100min, the reaction time is UV/H3Cit、UV/Na3Cit、UV/CuIIThe reduction rates of (Cit) to Cr (VI) were 28.0%, 78.4% and 100%, respectively.
Cu when the initial Cr (VI) concentration is 16mg/LII(cit) concentrations of 10, 20 and 30mg/L, respectively, further investigation of different CuII(cit) effect of concentration on Cr (VI) reduction efficiency and total chromium and total copper removal, UV treatment parameters were the same as in example 1, and the results are shown in FIGS. 2, 3 and 4. As can be seen from FIG. 2, for the reduction of Cr (VI), when the reaction time is 40min, Cu is presentII(cit) concentration is increased from 10mg/L to 30mg/L, and the reduction efficiency of Cr (VI) is increased from 60.6 percent to 100 percent; from FIGS. 3 and 4, it can be seen that for total chromium and total copper removal efficiency, when Cu is removedII(Cit) when the concentration is increased from 10mg/L to 20mg/L, no chromium element and copper ion residue is detected in the effluent water when the reaction is carried out for 80min, which indicates that the removal rate of chromium ions and copper ions can reach 100 percent, and the maximum allowable discharge concentration of the total chromium in the integrated wastewater discharge standard (GB 8978-1996) and the maximum allowable discharge concentration of the total copper in the primary discharge standard are 1.5mg/L and 0.5mg/L, so that the standard discharge of the wastewater containing chromium ions and copper ions can be realized; when CuIIWhen the concentration of (Cit) is continuously increased to 30mg/L from 20mg/L, the concentrations of residual chromium ions and copper ions in effluent are respectively 0.46mg/L and 0.75mg/L (more than 0.5mg/L standard) when the reaction is carried out for 100min, and the total chromium can reach the standard and be discharged.
For exploring the main reducing species and the reduction of Cr (VI) thereof under different systemsMechanism, which utilizes Electron Spin Resonance (ESR) to identify the main radical species in each system, using UV/H3cit、UV/CuII(cit)、UV/CuII(cit)/Cr (VI) three systems are respectively based on the peak intensity of the captured free radical signal under the condition of 15min of ultraviolet lamp irradiation in the same embodiment 1, wherein H is3cit and CuII(cit) concentrations were all 0.31mM (as citrate) and the ESR identification results for the three systems are shown in FIG. 5. As can be seen from the figure, in UV/H3cit、UV/CuII(cit)、UV/CuIIThe same two free radical signal peaks appear in the three systems (cit)/Cr (VI). ● in the figure, the peak ratio of four characteristic peaks in the signal peak is 1:2:2:1, and the hyperfine splitting constant is alphaN＝αHWhen 14.9G, 2.0055, the signal peak of DMPO-HO adduct is clear. The signal peak represented by ■ in the figure is compared with CO reported in the prior art2 ·-The peaks of the free radical signals are substantially identical, thus directly confirming HO.free radical and CO2 ·-Free radicals are all present in UV/H3cit、UV/CuIIIn the (Cit) system, it can be concluded that Cr (VI) is reduced mainly by the carbanion radical CO2 ·-And (4) promoting.
The free radical identification adopts an ESR detector (Bruker, A300) to detect and analyze the system reaction free radical. Adding DMPO solution with the concentration of 10ppm into a reaction system, sucking a proper amount of solution by a capillary pipette, adding the solution into a quartz nuclear magnetic tube, and putting the quartz nuclear magnetic tube into an electron spin resonance instrument for detection and analysis. Free radical detection conditions: a central magnetic field 3500.00G; the width of the sweeping field is 150.00G; the field sweeping time is 30.00 s; the microwave power is 3.99 mW; the modulation amplitude is 1.000G; the switching time is 40.0 ms.
Example 2
A method for synchronously removing citric acid complex copper and hexavalent chromium in wastewater comprises the following steps:
1) taking 50mL of Cr (VI) wastewater with the initial concentration of 32mg/L of Cr (VI), and adding 40mg/L of CuII(cit) 50mL of wastewater, without adjusting the initial pH;
2) a quartz round-bottom test tube is used as a reaction container, the reaction is carried out in a photocatalytic reactor (same as the example 1), before the reaction starts, a UV light source is started and preheated for 30min to ensure the light intensity to be stable in the reaction process, then the reaction test tube is placed in the photocatalytic reactor, the ultraviolet light source is started to carry out the photocatalytic reaction, and the sample is sampled and analyzed in a set time period.
3) After the reaction is finished, a water sample is properly diluted by deionized water, sodium hydroxide (0.1M) is added to adjust the pH value to 10.0, and then 0.5-5ml of anionic polyacrylamide solution is added into every 1L of wastewater, wherein the mass concentration of the anionic polyacrylamide solution is 0.1%. Standing for 2h, and filtering with 0.45 μm filter membrane to obtain supernatant.
When the UV light source irradiates and reacts for 80min, the reduction efficiency of Cr (VI) is 100 percent; after the reaction is carried out for 100min, no chromium element and copper ion residue is detected in the effluent, which indicates that the removal rate of chromium ions and copper ions can reach 100 percent, and the maximum allowable discharge concentration of the total chromium in the integrated wastewater discharge standard (GB 8978-1996) and the maximum allowable discharge concentration of the total copper in the primary discharge standard are 1.5mg/L and 0.5 mg/L.
The method for measuring the concentrations of hexavalent chromium, total chromium and total copper is the same as that in example 1.
Claims (4)
1. A method for synchronously removing low-concentration citric acid complex copper and hexavalent chromium in wastewater is characterized by comprising the following steps:
treating wastewater containing citric acid complex copper and hexavalent chromium by ultraviolet irradiation, adding alkali for precipitation, and separating;
the concentration of the citric acid complex copper in the wastewater is 10-30 mg/L, and the concentration of the hexavalent chromium is 8-16 mg/L;
the mechanism for synchronously removing low-concentration citric acid complex copper and hexavalent chromium in the wastewater is as follows: UV/citric acid complex copper Cu under ultraviolet irradiationII(Cit), the charge transfer occurs between the organic ligand in the complex copper structure and Cu (II), so that not only can corresponding ligand free radicals be generated, but also Cu (II) can be reduced into Cu (I), and due to the instability of the ligand free radicals, O can be further generated by the reaction with molecular oxygen in water2 •-/HO2 •-And a citric acid molecule,under the action of disproportionation reaction2 •-/HO2 •-Final conversion to H2O2In Cu (I) and H2O2The generation of HO. free radicals can be accelerated under the Fenton-like reaction in a coexisting system; further hydroxyl radical HO, by attacking-OH in citric acid, an oxygen radical is generated, the carboxyl group connected with oxygen is broken, and pyruvic acid and CO are formed2 •-Free radicals to realize efficient reduction of Cr (VI), so that chromium ions mainly exist in the form of Cr (III) in the solution, and Cu is complexed by citric acidII(Cit) in which copper ions are UV/citric acid-complexed copper Cu by UV irradiationII(Cit) decomplexation of ho. radicals generated in the system; on the other hand, the Cu is citrate-complexedII(Cit) charge transfer effects occurring in the structure; under the combined action of the two actions, not only is complex copper ions liberated to form Cu2+Can be removed together with Cr (III) by alkali precipitation, and enables citric acid H3The Cit organic ligand is effectively converted and decomposed, and Cr (III) and citric acid H are avoided3The further reaction of the Cit organic ligand to form a stable complex, and the simple alkali precipitation can realize the Cu2+And cr (iii) are removed efficiently.
2. The method according to claim 1, wherein the ultraviolet irradiation treatment time is 60 to 100 min.
3. The method of claim 1 or 2, wherein the alkali precipitation is performed by adding alkali to adjust the pH to 10.0.
4. The method of claim 1, wherein the supernatant is obtained by adding an alkali, standing for 1 hour, centrifuging at 5000r/min for 5min, and filtering with a 0.45 μm filter.
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