CN112645485A - Method for complex breaking and synchronous recovery of heavy metal-organic acid composite wastewater - Google Patents
Method for complex breaking and synchronous recovery of heavy metal-organic acid composite wastewater Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 106
- 239000002351 wastewater Substances 0.000 title claims abstract description 87
- 238000000034 method Methods 0.000 title claims abstract description 52
- 238000011084 recovery Methods 0.000 title claims abstract description 32
- 230000001360 synchronised effect Effects 0.000 title claims abstract description 12
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 67
- 239000012528 membrane Substances 0.000 claims abstract description 61
- 238000003795 desorption Methods 0.000 claims abstract description 20
- 238000005086 pumping Methods 0.000 claims abstract description 19
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 18
- 230000003647 oxidation Effects 0.000 claims abstract description 17
- 238000003756 stirring Methods 0.000 claims abstract description 11
- 150000007524 organic acids Chemical class 0.000 claims abstract description 10
- 239000003814 drug Substances 0.000 claims abstract description 4
- 238000001179 sorption measurement Methods 0.000 claims description 23
- 239000003795 chemical substances by application Substances 0.000 claims description 22
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 12
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 8
- 239000012621 metal-organic framework Substances 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 239000002033 PVDF binder Substances 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 6
- 239000003153 chemical reaction reagent Substances 0.000 claims description 5
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 5
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 claims description 5
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 claims description 5
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 239000011159 matrix material Substances 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 229920002492 poly(sulfone) Polymers 0.000 claims description 4
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 4
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 3
- 239000013177 MIL-101 Substances 0.000 claims description 3
- 239000013207 UiO-66 Substances 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 claims description 3
- 238000011068 loading method Methods 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 239000011975 tartaric acid Substances 0.000 claims description 3
- 235000002906 tartaric acid Nutrition 0.000 claims description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 2
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims description 2
- 239000004695 Polyether sulfone Substances 0.000 claims description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052793 cadmium Inorganic materials 0.000 claims description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 2
- 238000005266 casting Methods 0.000 claims description 2
- BFGKITSFLPAWGI-UHFFFAOYSA-N chromium(3+) Chemical compound [Cr+3] BFGKITSFLPAWGI-UHFFFAOYSA-N 0.000 claims description 2
- 229920006393 polyether sulfone Polymers 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims description 2
- 210000003462 vein Anatomy 0.000 claims description 2
- 238000004064 recycling Methods 0.000 claims 9
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims 1
- 235000015165 citric acid Nutrition 0.000 claims 1
- 238000002360 preparation method Methods 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 6
- 239000002253 acid Substances 0.000 abstract description 4
- 230000000536 complexating effect Effects 0.000 abstract description 3
- 238000004043 dyeing Methods 0.000 abstract description 3
- 238000009713 electroplating Methods 0.000 abstract description 3
- 238000007639 printing Methods 0.000 abstract description 3
- 238000009395 breeding Methods 0.000 abstract description 2
- 230000001488 breeding effect Effects 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000005516 engineering process Methods 0.000 description 18
- 238000010668 complexation reaction Methods 0.000 description 11
- 238000001914 filtration Methods 0.000 description 9
- 238000000926 separation method Methods 0.000 description 7
- 239000011701 zinc Substances 0.000 description 7
- 239000010949 copper Substances 0.000 description 6
- 239000011651 chromium Substances 0.000 description 5
- 238000001514 detection method Methods 0.000 description 5
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 4
- 239000008139 complexing agent Substances 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 238000009388 chemical precipitation Methods 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 150000004696 coordination complex Chemical class 0.000 description 2
- 229960001484 edetic acid Drugs 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000013110 organic ligand Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- PXRKCOCTEMYUEG-UHFFFAOYSA-N 5-aminoisoindole-1,3-dione Chemical compound NC1=CC=C2C(=O)NC(=O)C2=C1 PXRKCOCTEMYUEG-UHFFFAOYSA-N 0.000 description 1
- 229920012266 Poly(ether sulfone) PES Polymers 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000012982 microporous membrane Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002699 waste material 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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
-
- 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
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0084—Treating solutions
- C22B15/0086—Treating solutions by physical methods
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0084—Treating solutions
- C22B15/0089—Treating solutions by chemical methods
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B17/00—Obtaining cadmium
- C22B17/04—Obtaining cadmium by wet processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B19/00—Obtaining zinc or zinc oxide
- C22B19/20—Obtaining zinc otherwise than by distilling
- C22B19/26—Refining solutions containing zinc values, e.g. obtained by leaching zinc ores
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0453—Treatment or purification of solutions, e.g. obtained by leaching
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0453—Treatment or purification of solutions, e.g. obtained by leaching
- C22B23/0461—Treatment or purification of solutions, e.g. obtained by leaching by chemical methods
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/30—Obtaining chromium, molybdenum or tungsten
- C22B34/32—Obtaining chromium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
-
- 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
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
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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
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/16—Nature of the water, waste water, sewage or sludge to be treated from metallurgical processes, i.e. from the production, refining or treatment of metals, e.g. galvanic wastes
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/22—Nature of the water, waste water, sewage or sludge to be treated from the processing of animals, e.g. poultry, fish, or parts thereof
- C02F2103/24—Nature of the water, waste water, sewage or sludge to be treated from the processing of animals, e.g. poultry, fish, or parts thereof from tanneries
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/30—Nature of the water, waste water, sewage or sludge to be treated from the textile industry
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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
- C02F2303/00—Specific treatment goals
- C02F2303/16—Regeneration of sorbents, filters
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- 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
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Abstract
The invention belongs to the field of water treatment, and particularly relates to a method for complex breaking and heavy metal synchronous recovery of heavy metal-organic acid composite wastewater; the invention is mainly characterized in that: adding an oxidation composite medicament into heavy metal-organic acid complexing wastewater, stirring, pumping into a composite membrane system for complex breaking, and recovering heavy metal adsorbed on the composite membrane by an acid desorption method after the wastewater flows out of the system; the method has the advantages of simple process, environmental protection, controllability, high speed, simple process, low cost, no secondary pollution and the like for the heavy metal wastewater containing the organic acid, and can realize the integrated treatment of the heavy metal wastewater containing the organic acid; the invention is suitable for electroplating wastewater, printing and dyeing industry wastewater, breeding wastewater and the like, and has wide application range.
Description
Technical Field
The invention belongs to the field of water treatment, and particularly relates to a method for complex breaking and synchronous recovery of heavy metal-organic acid composite wastewater.
Background
With the acceleration of the industrialization process, a large amount of heavy metal wastewater containing organic acid is generated in the industries of electroplating, printing and dyeing, breeding and the like, heavy metal in the wastewater enters the environment and is difficult to precipitate, the heavy metal in the wastewater migrates and transforms along with the change of environmental conditions, the water ecosystem is damaged, and the heavy metal is continuously enriched in a food chain, so that the human health is harmed. When organic acid coexists in the wastewater, the conventional heavy metal treatment technology (chemical precipitation and adsorption method) is difficult to achieve ideal effects.
In recent years, the reported treatment technologies for heavy metal organic acid complex waste mainly include coordination precipitation technology, metal ion displacement technology, reduction technology and oxidation technology. The coordination precipitation technology is simple and easy to implement, but the dosage of the medicament is large, and the trapping agent is easy to decompose under the acidic condition; the metal ion replacement technology is simple, convenient and quick to operate, but poor in stability due to the fact that a complexing agent is released; the reduction technology is simple and efficient, but the application range is limited.
Fenton oxidation, electrochemistry, photochemistry and other oxidation complex breaking technologies are concerned, and can preferentially break the organic ligand, so that the complexing capacity of the organic ligand to heavy metals is weakened, and the resource recovery capacity of subsequent conventional adsorption separation technologies to the free heavy metals after complex breaking is effectively improved. Chinese patent No. 201810414761.X, patent with application date of 2018, 5 months and 3 days, discloses a method for treating three-price complex wastewater by combining a reducing compound agent and ultraviolet light and synchronously recovering chromium, wherein the reducing compound agent is added into the complex wastewater of chromium-organic acid to adjust the pH value, and after treatment under the irradiation of ultraviolet light, chromium precipitates are subjected to solid-liquid separation to recover heavy metal; chinese patent No. 201510926201.9, patent document 2015, 12 months and 14 days discloses a method for breaking complexation and synchronously removing heavy metals by using self-reinforced ozone, wherein heavy metal complexation wastewater with adjusted pH value and containing heavy metal A and complexing agent B is added into an ozone contact tank, ozone is continuously introduced through micropores at the bottom of the ozone contact tank, and after uniform reaction is ensured by assisting hydraulic circulation stirring, solid-liquid separation is further carried out by filtering with a microporous membrane device, so that the breaking complexation and the heavy metal removal are realized. Therefore, the technologies still need to be further combined with technologies such as adsorption and membrane separation for advanced treatment, and the process operation is complex, the operation cost is high, and the treatment efficiency is limited.
Disclosure of Invention
Aiming at the problems that the efficiency of treating heavy metal complex by methods such as chemical precipitation, adsorption separation, reduction, replacement and the like in the prior art is low, and advanced oxidation technologies such as photochemical oxidation and electrochemical oxidation are difficult to be applied industrially and need subsequent treatment technologies, the invention provides a method for breaking complexation of heavy metal-organic acid composite wastewater and synchronously recovering heavy metal. The method has the advantages of economy, high efficiency, simple and convenient operation and easy realization of engineering application, and can realize the integration of complex breaking and metal ion removal and recovery, thereby simplifying the process flow.
In order to solve the problems, the technical scheme of the invention is as follows:
a method for complex breaking and heavy metal synchronous recovery of heavy metal-organic acid composite wastewater comprises the following steps:
(1) administration: adding an oxidation compound agent into the heavy metal-organic acid complex wastewater and stirring;
(2) breaking collaterals-adsorption: pumping the uniformly stirred wastewater into a composite membrane system, and flowing out of the system at a certain flow velocity to perform vein breaking adsorption on the wastewater;
(3) and (3) recovering heavy metals: and (3) after the reaction in the step (2) is finished, pumping the desorption agent into a composite membrane system, and recovering the heavy metal adsorbed on the composite membrane by an acid desorption method.
Preferably, the oxidation complex reagent in the step (1) is one or more of potassium persulfate and sodium persulfate.
Preferably, in the step (1), after the oxidation composite reagent is added, the mass concentration of the oxidation composite reagent in the heavy metal-organic acid composite wastewater is 0.1-10%.
Preferably, in the step (2), the integrated composite membrane is obtained by loading MOF on a membrane matrix through a blending method, the MOF has catalytic complex breaking and adsorption separation performances, wherein the membrane matrix is any one of polyvinylidene fluoride (PVDF), polyether sulfone (PES), Polyacrylonitrile (PAN) and Polysulfone (PS), and the MOF is ZIF-8, UiO-66 and UiO-66-NH2、MIL-66、MIL-66-NH2、MIL-101、MIL-101-NH2Any one or more of the MOFs, wherein the total mass concentration of the MOFs in the membrane substrate casting solution is 0.1-10%.
Preferably, the flow rate of the wastewater in the step (2) which is introduced into the composite membrane system for filtration is 0.1-500 L.m-2·h-1And the removal rate of heavy metals in the obtained water is more than 61%.
Preferably, 10-100 mL of desorption agent is pumped in the heavy metal recovery process in the step (3), the desorption agent is dilute nitric acid, dilute sulfuric acid or dilute hydrochloric acid, the mass concentration of the desorption agent is 0.5-30%, and the flow rate of the desorption agent introduced into the composite membrane system is 0.1-100 L.m-2·h-1And the recovery rate of heavy metal in the obtained water is more than 88%.
Preferably, the composite wastewater comes from the industries of electroplating, tanning, printing and dyeing and the like, wherein the heavy metal ions are any one of copper (II), nickel (II), cadmium (II), zinc (II) and chromium (III), and the organic acid is Citric Acid (CA), Tartaric Acid (TA), Oxalic Acid (OA), Ethylene Diamine Tetraacetic Acid (EDTA) or salts thereof.
Compared with the prior art, the invention has the following beneficial effects because the technology is adopted:
(1) according to the method for breaking complexation of heavy metal-organic acid composite wastewater and synchronously recovering heavy metal, the oxidation composite medicament combines the processes of breaking complexation oxidation and adsorption separation in the heavy metal complexing wastewater treatment process into one, and acid and alkali are not required to be additionally added to adjust the pH value, so that the purposes of breaking complexation by a complexing agent and synchronously removing heavy metal are achieved, the water treatment process flow is simplified, the treatment efficiency is improved, and the method is a novel heavy metal complex treatment technology which is economical, effective and simple and convenient to operate.
(2) The method for breaking complexation of heavy metal-organic acid composite wastewater and synchronously recovering heavy metal solves the defects in the application of the prior advanced oxidation technology, is simple to operate, mild in reaction condition and environment-friendly, and is more expected to be applied to engineering application of heavy metal-organic acid complex wastewater treatment. In addition, compared with the prior art, the method can oxidize and degrade most of the organic acid complexing agent and degradation products thereof in the wastewater, and obviously improve the removal of COD and TOC.
(3) The invention discloses a method for breaking complexation of heavy metal-organic acid composite wastewater and synchronously recovering heavy metal, which is accompanied by gradual conversion of organic acid into micromolecular acid and CO in the process of breaking complexation oxidation2When the micromolecule product is obtained, the released heavy metal ions or the weak complex of the heavy metal are directly adsorbed by the composite membrane, and the heavy metal can be recovered through in-situ desorption, so that the operation is simple and the efficiency is high.
Detailed Description
The present invention will be further illustrated with reference to the following specific embodiments.
Example 1:
in the method for complex breaking and synchronous recovery of heavy metal-organic acid composite wastewater, 0.2 mmol/L Cr-EDTA composite wastewater is tested, and a composite membrane system loaded with a film is a 10% ZIF-8 PVDF composite membrane. The method comprises the following steps:
A. administration: adding sodium persulfate into the Cr-EDTA composite wastewater, and fully stirring to ensure that the mass concentration of the sodium persulfate in the composite wastewater is 3.0%;
B. breaking collaterals-adsorption: pumping the solution uniformly stirred in the step A into a composite membrane system, carrying out broken-channel adsorption on the wastewater, and controlling the filtering flow rate of the wastewater to be 20 L.m-2·h-1。
C. And (3) recovering heavy metals: after the reaction in the step B is finished, pumping 50 mL of dilute nitric acid solution with the mass concentration of 10% into the composite membrane system, recovering heavy metals adsorbed on the composite membrane, and controlling the flow rate of the desorption agent to be 50 L.m-2·h-1。
According to the detection, in the embodiment, the removal rate of Cr in the step B is 98%, namely the remaining total Cr is 0.21 mg/L, the removal rate of TOC is about 63%, and the recovery rate of Cr in the step C is 93%.
Example 2
In the method for complex breaking and heavy metal synchronous recovery of heavy metal-organic acid composite wastewater of the embodiment, 1.0 mmol/L Cu-TA composite wastewater is tested, and a membrane loaded by a composite membrane system is UiO-66-NH with the mass concentration of 1 percent2And a PES composite membrane with the mass concentration of 9% MIL-101. The method comprises the following steps:
A. administration: adding potassium persulfate into the Cu-TA composite wastewater, wherein the mass concentration of the potassium persulfate in the composite wastewater after full stirring is 10%;
B. breaking collaterals-adsorption: pumping the solution uniformly stirred in the step A into a composite membrane system, carrying out broken-channel adsorption on the wastewater, and controlling the filtering flow rate of the wastewater to be 0.1 L.m-2·h-1。
C. And (3) recovering heavy metals: after the reaction in the step B is finished, pumping 10 mL of dilute hydrochloric acid solution with the mass concentration of 30% into the composite membrane system, recovering heavy metals adsorbed on the composite membrane, and controlling the flow rate of the introduced desorption agent to be 0.1 L.m-2·h-1。
According to the detection, in the present embodiment, the Cu removal rate in step B is 99.8%, i.e. the remaining Cu concentration is 0.14 mg/L, the TOC removal rate is about 58%, and the recovery rate of Cu in step C is 91%.
Example 3
Heavy gold of this exampleA method for breaking complexation of organic acid composite wastewater and synchronously recovering heavy metal is used for testing 0.1 mmol/L Ni-OA composite wastewater, and a composite membrane system is used for loading MIL-101-NH with the mass concentration of 5%2The PAN composite membrane of (1). The method comprises the following steps:
A. administration: adding potassium persulfate into the Ni-OA composite wastewater, wherein the mass concentration of the potassium persulfate in the composite wastewater after full stirring is 0.1%;
B. breaking collaterals-adsorption: pumping the solution uniformly stirred in the step A into a composite membrane system, carrying out broken-network adsorption on the wastewater, and controlling the filtering flow rate of the wastewater to be 500 L.m-2·h-1。
C. And (3) recovering heavy metals: after the reaction in the step B is finished, pumping 100mL of dilute hydrochloric acid solution with the mass concentration of 0.5% into the composite membrane system, recovering heavy metals adsorbed on the composite membrane, and controlling the flow rate of the introduced desorption agent to be 100 L.m-2·h-1。
As a result of the examination, in this example, the Ni removal rate in step B was 99.7%, i.e., the remaining Ni concentration was 0.02 mg/L, the TOC removal rate was about 67%, and the recovery rate of Ni in step C was 92%.
Example 4
In the method for complex breaking and heavy metal synchronous recovery of heavy metal-organic acid composite wastewater of the embodiment, 0.5 mmol/L Zn-CA composite wastewater is tested, and a composite membrane system is loaded with a membrane of MIL-101-NH with the mass concentration of 8%2The PS composite membrane of (1). The method comprises the following steps:
A. administration: adding potassium persulfate into the Zn-CA composite wastewater, wherein the mass concentration of the potassium persulfate in the composite wastewater after full stirring is 2%;
B. breaking collaterals-adsorption: pumping the solution uniformly stirred in the step A into a composite membrane system, carrying out broken-network adsorption on the wastewater, and controlling the filtering flow speed of the wastewater to be 100 L.m-2·h-1。
C. And (3) recovering heavy metals: after the reaction in the step B is finished, pumping 80mL of dilute hydrochloric acid solution with the mass concentration of 8% into the composite membrane system, recovering heavy metals adsorbed on the composite membrane, and controlling the flow rate of the desorption agent to be 20 L.m-2·h-1。
In this example, the removal rate of Zn in step B was 99.5%, i.e. the remaining Zn concentration was 0.17 mg/L, the removal rate of TOC was about 57%, and the recovery rate of Zn in step C was 96%.
Example 5
In the method for complex breaking and heavy metal synchronous recovery of heavy metal-organic acid composite wastewater, 5.0 mmol/L Cd-EDTA composite wastewater is tested, and membranes loaded by a composite membrane system are a PVDF composite membrane with the mass concentration of 5% ZIF-8 and the mass concentration of 5% MIL-66. The method comprises the following steps:
A. administration: adding potassium persulfate into the Cd-EDTA composite wastewater, wherein the mass concentration of the potassium persulfate in the composite wastewater after full stirring is 10%;
B. breaking collaterals-adsorption: pumping the solution uniformly stirred in the step A into a composite membrane system, carrying out broken-channel adsorption on the wastewater, and controlling the filtering flow rate of the wastewater to be 300 L.m-2·h-1。
C. And (3) recovering heavy metals: after the reaction in the step B is finished, pumping 100mL of dilute sulfuric acid solution with the mass concentration of 25% into the composite membrane system, recovering heavy metals adsorbed on the composite membrane, and controlling the flow rate of the desorption agent to be 5 L.m-2·h-1。
Through detection, in the embodiment, the removal rate of Cd in the step B is 99.4%, namely the concentration of the remaining Cd is 3.1 mg/L, the removal rate of TOC is about 61%, and the recovery rate of Zn in the step C is 93%.
Example 6
In the method for complex breaking and heavy metal synchronous recovery of heavy metal-organic acid composite wastewater of the embodiment, 3.0 mmol/L Zn-OA composite wastewater is tested, and membranes loaded by a composite membrane system are PVDF composite membranes with the mass concentration of 2% UiO-66 and the mass concentration of 8% MIL-66. The method comprises the following steps:
A. administration: adding potassium persulfate into the Zn-OA composite wastewater, wherein the mass concentration of the potassium persulfate in the composite wastewater after full stirring is 8%;
B. breaking collaterals-adsorption: pumping the solution uniformly stirred in the step A into a composite membrane system, carrying out broken-network adsorption on the wastewater, and controlling the filtering flow rate of the wastewater to be 150 L.m-2·h-1。
C. And (3) recovering heavy metals: after the reaction in the step B is finished, pumping 80mL of thick matter into the composite membrane systemRecovering heavy metal adsorbed on the composite membrane by using dilute hydrochloric acid solution with the temperature of 15%, and controlling the flow rate of desorption agent to be 5 L.m-2·h-1。
According to the detection, in the present embodiment, the Zn removal rate in step B is 97.3%, i.e. the remaining Zn concentration is 5.3 mg/L, the TOC removal rate is about 65%, and the recovery rate of Zn in step C is 94%.
Example 7
In the method for complex breaking and heavy metal synchronous recovery of heavy metal-organic acid composite wastewater of the embodiment, 2.0 mmol/L Cu-EDTA composite wastewater is tested, and a composite membrane system is loaded with ZIF-8 with the mass concentration of 2.5% and MIL-66-NH with the mass concentration of 1.5%2The PAN composite membrane of (1). The method comprises the following steps:
A. administration: adding potassium persulfate into the Cu-EDTA composite wastewater, wherein the mass concentration of the potassium persulfate in the composite wastewater after full stirring is 10%;
B. breaking collaterals-adsorption: pumping the solution uniformly stirred in the step A into a composite membrane system, carrying out broken-channel adsorption on the wastewater, and controlling the filtering flow rate of the wastewater to be 20 L.m-2·h-1。
C. And (3) recovering heavy metals: after the reaction in the step B is finished, pumping 60 mL of dilute nitric acid solution with the mass concentration of 5% into the composite membrane system, recovering heavy metals adsorbed on the composite membrane, and controlling the flow rate of the desorption agent to be 2 L.m-2·h-1。
According to the detection, in the embodiment, the Cu removal rate in the step B is 99.8%, that is, the remaining Cu concentration is 0.3 mg/L, the TOC removal rate is about 69%, and the recovery rate of Cu in the step C is 98%.
The above-mentioned embodiments are merely preferred embodiments of the present invention, and should not be construed as limiting the present invention, and the scope of the present invention should be defined by the claims, and equivalents including technical features of the claims, i.e., equivalent modifications within the scope of the present invention.
Claims (10)
1. A method for complex breaking and heavy metal synchronous recovery of heavy metal-organic acid composite wastewater is characterized by comprising the following steps:
(1) adding an oxidation compound agent into the heavy metal-organic acid complex wastewater and stirring;
(2) pumping the wastewater into a composite membrane system, and performing vein breaking adsorption on the wastewater;
(3) and (3) after the reaction in the step (2) is finished, pumping the desorption agent into the composite membrane system, and recovering the heavy metal adsorbed on the composite membrane.
2. The method for synchronously recycling heavy metal-organic acid composite wastewater for complex breaking and heavy metal recovery according to claim 1, characterized by comprising the following steps: the oxidation composite medicament in the step (1) is any one or more of potassium persulfate and sodium persulfate.
3. The method for synchronously recycling heavy metal-organic acid composite wastewater for complex breaking and heavy metal recovery according to claim 1, characterized by comprising the following steps: after the oxidation composite reagent is added in the step (1), the mass concentration of the oxidation composite reagent in the heavy metal-organic acid complex wastewater is 0.1-10%.
4. The method for synchronously recycling heavy metal-organic acid composite wastewater for complex breaking and heavy metal recovery according to claim 1, characterized by comprising the following steps: and (3) loading MOF on the membrane matrix in the composite membrane system in the step (2).
5. The method for synchronously recycling heavy metal-organic acid composite wastewater through complex breaking and heavy metal recovery according to claim 4, characterized by comprising the following steps: in the step (2), the mass concentration of the MOF in the membrane substrate casting solution is 0.1-10%.
6. The method for synchronously recycling heavy metal-organic acid composite wastewater through complex breaking and heavy metal recovery according to claim 4, characterized by comprising the following steps: in the step (2), the membrane matrix is any one of polyvinylidene fluoride, polyethersulfone, polyacrylonitrile and polysulfone, and the MOF is ZIF-8, UiO-66 or UiO-66-NH2、MIL-66、MIL-66-NH2、MIL-101、MIL-101-NH2Any one or more ofAnd (4) seed preparation.
7. The method for synchronously recycling heavy metal-organic acid composite wastewater for complex breaking and heavy metal recovery according to claim 1, characterized by comprising the following steps: the flow rate of the wastewater introduced into the composite membrane system in the step (2) is 0.1-500 L.m-2·h-1。
8. The method for synchronously recycling heavy metal-organic acid composite wastewater for complex breaking and heavy metal recovery according to claim 1, characterized by comprising the following steps: in the step (3), the desorption agent is dilute nitric acid, dilute sulfuric acid or dilute hydrochloric acid.
9. The method for synchronously recycling heavy metal-organic acid composite wastewater through complex breaking and heavy metal recovery according to claim 8, characterized by comprising the following steps: the addition amount of the desorption agent in the step (3) is 10-100 mL; the mass concentration of the desorption agent is 0.5-30%; the flow rate of the desorption agent introduced into the composite membrane system is 0.1-100 L.m-2·h-1。
10. The method for synchronously recycling heavy metal-organic acid composite wastewater for complex breaking and heavy metal recovery according to claim 1, characterized by comprising the following steps: in the step (1), the heavy metal ions are any one of copper (II), nickel (II), cadmium (II), zinc (II) and chromium (III), and the organic acid in the step (1) is any one of citric acid, tartaric acid, oxalic acid and ethylenediamine tetraacetic acid.
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