CN109231638B - Lead zinc oxide ore dressing wastewater treatment and recycling device and method thereof - Google Patents
Lead zinc oxide ore dressing wastewater treatment and recycling device and method thereof Download PDFInfo
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- JQJCSZOEVBFDKO-UHFFFAOYSA-N lead zinc Chemical compound [Zn].[Pb] JQJCSZOEVBFDKO-UHFFFAOYSA-N 0.000 title claims abstract description 109
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 73
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 238000004064 recycling Methods 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 36
- 238000004065 wastewater treatment Methods 0.000 title claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 402
- 238000001223 reverse osmosis Methods 0.000 claims abstract description 224
- 239000002351 wastewater Substances 0.000 claims abstract description 57
- 239000012528 membrane Substances 0.000 claims abstract description 54
- 230000003647 oxidation Effects 0.000 claims abstract description 46
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 46
- 238000000926 separation method Methods 0.000 claims abstract description 41
- 238000002425 crystallisation Methods 0.000 claims abstract description 33
- 230000008025 crystallization Effects 0.000 claims abstract description 33
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000001704 evaporation Methods 0.000 claims abstract description 28
- 239000005083 Zinc sulfide Substances 0.000 claims abstract description 23
- 229910052984 zinc sulfide Inorganic materials 0.000 claims abstract description 23
- 230000008020 evaporation Effects 0.000 claims abstract description 22
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 14
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 14
- 239000007788 liquid Substances 0.000 claims abstract description 7
- 150000003839 salts Chemical class 0.000 claims abstract description 6
- 239000011734 sodium Substances 0.000 claims description 58
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 35
- 239000010802 sludge Substances 0.000 claims description 35
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 33
- 238000000108 ultra-filtration Methods 0.000 claims description 22
- 238000001556 precipitation Methods 0.000 claims description 20
- 238000004519 manufacturing process Methods 0.000 claims description 19
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 18
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 16
- 238000005456 ore beneficiation Methods 0.000 claims description 12
- 238000004062 sedimentation Methods 0.000 claims description 11
- 238000007599 discharging Methods 0.000 claims description 10
- 230000008719 thickening Effects 0.000 claims description 9
- 239000003814 drug Substances 0.000 claims description 8
- 239000000701 coagulant Substances 0.000 claims description 7
- 230000002829 reductive effect Effects 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 238000005516 engineering process Methods 0.000 claims description 3
- 239000007800 oxidant agent Substances 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- 229940079593 drug Drugs 0.000 claims 4
- 238000002848 electrochemical method Methods 0.000 claims 1
- 238000013461 design Methods 0.000 abstract description 5
- 239000011575 calcium Substances 0.000 description 27
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 14
- 229910052938 sodium sulfate Inorganic materials 0.000 description 14
- 235000011152 sodium sulphate Nutrition 0.000 description 14
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 13
- 238000009303 advanced oxidation process reaction Methods 0.000 description 13
- 229910001424 calcium ion Inorganic materials 0.000 description 13
- -1 SALT SALT Chemical class 0.000 description 10
- 229910052979 sodium sulfide Inorganic materials 0.000 description 8
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 8
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 7
- 229910052791 calcium Inorganic materials 0.000 description 7
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 6
- 239000012141 concentrate Substances 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- 238000011001 backwashing Methods 0.000 description 4
- TUZCOAQWCRRVIP-UHFFFAOYSA-N butoxymethanedithioic acid Chemical compound CCCCOC(S)=S TUZCOAQWCRRVIP-UHFFFAOYSA-N 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 235000010755 mineral Nutrition 0.000 description 3
- 238000005065 mining Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910000365 copper sulfate Inorganic materials 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- OSVXSBDYLRYLIG-UHFFFAOYSA-N dioxidochlorine(.) Chemical compound O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 description 2
- 238000005188 flotation Methods 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229920002401 polyacrylamide Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 description 2
- 229960001763 zinc sulfate Drugs 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000004155 Chlorine dioxide Substances 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 235000019398 chlorine dioxide Nutrition 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000013067 intermediate product Substances 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
- 238000010979 pH adjustment Methods 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D5/00—Sulfates or sulfites of sodium, potassium or alkali metals in general
-
- 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
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
-
- 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
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
-
- 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
- C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
-
- 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
- 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
- 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
- C02F2001/007—Processes including a sedimentation step
-
- 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
- C02F2103/10—Nature of the water, waste water, sewage or sludge to be treated from quarries or from mining activities
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2301/00—General aspects of water treatment
- C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Water Treatment By Sorption (AREA)
Abstract
The invention relates to a device and a method for treating and recycling lead-zinc oxide ore dressing wastewater, which mainly aims at the characteristics of lead-zinc oxide ore dressing wastewater, namely high pH value and high Ca value 2+ High S 2‑ The design of high COD is carried out by firstly adding LCO in a pretreatment section 2 (liquid carbon dioxide) lowering pH and removing Ca 2+ And then S is removed by using an advanced oxidation device and a membrane separation device 2‑ And COD; secondly, concentrating and reducing by using a twice reverse osmosis device in a concentrating section; finally producing Na in the evaporation crystallization section by utilizing an evaporation crystallization system 2 SO 4 . Reverse osmosis produced water and condensed water are recycled to lead-zinc sulfide ore dressing at the front end, na 2 SO 4 For producing Na 2 S, not only solves the problem of treatment and reuse of the lead zinc oxide ore dressing wastewater, but also forms better recycling of water and salt.
Description
Technical Field
The invention relates to a lead-zinc oxide ore dressing wastewater treatment and recycling device and a method thereof, belonging to the technical field of industrial wastewater treatment.
Background
Lead zinc sulfide ore is the main lead zinc ore in the lead zinc ore resources in China, but a large amount of lead zinc oxide ore exists. In partial mining areas, a large amount of lead-zinc oxide ore stripped on the ground surface or the left lead-zinc oxide ore in the lead-zinc ore mining process is piled up, so that the environment is influenced, and meanwhile, the resource waste is caused. For lead zinc ore, the lead zinc ore is generally selected according to the lead zinc ore sulfide when the oxidation rate is less than 10%, the lead zinc ore is selected according to the lead zinc ore oxide when the oxidation rate is more than 85%, and the lead zinc resource recovery rate is improved as much as possible by adopting a method of firstly selecting the lead zinc ore sulfide and then selecting the lead zinc ore oxide when the oxidation rate is between 10 and 85%.
The lead zinc oxide ore has high ore dressing difficulty and poor ore dressing index, and a large amount of Na is added in the ore dressing process 2 S (sodium sulfide) is difficult to treat in beneficiation wastewater. The current common lead zinc ore dressing wastewater treatment method comprises the following steps: "adding H 2 SO 4 (sulfuric acid) adjusting pH, adding Alumen for coagulation, adding Na 2 CO 3 (sodium carbonate) for removing calcium, adding PAC (powdered activated carbon) for adsorbing the organic mineral separation agent, and recycling the precipitated water; for example, the patent 201010244646.6 discloses a method for treating and recycling lead-zinc sulfide ore dressing wastewater, which mainly comprises the process of adding H 2 SO 4 (sulfuric acid) pH adjustment, feSO 4 (ferrous sulfate) oxidation, PAM (polyacrylamide) flocculation, precipitation, clO 2 (chlorine dioxide) oxidation, activated carbon bed or porous ceramsite catalytic oxidation adsorption "; the operation cost is high, and the treatment effect is poor. The existing patent 201610953502.5 discloses a method for recycling the lead zinc oxide ore dressing wastewater, which is directly aimed at the treatment of the lead zinc oxide ore dressing wastewater, and the technology is 'precipitation treatment and recycling by an alkaline flocculant', because Na is not removed well 2 S can only be partially used for the internal recycle of lead zinc oxide ores, but cannot return to the ore dressing of the lead zinc sulfide ores. At present, the development of a method for comprehensively reducing pH, removing calcium and Na is needed 2 S, treating and recycling the lead-zinc oxide ore beneficiation wastewater from which the organic beneficiation reagent is removed.
Disclosure of Invention
The invention provides a lead zinc oxide ore dressing wastewater treatment and recycling device and a method thereof, which aim at simple treatment and internal recycling of lead zinc sulfide ore dressing wastewater by a traditional method when lead zinc oxide ore with high oxidation rate is firstly selected and then selected, and lead zinc oxide ore dressing wastewater is treated by a pretreatment system PTS, a reverse osmosis device ROS, a reverse osmosis concentrated water treatment system CWTS, a concentrated water reverse osmosis device ROCS and an evaporation crystallization device MVR (mechanical steam recompression) and recycled to the front end of the sulfideAnd (3) beneficiation of lead zinc ore. pH of lead zinc oxide ore dressing wastewater before treatment: 9-13, the pH of the treated effluent: 6 to 8; lead zinc oxide ore dressing wastewater Ca before treatment 2+ ：100～750mg/L、S 2- ：300～1000mg/L、TDS：4000～10000mg/L、COD Cr : 500-2500 mg/L, and treated effluent Ca 2+ ≤5mg/L、S 2- ≤1mg/L、TDS≤100mg/L、COD Cr The removal rate is less than or equal to 10mg/L and respectively reaches Ca 2+ ：95～99%、S 2- ：99.7～99.9%、TDS：97.5～99%、COD Cr : 98-99.6. The method not only solves the treatment difficulty of lead zinc oxide ore dressing wastewater, the treated water meets the dressing requirement of lead zinc sulfide ore, but also returns the treated water to a front-end lead zinc sulfide ore dressing system, thereby achieving the purpose of saving water; at the same time, evaporate crystallized Na 2 SO 4 (sodium sulfate) can also be sold back to Na 2 S production unit for Na 2 S production, offset part of Na 2 S, the purchase cost is environment-friendly and economical, the lead zinc oxide ore dressing wastewater is treated, and the guarantee is provided for the development of enterprises.
The technical solution of the invention is as follows: the device for treating and recycling the lead zinc oxide ore dressing wastewater structurally comprises a pretreatment system PTS, a reverse osmosis device ROS, a reverse osmosis concentrated water treatment system CWTS, a concentrated water reverse osmosis device ROCS, an evaporation crystallization device MVR, a reverse osmosis water producing tank PWT and a sludge discharging tank SWT; the method comprises the steps that lead zinc oxide ore beneficiation wastewater WW is connected with a water inlet of a pretreatment system PTS, a water outlet of the pretreatment system PTS is connected with a water inlet of a reverse osmosis device ROS, a concentrated water outlet of the reverse osmosis device ROS is connected with a water inlet of a reverse osmosis concentrated water treatment system CWTS, a water outlet of the reverse osmosis concentrated water treatment system CWTS is connected with a water inlet of a concentrated water reverse osmosis device ROCS, a concentrated water outlet of the concentrated water reverse osmosis device ROCS is connected with a water inlet of an evaporation crystallization device MVR, and the evaporation crystallization device MVR produces crystal SALT SALT (sodium sulfate); the water outlet of the reverse osmosis device ROS, the water outlet of the concentrated water reverse osmosis device ROCS and the condensate water outlet of the evaporation crystallization device MVR are respectively connected with the water inlets No. 1, no. 2 and No. 3 of the reverse osmosis water producing tank PWT, and the reverse osmosis water producing tank PWT sends out reverse osmosis water and evaporation crystallization condensate water PW to be recycled for lead zinc sulfide ore dressing; the sludge discharge port of the pretreatment system PTS and the sludge discharge port of the reverse osmosis concentrated water treatment system CWTS are respectively connected with the No. 1 and No. 2 sludge inlet ports of the sludge discharge water tank SWT, and the sludge discharge water tank SWT sends out sludge discharge water SW to the tailing thickening tank.
The treatment and recycling of the lead zinc oxide ore dressing wastewater are to achieve the purposes of reducing pH, removing calcium and removing Na 2 S, reducing COD (chemical oxygen demand), removing organic mineral processing agent, concentrating, evaporating and crystallizing to obtain water and condensed water, recycling, crystallizing Na 2 SO 4 Is reused for producing Na 2 S, the purpose of treating and recycling the lead-zinc oxide ore dressing wastewater and comprehensively recycling the wastewater is achieved, and the maximum benefit of environmental protection engineering is formed.
Aiming at the characteristics of high calcium and high pH of lead zinc oxide ore dressing wastewater for reducing pH and removing calcium, the most ideal method for reducing pH and removing calcium is to add LCO 2 (liquid carbon dioxide) and Ca (OH) in wastewater 2 (calcium hydroxide) reaction to produce CaCO 3 (calcium carbonate) and H 2 O (water). Simultaneous precipitation of Ca 2+ (calcium ions), lowering pH, and lowering TDS (total dissolved solids). The main chemical reaction equation is as follows:
CO 2 (g) ←→ CO 2 (l) ①
CO 2 (l) + OH - ←→ HCO 3 - ②
HCO 3 - + OH - ←→ CO 3 2- + H 2 O ③
Ca 2+ + CO 3 2- = CaCO 3 (s) ④
wherein (g) represents a gaseous state, (l) represents a liquid state, and(s) represents a solid state.
Generally, the conventional method for removing calcium is to add Na 2 CO 3 (sodium carbonate) forms CaCO 3 Precipitation, because sodium carbonate is expensive, 2 Na + Ion to 1 Ca 2+ The ions are heavy, so that the operation cost is high, and the TDS and the pH value of water are increased. The chemical reaction equation is as follows:
Na 2 CO 3 (l) + Ca(OH) 2 (l) = CaCO 3 (s) + 2NaOH(l) ⑤
for removing Na 2 S, reducing COD, removing organic mineral processing reagent, na 2 S is an important reducing agent, which forms a high COD (chemical oxygen demand) with organic beneficiation chemicals. Na (Na) 2 S is also a strong alkali weak acid salt, and can be used for vulcanizing (activating) lead zinc oxide ore, inhibiting various sulfides, regulating ion components of ore pulp and Na 2 The S is put into water to generate hydrolysis reaction. Na (Na) 2 The reaction equation for S hydrolysis is as follows:
Na 2 S = 2Na + + S 2- ⑥
Na 2 S + H 2 O = NaOH + NaHS ⑦
S 2- + H 2 O ←→ OH - + HS - ⑧
HS - + H 2 O ←→ OH - + H 2 S(g) ⑨
the equilibrium of equations (8), (9) is shifted to the right at low pH, giving off H 2 S (hydrogen sulfide) gas, and at high pH, is converted to the left, at this time, the water mainly contains S 2- (Sulfur ions), HS - (sulfhydryl ion).
Na 2 S is reducing and can use various oxidants such as O 2 (oxygen), H 2 O 2 (Hydrogen peroxide), naClO (sodium hypochlorite), HO (hydroxyl radical), O (active oxygen) oxidation S 2- (sulfide ions). Of course, the strongest oxidants here are HO (hydroxyl radical), O (active oxygen), which can be electrochemically generated to oxidize S 2- (sulfide ions) and organic beneficiation reagents. S is S 2- The oxidized intermediate products are S (elemental sulfur), SO 3 2- (sulfite ion), S 2 O 3 2- (thiosulfate ions). Will finally S 2- (Sulfur ion) oxidation to SO 4 2- (sulfate ions). Na in lead zinc oxide ore dressing wastewater 2 S (sodium sulfide) is totally oxidized into Na 2 SO 4 (sodium sulfate) oxidation of organic beneficiation reagent to CO 2 (carbon dioxide) and H 2 O (water). S is S 2- The oxidation equation for (sulfide ion) is as follows:
[O] [O]
S 2- ---→ S、SO 3 2- 、S 2 O 3 2- ---→ SO 4 2- ⑩
Na 2 SO 4 (sodium sulfate) Na can be produced by a method of reducing and roasting by adding C (carbon) 2 S (sodium sulfide). Na (Na) 2 SO 4 The (sodium sulfate) reduction reaction equation is as follows:
Na 2 SO 4 + 2C = Na 2 S + 2CO 2 (g) -49Kcal ⑪
Na 2 SO 4 + 4C = Na 2 S + 4CO(g) -129Kcal ⑫
Na 2 SO 4 + 4CO(g) = Na 2 S + 4CO 2 (g) +31Kcal ⑬
for concentrating, evaporating and crystallizing, ca is removed by a reverse osmosis device 2+ (calcium ion) and S 2- Concentrating (sulfur ions), pH-lowering and COD-lowering lead zinc oxide ore dressing wastewater, and concentrating sodium sulfate and Ca due to reverse osmosis of concentrated water 2+ (calcium ions) and COD are concentrated, so that Ca is reduced again by using a reverse osmosis concentrated water treatment system 2+ (calcium ions) and COD to ensure lower Ca for further concentration and evaporative crystallization 2+ (calcium ion) and COD concentration. And concentrating and reducing by using a concentrated water reverse osmosis device, and finally concentrating the lead zinc oxide ore dressing wastewater by 12-32 times. Then the evaporation crystallization device is utilized to carry out evaporation crystallization to produce Na 2 SO 4 (sodium sulfate). Water production of reverse osmosis device, water production of concentrated water reverse osmosis device and evaporative crystallization deviceThe condensed water is recycled to the beneficiation of lead zinc sulfide ore.
The method for treating and recycling the lead zinc oxide ore dressing wastewater comprises the following steps:
(1) Pretreatment: the lead zinc oxide ore dressing wastewater passes through a pretreatment system and LCO is added 2 (liquid carbon dioxide) reducing the pH from 9 to 13 to 6 to 8 and removing Ca 2+ (calcium ion) and S is removed by a pretreatment system advanced oxidation device and a pretreatment system membrane separation device 2- (sulfide ion) and COD;
(2) And (3) performing reverse osmosis primary concentration treatment: preliminary concentrating pretreated lead zinc oxide ore dressing wastewater by a reverse osmosis device, and concentrating TDS (main component is Na 2 SO 4 ) Concentrating from 4000-10000 mg/L to 26600-66700 mg/L;
(3) Reverse osmosis concentrated water treatment: through a reverse osmosis concentrated water treatment system, na is added 2 CO 3 (sodium carbonate) and PAC (powdered activated carbon), and further removing Ca by utilizing a high-grade oxidation device of a reverse osmosis concentrated water treatment system and a membrane separation device of the reverse osmosis concentrated water treatment system 2+ (calcium ions) and COD; the sludge discharged by the pretreatment system and the reverse osmosis concentrated water treatment system is sent to a tailing thickening tank;
(4) And (3) reverse osmosis and concentration treatment of concentrated water: the effluent of the reverse osmosis concentrated water treatment system is re-concentrated and reduced by a concentrated water reverse osmosis device, and TDS (the main component is Na) 2 SO 4 ) Concentrating from 26600-66700 mg/L to 133000 ～ 180000mg/L;
(5) And (3) evaporating and crystallizing: production of Na by means of an evaporative crystallization device 2 SO 4 (sodium sulfate), returning Na 2 S (sodium sulfide) is recycled in a production plant; the condensed water of the reverse osmosis device and the concentrated water reverse osmosis device is recycled to the lead-zinc sulfide ore at the front end for beneficiation.
The invention has the advantages that the invention relates to a device and a method for treating and recycling lead-zinc oxide ore beneficiation wastewater, which mainly aims at the characteristics of lead-zinc oxide ore beneficiation wastewater, namely high pH and high Ca 2+ (calcium ion), high S 2- (Sulfur ions), high COD inLine design, firstly, adding LCO in the pretreatment section 2 (liquid carbon dioxide) lowering pH and removing Ca 2+ And then S is removed by using an advanced oxidation device and a membrane separation device 2- And COD; secondly, concentrating and reducing by using a twice reverse osmosis device in a concentrating section; finally producing Na in the evaporation crystallization section by utilizing an evaporation crystallization system 2 SO 4 (sodium sulfate). Reverse osmosis produced water and condensed water are recycled to lead-zinc sulfide ore dressing at the front end, na 2 SO 4 For producing Na 2 S, not only solves the problem of treatment and reuse of the lead zinc oxide ore dressing wastewater, but also forms better recycling of water and salt.
Drawings
FIG. 1 is a schematic diagram of the overall structure of a lead zinc oxide ore dressing wastewater treatment and recycling device.
WW in the figure 1 represents lead zinc oxide ore dressing wastewater, SALT represents crystal SALT (sodium sulfate), PW represents reverse osmosis produced water and evaporated crystal condensate water, and SW represents mud water; PTS represents a pretreatment system, ROS represents a reverse osmosis device, CWTS represents a reverse osmosis concentrate treatment system, ROCS represents a concentrate reverse osmosis device, MVR (mechanical vapor recompression) represents an evaporative crystallization device, PWT represents a reverse osmosis water production tank, and SWT represents a sludge discharge tank.
Fig. 2 is a schematic diagram of the overall structure of a pretreatment system of a lead zinc oxide ore dressing wastewater treatment and recycling device.
The PTS in FIG. 2 represents a preprocessing system; WW represents lead zinc oxide ore dressing wastewater, 1# SWTin represents a 1# water inlet of a sludge discharge water tank, and ROSin represents a water inlet of a reverse osmosis device; d (D) 1 Represents carbon dioxide/sodium carbonate/coagulant aid adding device, D 2 Means sulfuric acid and powder active carbon adding device, BT means raw water tank, ST means precipitation device and AOP 1 Represents advanced oxidation device and MSD of pretreatment system 1 Representing a pretreatment system membrane separation device, and PTWT representing a pretreatment water tank; p (P) 1 Representing the raw water pump, P 2 Represents an ultrafiltration membrane suction pump and P of a pretreatment system 3 Represents the water supply pump and P of the reverse osmosis device 4 Represents an ultrafiltration backwashing water pump and P of a pretreatment system 5 Representing the sediment device sludge pump.
FIG. 3 is a schematic diagram of the overall structure of the reverse osmosis concentrated water treatment system of the lead zinc oxide ore dressing wastewater treatment and recycling device.
CWTS in fig. 3 represents a reverse osmosis concentrate treatment system; ROSout represents the concentrate outlet of the reverse osmosis unit, ROCSin represents the concentrate inlet of the reverse osmosis unit, and 2#SWTin represents the 2#inlet of the mud discharge tank; d (D) 3 Represents sodium carbonate and powdered activated carbon adding device and CWT 1 Represents the water inlet tank and AOP of the reverse osmosis concentrated water treatment system 2 Represents advanced oxidation device and MSD of reverse osmosis concentrated water treatment system 2 Represents membrane separation device and CWT of reverse osmosis concentrated water treatment system 2 Indicating the water outlet tank of the reverse osmosis concentrated water treatment system; p (P) 6 Represents the water supply pump and P of the reverse osmosis concentrated water treatment system 7 Represents an ultrafiltration membrane suction pump and P of a reverse osmosis concentrated water treatment system 8 Represents the water supply pump and P of the dense water reverse osmosis device 9 The ultrafiltration backwashing water pump of the reverse osmosis concentrated water treatment system is shown.
FIG. 4 is a water quantity and water quality balance diagram of a lead zinc oxide ore dressing wastewater treatment and reuse device and a method embodiment thereof.
Detailed Description
Referring to fig. 1, the lead zinc oxide ore dressing wastewater treatment and recycling device structurally comprises a pretreatment system PTS, a reverse osmosis device ROS, a reverse osmosis concentrated water treatment system CWTS, a concentrated water reverse osmosis device ROCS, an evaporation crystallization device MVR, a reverse osmosis water production tank PWT and a sludge discharge tank SWT; the method comprises the steps that lead zinc oxide ore beneficiation wastewater WW is connected with a water inlet of a pretreatment system PTS, a water outlet of the pretreatment system PTS is connected with a water inlet of a reverse osmosis device ROS, a concentrated water outlet of the reverse osmosis device ROS is connected with a water inlet of a reverse osmosis concentrated water treatment system CWTS, a water outlet of the reverse osmosis concentrated water treatment system CWTS is connected with a water inlet of a concentrated water reverse osmosis device ROCS, a concentrated water outlet of the concentrated water reverse osmosis device ROCS is connected with a water inlet of an evaporation crystallization device MVR, and the evaporation crystallization device MVR produces crystal SALT SALT (sodium sulfate); the water outlet of the reverse osmosis device ROS, the water outlet of the concentrated water reverse osmosis device ROCS and the condensate water outlet of the evaporation crystallization device MVR are respectively connected with the water inlets No. 1, no. 2 and No. 3 of the reverse osmosis water producing tank PWT, and the reverse osmosis water producing tank PWT sends out reverse osmosis water and evaporation crystallization condensate water PW to be recycled for lead zinc sulfide ore dressing; the sludge discharge port of the pretreatment system PTS and the sludge discharge port of the reverse osmosis concentrated water treatment system CWTS are respectively connected with the No. 1 and No. 2 sludge inlet ports of the sludge discharge water tank SWT, and the sludge discharge water tank SWT sends out sludge discharge water SW to the tailing thickening tank.
Referring to FIG. 2, the pretreatment system PTS comprises a raw water tank BT, a precipitation device ST and an advanced oxidation device AOP of the pretreatment system 1 Membrane separation device MSD of pretreatment system 1 Pretreatment water tank PTWT, carbon dioxide/sodium carbonate/coagulant aid adding device D 1 Sulfuric acid and powdered activated carbon adding device D 2 Raw water pump P 1 Ultrafiltration membrane suction pump P of pretreatment system 2 Water supply pump P of reverse osmosis device 3 Ultrafiltration backwashing water pump P of pretreatment system 4 Sludge pump P of sedimentation device 5 The method comprises the steps of carrying out a first treatment on the surface of the Wherein the lead zinc oxide ore dressing wastewater WW is connected to the water inlet of the raw water tank BT, and the water outlet of the raw water tank BT passes through the raw water pump P 1 Is connected to the water inlet of the precipitation device ST, and the carbon dioxide/sodium carbonate/coagulant aid adding device D 1 The medicine outlet of the sedimentation device ST is connected with the medicine inlet of the sedimentation device ST, and the mud discharged by the sedimentation device ST passes through the mud discharge pump P of the sedimentation device 5 The water outlet of the sedimentation device ST is connected to the advanced oxidation device AOP of the pretreatment system 1 Is added with the sulfuric acid and the powdered activated carbon by the water inlet of the device D 2 Is connected with an advanced oxidation device AOP of a pretreatment system 1 Is arranged at the medicine inlet of the advanced oxidation device AOP of the pretreatment system 1 Is connected with a membrane separation device MSD of a pretreatment system 1 Is a water inlet of a membrane separation device MSD of a pretreatment system 1 Is also connected to the sludge discharge water tank 1# water inlet 1# SWTin, and the pretreatment system membrane separation device MSD 1 Is pumped by an ultrafiltration membrane of a pretreatment system 2 Is connected to the water inlet of the pretreatment water tank PTWT, and the backwash water outlet of the pretreatment water tank PTWT is ultrafiltered by a pretreatment system to backwash water pump P 4 Membrane separation device MSD connected with pretreatment system 1 The water outlet of the pretreatment water tank PTWT is supplied with water by a reverse osmosis device through a water pump P 3 Is connected to the reverseThe inlet ROSin of the infiltration device.
Referring to FIG. 3, the reverse osmosis concentrated water treatment system CWTS structurally comprises a water inlet tank CWT of the reverse osmosis concentrated water treatment system 1 Advanced oxidation device AOP of reverse osmosis concentrated water treatment system 2 Membrane separation device MSD of reverse osmosis concentrated water treatment system 2 CWT (continuous wave) of water outlet tank of reverse osmosis concentrated water treatment system 2 Sodium carbonate and powdered activated carbon adding device D 3 Water supply pump P of reverse osmosis concentrated water treatment system 6 Ultrafiltration membrane suction pump P of reverse osmosis concentrated water treatment system 7 Water supply pump P of concentrated water reverse osmosis device 8 Ultrafiltration backwashing water pump P of reverse osmosis concentrated water treatment system 9 The method comprises the steps of carrying out a first treatment on the surface of the Wherein the concentrated water outlet ROSout of the reverse osmosis device is connected to the water inlet tank CWT of the reverse osmosis concentrated water treatment system 1 Is arranged at the water inlet of the water inlet tank CWT of the reverse osmosis concentrated water treatment system 1 Water supply pump P of reverse osmosis concentrated water treatment system 6 High-grade oxidation device AOP connected to reverse osmosis concentrated water treatment system 2 Is arranged in the reverse osmosis concentrated water treatment system advanced oxidation device AOP 2 Is connected to a membrane separation device MSD of a reverse osmosis concentrated water treatment system 2 Is added with powdered activated carbon and sodium carbonate 3 Is connected with a membrane separation device MSD of a reverse osmosis concentrated water treatment system 2 Is arranged at the medicine inlet of a membrane separation device MSD of a reverse osmosis concentrated water treatment system 2 Is connected to the water outlet of the mud discharging water tank 2# water inlet 2# SWTin, and the membrane separation device MSD of the reverse osmosis concentrated water treatment system 2 Is pumped and sucked by an ultrafiltration membrane of a reverse osmosis concentrated water treatment system 7 CWT connected to water outlet tank of reverse osmosis concentrated water treatment system 2 Is arranged at the water inlet of the water outlet tank CWT of the reverse osmosis concentrated water treatment system 2 The backwash water pump P is ultrafiltered and backwashed through a reverse osmosis concentrated water treatment system at the backwash water outlet 9 Membrane separation device MSD connected to reverse osmosis concentrated water treatment system 2 Is backwashed water inlet of a reverse osmosis concentrated water treatment system water outlet tank CWT 2 Water supply pump P passing through concentrated water reverse osmosis device 8 Is connected with a water inlet ROCSin of the concentrated water reverse osmosis device.
The method for treating and recycling the lead zinc oxide ore dressing wastewater comprises the following steps:
(1) Pretreatment: the lead zinc oxide ore dressing wastewater passes through a pretreatment system and LCO is added 2 (liquid carbon dioxide) reducing the pH from 9 to 13 to 6 to 8 and removing Ca 2+ (calcium ion) and S is removed by a pretreatment system advanced oxidation device and a pretreatment system membrane separation device 2- (sulfide ion) and COD;
(2) And (3) performing reverse osmosis primary concentration treatment: preliminary concentrating pretreated lead zinc oxide ore dressing wastewater by a reverse osmosis device, and concentrating TDS (main component is Na 2 SO 4 ) Concentrating from 4000-10000 mg/L to 26600-66700 mg/L;
(3) Reverse osmosis concentrated water treatment: through a reverse osmosis concentrated water treatment system, na is added 2 CO 3 (sodium carbonate) and PAC (powdered activated carbon), and further removing Ca by utilizing a high-grade oxidation device of a reverse osmosis concentrated water treatment system and a membrane separation device of the reverse osmosis concentrated water treatment system 2+ (calcium ions) and COD; the sludge discharged by the pretreatment system and the reverse osmosis concentrated water treatment system is sent to a tailing thickening tank;
(4) And (3) reverse osmosis and concentration treatment of concentrated water: the effluent of the reverse osmosis concentrated water treatment system is re-concentrated and reduced by a concentrated water reverse osmosis device, and TDS (the main component is Na) 2 SO 4 ) Concentrating from 26600-66700 mg/L to 133000 ～ 180000mg/L;
(5) And (3) evaporating and crystallizing: production of Na by means of an evaporative crystallization device 2 SO 4 (sodium sulfate), returning Na 2 S (sodium sulfide) is recycled in a production plant; the condensed water of the reverse osmosis device and the concentrated water reverse osmosis device is recycled to the lead-zinc sulfide ore at the front end for beneficiation.
The lead zinc oxide ore dressing wastewater in the step (1) passes through a pretreatment system, specifically, the lead zinc oxide ore dressing wastewater sequentially passes through a raw water tank, a raw water pump, a precipitation device, a pretreatment system advanced oxidation device, a pretreatment system membrane separation device, a pretreatment system ultrafiltration membrane suction pump, a pretreatment water tank and a reverse osmosis device water supply pump until pretreated water is sent out to a water inlet of the reverse osmosis device; wherein the use is made of the apparatus for precipitation and pre-treatmentAdding carbon dioxide, sodium carbonate, coagulant aid, sulfuric acid and powdered activated carbon into a high-grade oxidation device of a treatment system respectively to reduce the pH value from 9-13 to 6-8, and removing Ca by precipitation 2+ (calcium ion) and oxidizing S by means of advanced oxidation apparatus of pretreatment system 2- (sulfide ion) and COD, and further removing Ca by using a pretreatment system membrane separation device 2+ (calcium ions) and COD. The mud discharged from the sedimentation device is discharged to a mud discharge water tank together with ultrafiltration backwash water of a membrane separation device of a pretreatment system through a mud discharge pump of the sedimentation device.
The step (2) is carried out preliminary concentration by a reverse osmosis device, specifically the pretreated effluent water sequentially passes through a reverse osmosis cartridge filter, a reverse osmosis high-pressure pump and a reverse osmosis device, and TDS (the main component is Na) 2 SO 4 ) Concentrating from 4000-10000 mg/L to 26600-66700 mg/L.
The step (3) is carried out by passing through a reverse osmosis concentrated water treatment system, in particular a concentrated water outlet ROSout of a reverse osmosis device, sequentially through a water inlet tank of the reverse osmosis concentrated water treatment system, a water supply pump of the reverse osmosis concentrated water treatment system, a high-grade oxidation device of the reverse osmosis concentrated water treatment system, a membrane separation device of the reverse osmosis concentrated water treatment system, an ultrafiltration membrane suction pump of the reverse osmosis concentrated water treatment system, a water outlet tank of the reverse osmosis concentrated water treatment system, and a water supply pump of the concentrated water reverse osmosis device until the water outlet of the reverse osmosis concentrated water treatment system is sent to a water inlet ROCSin of the concentrated water reverse osmosis device; wherein Na is added 2 CO 3 (sodium carbonate) and PAC (powdered activated carbon) and further removing Ca by utilizing advanced oxidation device of reverse osmosis concentrated water treatment system and membrane separation device of reverse osmosis concentrated water treatment system 2+ (calcium ions) and COD; and the sludge discharged by the pretreatment system and the reverse osmosis concentrated water treatment system is sent to a tailing thickening tank through a sludge discharge water tank.
The step (4) is carried out by passing through a concentrated water reverse osmosis device, in particular to the effluent of a reverse osmosis concentrated water treatment system, sequentially passing through a concentrated water reverse osmosis cartridge filter, a concentrated water reverse osmosis high-pressure pump and a concentrated water reverse osmosis device, re-concentrating and reducing the amount, and obtaining the TDS (the main component is Na 2 SO 4 ) Concentrating from 26600-66700 mg/L to 133000 ～ 180000mg/L.
The step (5) is to produce Na by an evaporation crystallization device, in particular to adopting MVR (mechanical vapor recompression) technology 2 SO 4 (sodium sulfate), returning Na 2 S (sodium sulfide) is recycled in a production plant; the quality of the condensed water of the water producing and evaporating crystallization devices of the reverse osmosis device and the concentrated water reverse osmosis device reaches TDS less than or equal to 100mg/L, COD Cr And the concentration of lead zinc sulfide ore recycled to the front end is less than or equal to 10 mg/L.
Examples
For 100 tens of thousands tons of piled lead zinc oxide ores, a lead zinc oxide ore dressing plant with 500 tons/day of raw ore treatment capacity is built in a lead zinc oxide ore dressing plant of a mining company, and the flotation adopts a dressing process of firstly selecting lead zinc sulfide ores and then selecting lead zinc oxide ores because the oxidation rate of the lead zinc oxide ores is 50-60 percent. Lime (CaO) and a small amount of sodium sulfide (Na) are mainly added in the flotation of lead zinc sulfide ore 2 S), zinc sulfate (ZnSO 4 ) Copper sulfate (CuSO) 4 ) Butyl xanthate (CH) 3 CH 2 CH 2 CH 2 OSSNa), ethionazide ((C) 2 H 5 ) 2 NCSSNa), nigrosine (C 6 H 5 NH) 2 PSSH) and the like, and the lead zinc sulfide ore dressing wastewater is simply treated by a traditional method and recycled in the section. While sodium sulfide (Na) is added in large quantity during the ore dressing of lead zinc oxide ore 2 S), and adding zinc sulfate (ZnSO) 4 ) Copper sulfate (CuSO) 4 ) Butyl xanthate (CH) 3 CH 2 CH 2 CH 2 OSSNa), ethionazide ((C) 2 H 5 ) 2 NCSSNa), nigrosine (C 6 H 5 NH) 2 PSSH), dodecylamine (C 12 H 27 N), and the like, the lead zinc oxide ore dressing wastewater is difficult to treat, and advanced treatment is needed to recycle the lead zinc sulfide ore dressing flow at the front end.
The main design parameters of the lead zinc sulfide ore dressing wastewater advanced treatment recycling system are as follows:
1) Design water inlet and outlet quality and quantity
The treatment capacity of lead zinc oxide ore dressing wastewater is designed: 1500T/D (62.5T/H);
and (3) designing the water reuse amount: 1431T/D (59.6T/H);
designing the mud discharge amount (mud content is 5%): 60T/D (2.5T/H);
designing sodium sulfate yield: 9T/D (0.375T/H).
The water quality of inlet water and outlet water is designed as follows:
the technological process for treating and recycling the lead zinc oxide ore dressing wastewater is designed as follows:
(1) the main process comprises the following steps:
(2) the mud discharging process comprises the following steps:
reaction sedimentation tank, MSD 1 MSD (MSD) 2 Is arranged, a mud discharging water tank, a mud discharging pump and a tailing thickening tank
(3) The water production process comprises the following steps:
RO device, condensate water of water and MVR of ROC device, RO water producing tank, recycling water pump, recycling lead-zinc sulfide ore dressing
Wherein AOP is an advanced oxidation process, MSD is a membrane separation device, RO is reverse osmosis, and ROC is concentrated water reverse osmosis.
2) Balance of water quantity and water quality
The balance of water quantity and water quality is shown in the water quantity and water quality balance diagram of the lead zinc oxide ore dressing wastewater treatment and recycling device and the method embodiment of the device in figure 4.
3) Main design parameters of system
Civil engineering:
one-layer arrangement of a comprehensive factory building: control room, distribution room and sinkStarch equipment and AOP device 1 、MSD 1 And raw water tank, middle water tank, backwash water drainage tank, RO water production tank and concentrate tank 1 Concentrated water tank 2 Concentrated water tank 3 ；
Comprehensive factory building two-layer setting: dosing chamber, RO device and AOP device 2 、MSD 2 ROC device.
The main equipment comprises:
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Claims (7)
1. the lead zinc oxide ore dressing wastewater treatment and recycling device is characterized by comprising a pretreatment system, a reverse osmosis device, a reverse osmosis concentrated water treatment system, a concentrated water reverse osmosis device, an evaporation crystallization device, a reverse osmosis water production tank and a sludge discharge tank; the water inlet of the pretreatment system is connected with lead zinc oxide ore dressing wastewater, the water outlet of the pretreatment system is connected with the water inlet of the reverse osmosis device, the concentrated water outlet of the reverse osmosis device is connected with the water inlet of the reverse osmosis concentrated water treatment system, the water outlet of the reverse osmosis concentrated water treatment system is connected with the water inlet of the concentrated water reverse osmosis device, the concentrated water outlet of the concentrated water reverse osmosis device is connected with the water inlet of the evaporation crystallization device, and the evaporation crystallization device produces crystalline salt; the water outlet of the reverse osmosis device, the water outlet of the concentrated water reverse osmosis device and the condensed water outlet of the evaporative crystallization device are respectively connected with a No. 1 water inlet, a No. 2 water inlet and a No. 3 water inlet of a reverse osmosis water production tank, and the reverse osmosis water production tank sends out reverse osmosis water and evaporative crystallization condensed water to be recycled to lead zinc sulfide ore dressing; the sludge discharge port of the pretreatment system and the sludge discharge port of the reverse osmosis concentrated water treatment system are respectively connected with a 1# sludge inlet and a 2# sludge inlet of a sludge discharge water tank, and the sludge discharge water tank sends out sludge discharge water to a tailing thickening tank;
the pretreatment system structurally comprises a raw water tank, a precipitation device, a pretreatment system advanced oxidation device, a pretreatment system membrane separation device, a pretreatment water tank, a carbon dioxide/sodium carbonate/coagulant aid adding device, a sulfuric acid and powder activated carbon adding device, a raw water pump, a pretreatment system ultrafiltration membrane suction pump, a reverse osmosis device water supply pump, a pretreatment system ultrafiltration backwash pump and a precipitation device sludge pump; the water inlet of the raw water tank is connected with lead zinc oxide ore dressing wastewater, the water outlet of the raw water tank is connected with the water inlet of the precipitation device through a raw water pump, the drug outlet of the carbon dioxide/sodium carbonate/coagulant aid adding device is connected with the drug inlet of the precipitation device, the mud discharging of the precipitation device is connected with the 1# water inlet of the mud discharging water tank through a mud discharging pump of the precipitation device, the water outlet of the precipitation device is connected with the water inlet of the advanced oxidation device of the pretreatment system, the drug outlet of the sulfuric acid and powder active carbon adding device is connected with the drug inlet of the advanced oxidation device of the pretreatment system, the water outlet of the advanced oxidation device of the pretreatment system is connected with the water inlet of the membrane separation device of the pretreatment system, the mud discharging of the membrane separation device of the pretreatment system is also connected with the 1# water inlet of the mud discharging water tank, the water outlet of the membrane separation device of the pretreatment system is connected with the water inlet of the pretreatment water tank through an ultrafiltration membrane suction pump of the pretreatment system, and the water outlet of the pretreatment water tank is connected with the water inlet of the reverse osmosis device through a reverse osmosis device;
the reverse osmosis concentrated water treatment system structurally comprises a reverse osmosis concentrated water treatment system water inlet tank, a reverse osmosis concentrated water treatment system advanced oxidation device, a reverse osmosis concentrated water treatment system membrane separation device, a reverse osmosis concentrated water treatment system water outlet tank, a sodium carbonate and powder activated carbon feeding device, a reverse osmosis concentrated water treatment system water supply pump, a reverse osmosis concentrated water treatment system ultrafiltration membrane suction pump, a concentrated water reverse osmosis device water supply pump and a reverse osmosis concentrated water treatment system ultrafiltration backwash pump; the water outlet of the reverse osmosis device is connected with the water inlet of the membrane separation device of the reverse osmosis concentrated water treatment system, the water outlet of the membrane separation device of the reverse osmosis concentrated water treatment system is connected with the water inlet of the 2# water outlet of the mud discharge tank through an ultrafiltration membrane suction pump of the reverse osmosis concentrated water treatment system, the water outlet of the water outlet tank of the reverse osmosis concentrated water treatment system is connected with the water inlet of the membrane separation device of the reverse osmosis concentrated water treatment system through a backwash pump of the reverse osmosis concentrated water treatment system, and the water outlet of the water outlet tank of the reverse osmosis concentrated water treatment system is connected with the water inlet of the reverse osmosis device through a backwash pump of the reverse osmosis concentrated water treatment system; the advanced oxidation device of the pretreatment system and the advanced oxidation device of the reverse osmosis concentrated water treatment system both generate a strong oxidant by an electrochemical method.
2. The method for treating and recycling the lead zinc oxide ore beneficiation wastewater by using the device for treating and recycling the lead zinc oxide ore beneficiation wastewater according to claim 1, which is characterized by comprising the following steps:
(1) Pretreatment: the lead zinc oxide ore dressing wastewater passes through a pretreatment system, the pH value is reduced from 9 to 13 to 6 to 8 by using liquid carbon dioxide, and Ca is removed 2+ Meanwhile, S is removed by utilizing a high-grade oxidation device of the pretreatment system and a membrane separation device of the pretreatment system 2- And COD;
(2) And (3) performing reverse osmosis primary concentration treatment: preliminary concentrating the pretreated lead zinc oxide ore dressing wastewater by a reverse osmosis device, wherein the main component of the wastewater is Na 2 SO 4 The TDS of (2) is concentrated from 4000-10000 mg/L to 26600-66700 mg/L;
(3) Reverse osmosis concentrated water treatment: through a reverse osmosis concentrated water treatment system, na is added 2 CO 3 And powdered activated carbon, and further removing Ca by utilizing a high-grade oxidation device of the reverse osmosis concentrated water treatment system and a membrane separation device of the reverse osmosis concentrated water treatment system 2+ And COD; the sludge discharged by the pretreatment system and the reverse osmosis concentrated water treatment system is sent to a tailing thickening tank;
(4) And (3) reverse osmosis and concentration treatment of concentrated water: the effluent of the reverse osmosis concentrated water treatment system is re-concentrated and reduced by a concentrated water reverse osmosis device, and the TDS is concentrated from 26600 mg/L to 66700mg/L to 133000 ～ 180000mg/L;
(5) And (3) evaporating and crystallizing: production of Na by means of an evaporative crystallization device 2 SO 4 Back feeding Na 2 S, recycling in a production factory; the condensed water of the reverse osmosis device and the concentrated water reverse osmosis device is recycled to the lead-zinc sulfide ore at the front end for beneficiation.
3. The method for treating and recycling the lead-zinc oxide ore beneficiation wastewater according to claim 2, wherein the step (1) is characterized in that the lead-zinc oxide ore beneficiation wastewater sequentially passes through a raw water tank, a raw water pump, a precipitation device, a pretreatment system advanced oxidation device, a pretreatment system membrane separation device, a pretreatment system ultrafiltration membrane suction pump, a pretreatment water tank and a reverse osmosis device water supply pump until pretreated water is sent out to a water inlet of the reverse osmosis device; wherein, carbon dioxide, sodium carbonate, coagulant aid, sulfuric acid and powdered activated carbon are respectively added into a precipitation device and a high-grade oxidation device of a pretreatment system to reduce the pH value from 9 to 13 to 6 to 8, and Ca is removed by precipitation 2+ And oxidizing S by using advanced oxidation device of pretreatment system 2- And COD, and further removing Ca by utilizing a membrane separation device of a pretreatment system 2+ And COD; the mud discharged from the sedimentation device is discharged to a mud discharge water tank together with ultrafiltration backwash water of a membrane separation device of a pretreatment system through a mud discharge pump of the sedimentation device.
4. The method for treating and recycling the lead-zinc oxide ore beneficiation wastewater, which is characterized in that the step (2) is reverse osmosis preliminary concentration treatment, specifically, the pretreated effluent is subjected to preliminary concentration sequentially through a reverse osmosis cartridge filter, a reverse osmosis high-pressure pump and a reverse osmosis device, and the TDS of the pretreated effluent is concentrated from 4000 to 10000mg/L to 26600 to 66700mg/L.
5. The method for treating and recycling the lead-zinc oxide ore beneficiation wastewater is characterized in that the step (3) is reverse osmosis concentrated water treatment, and particularly concentrated water outlet of a reverse osmosis device sequentially passes through a water inlet tank of a reverse osmosis concentrated water treatment system, a water supply pump of the reverse osmosis concentrated water treatment system, a high-grade oxidation device of the reverse osmosis concentrated water treatment system, a membrane separation device of the reverse osmosis concentrated water treatment system, an ultrafiltration membrane suction pump of the reverse osmosis concentrated water treatment system, a water outlet tank of the reverse osmosis concentrated water treatment system and a water supply pump of the concentrated water reverse osmosis device until the water outlet of the reverse osmosis concentrated water treatment system is sent to a water inlet of the concentrated water reverse osmosis device; wherein Na is added 2 CO 3 And powdered activated carbon, and further removing Ca by utilizing a high-grade oxidation device of the reverse osmosis concentrated water treatment system and a membrane separation device of the reverse osmosis concentrated water treatment system 2+ And COD; and the sludge discharged by the pretreatment system and the reverse osmosis concentrated water treatment system is sent to a tailing thickening tank through a sludge discharge water tank.
6. The method for treating and recycling the lead-zinc oxide ore beneficiation wastewater is characterized in that the concentrated water in the step (4) is subjected to reverse osmosis and re-concentration treatment, and particularly the effluent of a reverse osmosis concentrated water treatment system is subjected to re-concentration and decrement by a concentrated water reverse osmosis security filter, a concentrated water reverse osmosis high-pressure pump and a concentrated water reverse osmosis device in sequence, so that the TDS is concentrated from 26600 mg/L to 66700mg/L to 133000 ～ 180000mg/L.
7. The method for treating and recycling lead zinc oxide ore dressing wastewater according to claim 2, wherein the step (5) is an evaporative crystallization treatment, in particular to a Mechanical Vapor Recompression (MVR) technology, and Na is produced by an evaporative crystallization device 2 SO 4 Back feeding Na 2 S, recycling in a production factory; the quality of the condensed water of the reverse osmosis device and the produced water of the concentrated water reverse osmosis device and the evaporation crystallization device reaches TDS less than or equal to 100mg/L,COD Cr And the concentration of lead zinc sulfide ore recycled to the front end is less than or equal to 10 mg/L.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811411587.XA CN109231638B (en) | 2018-11-24 | 2018-11-24 | Lead zinc oxide ore dressing wastewater treatment and recycling device and method thereof |
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