CN111018221B - Method for recycling smelting waste acid wastewater - Google Patents
Method for recycling smelting waste acid wastewater Download PDFInfo
- Publication number
- CN111018221B CN111018221B CN201911356731.9A CN201911356731A CN111018221B CN 111018221 B CN111018221 B CN 111018221B CN 201911356731 A CN201911356731 A CN 201911356731A CN 111018221 B CN111018221 B CN 111018221B
- Authority
- CN
- China
- Prior art keywords
- microfiltration
- acid
- waste acid
- nanofiltration
- wastewater
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000002253 acid Substances 0.000 title claims abstract description 104
- 238000000034 method Methods 0.000 title claims abstract description 62
- 239000002699 waste material Substances 0.000 title claims abstract description 55
- 239000002351 wastewater Substances 0.000 title claims abstract description 42
- 238000003723 Smelting Methods 0.000 title claims abstract description 40
- 238000004064 recycling Methods 0.000 title claims abstract description 24
- 238000001471 micro-filtration Methods 0.000 claims abstract description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000001728 nano-filtration Methods 0.000 claims abstract description 28
- 238000001704 evaporation Methods 0.000 claims abstract description 23
- 230000008020 evaporation Effects 0.000 claims abstract description 20
- 238000011282 treatment Methods 0.000 claims abstract description 18
- 238000004073 vulcanization Methods 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 239000007788 liquid Substances 0.000 claims description 30
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 29
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 25
- 238000000746 purification Methods 0.000 claims description 23
- 239000012528 membrane Substances 0.000 claims description 22
- 239000000706 filtrate Substances 0.000 claims description 18
- 239000007789 gas Substances 0.000 claims description 15
- 239000010949 copper Substances 0.000 claims description 12
- -1 iron ions Chemical class 0.000 claims description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 10
- 229910052802 copper Inorganic materials 0.000 claims description 10
- 230000000694 effects Effects 0.000 claims description 10
- 229910052785 arsenic Inorganic materials 0.000 claims description 9
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 8
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 229910052793 cadmium Inorganic materials 0.000 claims description 6
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 229910052797 bismuth Inorganic materials 0.000 claims description 5
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 5
- 239000000084 colloidal system Substances 0.000 claims description 4
- 239000003921 oil Substances 0.000 claims description 4
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims description 3
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 3
- 229910001424 calcium ion Inorganic materials 0.000 claims description 3
- 229910000856 hastalloy Inorganic materials 0.000 claims description 3
- 229910001453 nickel ion Inorganic materials 0.000 claims description 3
- 238000005987 sulfurization reaction Methods 0.000 claims description 3
- 238000007664 blowing Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 15
- 239000002184 metal Substances 0.000 abstract description 15
- 150000002739 metals Chemical class 0.000 abstract description 12
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 11
- 238000000926 separation method Methods 0.000 abstract description 8
- 239000000377 silicon dioxide Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 238000011084 recovery Methods 0.000 description 9
- 239000000460 chlorine Substances 0.000 description 8
- 235000012239 silicon dioxide Nutrition 0.000 description 7
- 229910052731 fluorine Inorganic materials 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 239000002893 slag Substances 0.000 description 6
- 239000011701 zinc Substances 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 5
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 5
- 239000011575 calcium Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000011737 fluorine Substances 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 239000005083 Zinc sulfide Substances 0.000 description 2
- HXELGNKCCDGMMN-UHFFFAOYSA-N [F].[Cl] Chemical compound [F].[Cl] HXELGNKCCDGMMN-UHFFFAOYSA-N 0.000 description 2
- 239000012267 brine Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000011859 microparticle Substances 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 229910052979 sodium sulfide Inorganic materials 0.000 description 2
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- 239000002918 waste heat Substances 0.000 description 2
- 229910052984 zinc sulfide Inorganic materials 0.000 description 2
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- JQJCSZOEVBFDKO-UHFFFAOYSA-N lead zinc Chemical compound [Zn].[Pb] JQJCSZOEVBFDKO-UHFFFAOYSA-N 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000009287 sand filtration Methods 0.000 description 1
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/69—Sulfur trioxide; Sulfuric acid
- C01B17/88—Concentration of sulfuric acid
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/69—Sulfur trioxide; Sulfuric acid
- C01B17/90—Separation; Purification
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/69—Sulfur trioxide; Sulfuric acid
- C01B17/90—Separation; Purification
- C01B17/901—Recovery from spent acids containing metallic ions, e.g. hydrolysis acids, pickling acids
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/69—Sulfur trioxide; Sulfuric acid
- C01B17/90—Separation; Purification
- C01B17/907—Removal of arsenic
-
- 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
- C02F1/048—Purification of waste water by 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
- C02F1/20—Treatment of water, waste water, or sewage by degassing, i.e. liberation of dissolved gases
-
- 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
- C02F1/442—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
-
- 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
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
- C02F1/62—Heavy metal compounds
-
- 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
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
- C02F1/62—Heavy metal compounds
- C02F1/64—Heavy metal compounds of iron or manganese
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/203—Iron or iron compound
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Removal Of Specific Substances (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses a method for recycling smelting waste acid wastewater, which comprises the following steps: and carrying out vulcanization reaction, microfiltration, nanofiltration, evaporation concentration and stripping on the smelting waste acid wastewater to finish the resource treatment of the smelting waste acid wastewater. The method for recycling the smelting waste acid wastewater realizes the effective separation of acid, water, valuable metals and harmful heavy metals in the smelting wastewater and the recycling of the acid, the water and the valuable metals, has the advantages of simple process, convenient operation, low cost and the like, and has very high use value and good application prospect.
Description
Technical Field
The invention belongs to the technical field of waste acid recycling treatment, and relates to a method for recycling waste acid smelting wastewater.
Background
At present, heavy metals such as arsenic, copper and the like contained in smelting waste acid wastewater are generally removed by sodium sulfide vulcanization, and then a lime neutralization method is adopted to treat the vulcanized liquid, and the treatment method has the problems of large gypsum residue, serious waste of waste acid, incapability of realizing resource utilization of valuable metals in the wastewater and the like. Therefore, in combination with the defects of the conventional waste acid wastewater treatment process, through the development and application of the membrane technology, relevant scholars research the separation of acid in the waste acid wastewater by taking the membrane technology as a main body, solve the problem of slag neutralization and realize the recycling of the acid.
Patent CN101966400A discloses a method for separating inorganic acid from inorganic acid salt in waste acid, which comprises the steps of firstly removing salt and other soluble substances in the waste acid by adopting a resin desalter, separating clear acid from concentrated salt by using a nanofiltration membrane after reducing salinity of the original acid, and returning the concentrated acid salt to the resin desalter. The technology adopts an ion exchange resin method to purify the original waste acid solution, the washing process can cause the water expansion of the system to be doubled, and the water quantity of the system and the load pressure of water circulation are increased. In addition, the technology only introduces the realization of acid salt separation of the waste acid solution, but does not solve the problems of fluorine and chlorine contained in the separated purified acid solution, heavy metal arsenic and the like, and limits the recycling of the purified acid solution.
Patent CN108675502A proposes a method for recycling waste acid, which comprises the steps of firstly, deeply filtering the waste acid solution, obtaining trapped fluid and permeate liquid from the filtrate through a nanofiltration system, and then respectively carrying out vulcanization treatment: and carrying out evaporation concentration or hot blowing concentration removal on the obtained intermediate sulfuric acid product to obtain a concentrated sulfuric acid product. The technical method has the problems that the waste acid solution is directly subjected to nanofiltration after pretreatment, the permeation pressure of a nanofiltration system is increased due to the existence of heavy metal ions such as high-concentration arsenic, copper, lead, cadmium and the like in the solution, the recovery rate is low due to overhigh system pressure in the actual operation process, and the separation effect is poor; the technology explains a method for removing fluorine ions, but the problem of removing chlorine ions in a solution is not solved, and the market range of purified acid is restricted. The technical method is only limited to the application of the waste acid for disassembling the lead storage battery and the waste acid for pickling in a steel mill.
In addition, in the existing treatment method for the smelting waste acid wastewater, only the acid, water and valuable metals can be recovered independently, but a method for simultaneously recovering the acid, water and valuable metals in the smelting waste acid wastewater is not found. Therefore, aiming at the characteristics of complex heavy metal types, high acidity and high fluorine-chlorine ion concentration in the waste acid wastewater generated by non-ferrous metal smelting enterprises, the method for recycling the waste acid wastewater from smelting, which has the advantages of simple process, convenient operation and low cost and can simultaneously realize the recycling of acid, water and valuable metals, is provided, and has very important significance for the effective treatment of the waste acid wastewater from smelting and the recycling of important resources.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a method for recycling the waste acid-smelting wastewater, which has the advantages of simple process, convenient operation and low cost and can simultaneously realize the recycling of acid, water and valuable metals.
In order to solve the technical problems, the invention adopts the following technical scheme:
a method for recycling smelting waste acid wastewater comprises the following steps:
s1, introducing hydrogen sulfide gas into the smelting waste acid wastewater to perform a vulcanization reaction, and recovering arsenic, copper, lead, cadmium and bismuth in the smelting waste acid wastewater to obtain a vulcanized purified liquid;
s2, carrying out microfiltration on the vulcanized and purified liquid obtained in the step S1, and removing suspended matters, solid particles, colloids, organic matters and oil substances in the vulcanized and purified liquid to obtain microfiltration and purification filtrate;
s3, carrying out nanofiltration on the microfiltration purification filtrate obtained in the step S2, and recovering nickel ions, zinc ions, iron ions and calcium ions in the microfiltration purification filtrate to obtain a deep-purified liquid;
s4, evaporating and concentrating the deep purified liquid obtained in the step S3, and recovering condensed water to obtain concentrated acid;
s5, the concentrated acid obtained in the step S4 is subjected to air stripping, fluoride ions and chloride ions in the concentrated acid are removed, purified acid is obtained, and the resource treatment of the waste acid smelting wastewater is completed.
In the above method, in a further improvement, in step S2, the microfiltration module used in the microfiltration process uses carbon powder and silica powder as a substrate; the mass ratio of the carbon powder to the silicon dioxide powder is 6-7: 3-4.
The method is further improved, and the purity of the carbon powder is more than or equal to 99.9 percent; the purity of the silicon dioxide powder is more than or equal to 99.9 percent.
In the step S2, the operating pressure during the microfiltration process is controlled to be 0.1MPa to 0.3 MPa; the microfiltration time is 20 min-40 min.
In the step S2, the particle size of the solid in the microfiltration purification filtrate is reduced to below 0.1 micron and SDI is less than or equal to 5.
In the above method, further improvement, in step S1, the purity of the sulfuration gas is greater than or equal to 99.5%; the time of the sulfuration reaction is 15 min-20 min.
In the step S3, a hastelloy C3000 high-pressure plunger pump is used to deliver the microfiltration purified filtrate to the nanofiltration module; the nanofiltration membrane in the nanofiltration component is an acid-resistant membrane; the working pressure is controlled to be 4 MPa-6 MPa in the nanofiltration process; the nanofiltration time is 40 min-60 min.
In the step S4, the deep-purified liquid is evaporated and concentrated in a triple-effect forward-flow manner; the temperature of the first-effect evaporation in the evaporation concentration process is 125-130 ℃, and the gas phase pressure is 0.2 MPa; the temperature of the two-effect evaporation in the evaporation concentration process is 100-105 ℃, and the gas phase pressure is 0-0.05 MPa; the temperature of triple effect evaporation in the evaporation concentration process is 70-80 ℃, and the gas phase pressure is-0.01 MPa-0.08 MPa; the time of evaporation concentration is 6-8 h.
In a further improvement of the above method, in step S5, hot air at a temperature of 70-80 ℃ or tail gas generated in step S4 is used to blow off the concentrated acid; the stripping time is 1.5-2 h.
Compared with the prior art, the invention has the advantages that:
the invention provides a method for recycling smelting waste acid wastewater, which realizes effective recovery of acid, water and valuable metals in the smelting waste acid wastewater by sequentially carrying out treatments such as vulcanization reaction, microfiltration, nanofiltration, concentration evaporation, air stripping and the like, and completes recycling treatment of the smelting waste acid wastewater. According to the invention, firstly, hydrogen sulfide gas is adopted to replace the traditional sodium sulfide (or sodium hydrosulfide) to carry out enhanced vulcanization reaction with the waste acid water from smelting, so that heavy metals such as arsenic, copper, lead, cadmium, bismuth and the like in the waste acid water can be converted into sulfide precipitate substances, the recovery of heavy metals such as arsenic, copper, lead, cadmium, bismuth and the like in the waste acid water can be realized through filtering, the sulfide slag obtained through the recovery can be further treated to recover valuable metals, and in the vulcanization reaction process, according to the concentration and the economic value of metallic copper, the step-by-step vulcanization can be adopted to realize the step-by-step vulcanization precipitation of copper and arsenic, so that the independent open circuit recovery of copper is realized; meanwhile, the concentration of heavy metal ions in the vulcanized and purified liquid obtained after filtration is low, and the problem of overhigh pressure caused by the permeation of a membrane system in the subsequent deep purification and impurity removal process cannot be caused. In the invention, microfiltration is carried out on the vulcanized purified liquid obtained after the vulcanization reaction, so that suspended matters, solid particles, colloids, organic matters and oil substances in the vulcanized purified liquid can be effectively intercepted, and the vulcanized purified liquid is purified and filtered, wherein SDI in microfiltration purified filtrate obtained after microfiltration is less than or equal to 5, so that the pollution impact risk of the microfiltration purified filtrate on a subsequent membrane system is greatly reduced, and compared with conventional sand filtration, carbon filtration and ultrafiltration, the microfiltration adopted in the invention can realize solid-liquid separation in the physical sense, and can not cause the problem of water expansion of the system. In the invention, the microfiltration purification filtrate is subjected to nanofiltration, heavy metal ions (nickel, zinc, iron and calcium) which are not vulcanized and removed are effectively separated from the acid liquor, so that the problems of crystallization, scaling and blockage in the subsequent evaporation and concentration process are solved while the recovery of the heavy metal ions (nickel, zinc, iron and calcium) is realized. In the invention, the liquid after deep purification is evaporated and concentrated to realize the separation of acid and water, the acidity of the acid is further improved while the water is recovered, wherein the acidity is improved from 2-10% to 40-60%, and the obtained condensed water can be used as recycled water to return to a production system for use, thereby realizing the purpose of recycling the water. In the invention, the concentrated acid is subjected to stripping, and fluorine ions and chloride ions in the concentrated acid are converted into HF and HCl through stripping, so that the purified acid is obtained. The method for recycling the smelting waste acid wastewater realizes the effective separation of acid, water, valuable metals and harmful heavy metals in the smelting wastewater and the recycling of the acid, the water and the valuable metals, has the advantages of simple process, convenient operation, low cost and the like, and has very high use value and good application prospect.
Drawings
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention.
FIG. 1 is a process flow diagram of the resource treatment of the waste acid smelting wastewater in embodiment 1 of the invention.
Detailed Description
The invention is further described below with reference to the drawings and specific preferred embodiments of the description, without thereby limiting the scope of protection of the invention.
Example 1
A method for recycling smelting waste acid wastewater is shown in a process flow diagram in figure 1 and comprises the following steps:
s1, introducing hydrogen sulfide gas with the purity of 99.8% into the waste water of the smelting waste acid to carry out a vulcanization reaction, controlling the vulcanization reaction time to be 20min, and recovering arsenic, copper, lead, cadmium and bismuth in the waste water of the smelting waste acid to obtain a liquid after the vulcanization purification. The hydrogen sulfide gas is prepared by adopting hydrogen and sulfur in a synthesis reaction tower, wherein the reaction temperature is 450-470 ℃, and the pressure is within 0.7 Mpa; wherein the sulfur is a first-grade industrial sulfur product on the market, the purity is more than 99.5 percent, the hydrogen is prepared by adopting methanol or natural gas, and the hydrogen production process belongs to modular equipment.
In the step, the smelting waste acid water is waste acid water generated in the purification process of preparing acid from flue gas of a certain lead-zinc smelting plant, and the amount of the waste acid water is 200-300 m3The water quality components are as follows: 5000-10000 mg/L, Cu 10-20 mg/L, Pb 20-50 mg/L, Cd 50-200 mg/L, Zn 300-1000 mg/L, F500-2000 mg/L, Cl 500-500 mg/L, Ca 100-300 mg/L of As, and 3-5% of acidity.
In the step, the consumption of the hydrogen sulfide is 1.8t/d, the yield of the sulfide slag is 7.64t/d, and the yield of the liquid after the sulfide purification is 300m3/d。
S2, carrying out microfiltration on the vulcanized and purified liquid obtained in the step S1, wherein the operating pressure in the microfiltration process is 0.2MPa, the microfiltration time is 40min, and recovering suspended matters, solid particles, colloids, organic matters and oil substances in the vulcanized and purified liquid to obtain microfiltration and purification filtrate. The microfiltration component adopted in the microfiltration process comprises a cylindrical shell with the diameter of 40-80cm and the height of 90-150cm, and carbon/silicon dioxide mixed powder (the carbon/silicon dioxide mixed powder is prepared by mixing carbon powder and silicon dioxide powder, the mass ratio of the carbon powder to the silicon dioxide powder is 7: 3, and the purities of the carbon powder and the silicon dioxide powder are both 99.9%) which is resistant to acid, alkali and fluorine-chlorine corrosion is filled in the cylindrical shell. The concentrated water produced by the microfiltration is returned to the system for circular treatment, and the filtrate is sent to the next working section. The water yield of the working section is 70-80%. The particle size of the wastewater solid in the filtrate is reduced to be less than 0.1 micron, and the SDI is less than or equal to 5.
And S3, conveying the microfiltration purification filtrate obtained in the step S2 to a nanofiltration component for nanofiltration by adopting a Hastelloy C3000 high-pressure plunger pump (commercially available), wherein the nanofiltration time is 60min, and separating and removing nickel ions, zinc ions, iron ions and calcium ions in the microfiltration purification filtrate to obtain the liquid after deep purification. The nanofiltration component adopts an acid-resistant membrane (commercially available acid-resistant membrane is a combined component which comprises a membrane element and a membrane jacket and belongs to commercially available products, wherein the membrane element adopts a separation net and a polysulfone fitting, the membrane jacket is made of glass fiber reinforced plastic or epoxy resin, and all materials have reliable acid stability). The recovery rate of acid water (after deep purification) is about 85-90%; the removal rate of metals (concentrated salt solution) such as zinc, iron, calcium, magnesium and the like is kept above 95%. The Hardgrove alloy C3000 high-pressure plunger pump adopted in the step is used as a feeding pump for nanofiltration membrane treatment, so that the application range of the treated feed liquid is effectively expanded, and the high-acid wastewater purification treatment with the concentration of F ions less than or equal to 2000mg/L is met.
In the step, the working pressure of the nanofiltration system is 4-6 Mpa. The nanofiltration system adopts 2-stage series connection work. After nanofiltration treatment, the yield of the liquid after deep purification is 162m3D, the yield of the concentrated brine is 135m3And d. After the concentrated acid salt is treated by the metal recovery system, the yield of the zinc sulfide wet slag is 504.67 kg/d.
And S4, evaporating and concentrating the deep purified liquid obtained in the step S3 for 6 hours in a triple-effect forward flow mode, and recovering condensed water to obtain concentrated acid. Wherein, the evaporation temperature of the first effect, the second effect and the third effect is 130 ℃, 105 ℃ and 75 ℃ respectively; the gas phase pressure of the first effect, the second effect and the third effect is 0.2MPa, 0.03MPa and-0.05 MPa respectively. In this step, the production of condensed waterThe amount is 140m3/d。
S5, heating the air to 75 ℃ by adopting the waste heat generated in the evaporation concentration process in the step S4, then carrying out air stripping on the concentrated acid obtained in the step S4 for 2h by utilizing the heated air, recovering fluorine ions and chlorine ions in the concentrated acid to obtain purified acid, and completing the resource treatment of the smelting waste acid wastewater. Compared with the conventional method for heating air by using an external source, the method has the advantages that the waste heat in the treatment process is used for heating the air, so that the energy consumption is reduced, the operation cost is reduced, and the fluorine and chlorine removal cost is reduced by more than 30%. In this step, the yield of purified acid was 22.4m3The acidity was 41%, and the F content was 130mg/L, Cl and 170 mg/L.
In the present example, the influence of the mass ratio of different carbon powder and silica powder on the microfiltration effect was also examined, and except that the mass ratio of carbon powder and silica powder was different, the other conditions were the same as in example 1:
a first group: carbon powder (80% by mass), silicon dioxide (20% by mass).
Second group: carbon powder (60% by mass) and silicon dioxide (40% by mass).
Third group: carbon powder (50% by mass), silicon dioxide (50% by mass).
The experiment shows that: the mass ratio of the carbon powder is too high, so that the strength of the microfiltration membrane component is influenced, and the pressure resistance is reduced; when the mass percentage of the carbon powder is increased to be more than 70 percent, the strength of the membrane component is gradually reduced, for example, when the mass percentage of the carbon powder is 80 percent, the compressive strength is reduced by about 40 percent compared with that when the mass percentage of the carbon powder is 70 percent. In addition, when the mass ratio of the carbon powder is too low, the membrane gap of the microfiltration membrane component is enlarged, and the intercepted particle size of suspended solids and micro-particles is increased. When the mass percentage of the carbon powder is 60 percent and the mass percentage of the silicon dioxide is 40 percent, the effective interception grain size of the micro-filtration membrane is less than 0.1 micron, and when the mass percentage of the carbon powder is reduced to 50 percent and the mass percentage of the silicon dioxide is increased to more than 50 percent, the effective interception grain size of the micro-filtration membrane is increased to more than 0.5 micron. According to the experiment comparison, when the mass ratio of the carbon powder to the silicon dioxide powder in the microfiltration component adopted in the microfiltration process is 6-7: 3-4, the strength is good, and meanwhile, the suspended solids and the micro-particles in the wastewater can be effectively intercepted.
Example 2
The method for recycling the smelting waste acid wastewater is basically the same as the embodiment 1, and the difference is only that: different in smelting waste acid and waste water, wherein the smelting waste acid and waste water adopted in the embodiment 2 is the water discharged from the purification section of a sulfuric acid workshop of a certain zinc smelting plant, and the quantity of the waste acid and waste water is 260-330 m3The water quality components are as follows: 200-1000 mg/L, Cu 10-20 mg/L, Pb 30-50 mg/L, Cd 50-150 mg/L, Zn 300-500 mg/L, F300-1500 mg/L, Cl 300-1500 mg/L, Ca 200-500 mg/L of As, and 4-5% of acidity.
In this example, the consumption of hydrogen sulfide was 0.3t/d, the yield of sulfide slag was 1.64t/d, and the yield of the liquid after purification by sulfidization was 280m3/d。
In this example, the yield of the deeply purified liquid after nanofiltration treatment was 168m3D, the yield of the concentrated brine is 110m3And d. After the concentrated acid salt is treated by the metal recovery system, the yield of the zinc sulfide wet slag is 447.69 kg/d.
In this embodiment, the yield of condensed water is 130m3/d。
In this example, the yield of purified acid was 35m3D, acidity of 40%, F content of 105mg/L, Cl content of 86 mg/L.
The above examples are merely preferred embodiments of the present invention, and the scope of the present invention is not limited to the above examples. All technical schemes belonging to the idea of the invention belong to the protection scope of the invention. It should be noted that modifications and embellishments within the scope of the invention may be made by those skilled in the art without departing from the principle of the invention, and such modifications and embellishments should also be considered as within the scope of the invention.
Claims (8)
1. A method for recycling smelting waste acid wastewater is characterized by comprising the following steps:
s1, introducing hydrogen sulfide gas into the smelting waste acid wastewater to perform a vulcanization reaction, and recovering arsenic, copper, lead, cadmium and bismuth in the smelting waste acid wastewater to obtain a vulcanized purified liquid;
s2, carrying out microfiltration on the vulcanized and purified liquid obtained in the step S1, and removing suspended matters, solid particles, colloids, organic matters and oil substances in the vulcanized and purified liquid to obtain microfiltration and purification filtrate; the microfiltration component adopted in the microfiltration process takes carbon powder and silicon dioxide powder as base materials; the mass ratio of the carbon powder to the silicon dioxide powder is 6-7: 3-4;
s3, conveying the microfiltration purification filtrate obtained in the step S2 to a nanofiltration component for nanofiltration by adopting a Hastelloy C3000 high-pressure plunger pump, and recovering nickel ions, zinc ions, iron ions and calcium ions in the microfiltration purification filtrate to obtain a deep-purified liquid; the nanofiltration membrane in the nanofiltration component is an acid-resistant membrane;
s4, evaporating and concentrating the deep purified liquid obtained in the step S3, and recovering condensed water to obtain concentrated acid;
s5, the concentrated acid obtained in the step S4 is subjected to air stripping, fluoride ions and chloride ions in the concentrated acid are removed, purified acid is obtained, and the resource treatment of the waste acid smelting wastewater is completed.
2. The method as claimed in claim 1, wherein in step S2, the purity of the carbon powder is not less than 99.9%; the purity of the silicon dioxide powder is more than or equal to 99.9 percent.
3. The method according to claim 2, wherein in step S2, the operating pressure during the microfiltration process is controlled to be 0.1 to 0.3 MPa; the microfiltration time is 20 min-40 min.
4. The method of claim 3, wherein in step S2, the particle size of the solid in the microfiltration purification filtrate is reduced to below 0.1 micron and SDI ≦ 5.
5. The method according to any one of claims 1 to 4, wherein in the step S1, the purity of the hydrogen sulfide gas is not less than 99.5%; the time of the sulfuration reaction is 15 min-20 min.
6. The method according to any one of claims 1 to 4, wherein in the step S3, the operating pressure during the nanofiltration process is controlled to be 4MPa to 6 MPa; the nanofiltration time is 40 min-60 min.
7. The method according to any one of claims 1 to 4, wherein in the step S4, the deeply purified liquid is subjected to evaporative concentration by a triple-effect concurrent flow mode; the temperature of the first-effect evaporation in the evaporation concentration process is 125-130 ℃, and the gas phase pressure is 0.2 MPa; the temperature of the two-effect evaporation in the evaporation concentration process is 100-105 ℃, and the gas phase pressure is 0-0.05 MPa; the temperature of triple effect evaporation in the evaporation concentration process is 70-80 ℃, and the gas phase pressure is-0.01 MPa-0.08 MPa; the time of evaporation concentration is 6-8 h.
8. The method according to any one of claims 1 to 4, wherein in the step S5, hot air with the temperature of 70-80 ℃ is used for blowing off the concentrated acid; the stripping time is 1.5-2 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911356731.9A CN111018221B (en) | 2019-12-25 | 2019-12-25 | Method for recycling smelting waste acid wastewater |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911356731.9A CN111018221B (en) | 2019-12-25 | 2019-12-25 | Method for recycling smelting waste acid wastewater |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111018221A CN111018221A (en) | 2020-04-17 |
| CN111018221B true CN111018221B (en) | 2021-02-26 |
Family
ID=70213219
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911356731.9A Active CN111018221B (en) | 2019-12-25 | 2019-12-25 | Method for recycling smelting waste acid wastewater |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111018221B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111573934A (en) * | 2020-05-29 | 2020-08-25 | 赛恩斯环保股份有限公司 | Method and device for removing sulfide in liquid after sulfuration of smelting waste acid |
| CN111661971A (en) * | 2020-06-29 | 2020-09-15 | 株洲冶炼集团科技开发有限责任公司 | Lead-zinc smelting flue gas washing high-concentration waste acid zero-discharge process |
| CN114249303A (en) * | 2020-09-23 | 2022-03-29 | 净宝化工股份有限公司 | Method for removing hydrogen peroxide in sulfuric acid |
| CN112387096A (en) * | 2020-10-16 | 2021-02-23 | 楚雄滇中有色金属有限责任公司 | Novel method for purifying and recycling arsenic-containing flue gas by using acidic liquid medium |
| CN112759162B (en) * | 2020-12-30 | 2021-11-19 | 武汉飞博乐环保工程有限公司 | Method and system for recycling waste acid |
| CN113104818A (en) * | 2021-04-20 | 2021-07-13 | 昆明冶金研究院有限公司 | Method for removing fluorine and chlorine from nonferrous metal smelting waste acid |
| CN113511768A (en) * | 2021-06-12 | 2021-10-19 | 广州绿邦环境技术有限公司 | Smelting waste acid treatment method and equipment |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104973714A (en) * | 2015-06-23 | 2015-10-14 | 广西冶金研究院 | Deep purification and recycling method for waste water containing heavy metal ions |
| CN105439355A (en) * | 2015-12-28 | 2016-03-30 | 中南大学 | Polluted acid resource recovery and advanced treatment method and device |
| CN108675502A (en) * | 2018-06-13 | 2018-10-19 | 武汉飞博乐环保工程有限公司 | A kind of waste acid resource method |
| CN208594131U (en) * | 2018-06-13 | 2019-03-12 | 武汉飞博乐环保工程有限公司 | A kind of waste acid resource system |
-
2019
- 2019-12-25 CN CN201911356731.9A patent/CN111018221B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104973714A (en) * | 2015-06-23 | 2015-10-14 | 广西冶金研究院 | Deep purification and recycling method for waste water containing heavy metal ions |
| CN105439355A (en) * | 2015-12-28 | 2016-03-30 | 中南大学 | Polluted acid resource recovery and advanced treatment method and device |
| CN108675502A (en) * | 2018-06-13 | 2018-10-19 | 武汉飞博乐环保工程有限公司 | A kind of waste acid resource method |
| CN208594131U (en) * | 2018-06-13 | 2019-03-12 | 武汉飞博乐环保工程有限公司 | A kind of waste acid resource system |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111018221A (en) | 2020-04-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111018221B (en) | Method for recycling smelting waste acid wastewater | |
| US10662075B2 (en) | Method and apparatus for the recovery and deep treatment of polluted acid | |
| CN101161596B (en) | A method for resource processing non-ferro metals processing wastewater containing ammonia and sulfate radical | |
| CN111268701B (en) | Method for preparing battery-grade lithium hydroxide by using lepidolite | |
| CN106746113B (en) | Process and system for recycling and reusing fluorine-containing wastewater in photovoltaic industry | |
| CN109437463B (en) | Advanced treatment and recycling device for stone coal blank roasting vanadium extraction high-salt wastewater and using method | |
| CN113511663A (en) | Process for preparing lithium carbonate by extracting lithium from oil field underground brine | |
| CN108396158A (en) | A kind of processing method of the complex salt crystal object of electrolytic manganese process | |
| CN104108740B (en) | A kind of novel method of selectivity production high-quality copper sulfate from copper-bearing waste material | |
| CN102086521A (en) | Adsorption and ceramic membrane coupling process for removing sulfate ions from saline water | |
| CN111137909B (en) | Method for stepwise recovering lithium and magnesium in salt lake brine | |
| CN113336260B (en) | Method for recovering copper sulfate in acidic copper sulfate waste liquid | |
| CN110844890A (en) | Resource recycling method of waste sulfuric acid of storage battery | |
| CN201999826U (en) | Recycle treatment equipments for electroplating wastewater | |
| CN111170519A (en) | Treatment process and treatment system for desulfurization wastewater | |
| CN110436679B (en) | Device and method for recycling and comprehensively utilizing washing water of lithium carbonate | |
| CN110015795B (en) | Recycling and zero-discharge treatment system and process for binary high-salt complex system nickel hydrometallurgy wastewater | |
| JP2019125464A (en) | Lithium recovery method | |
| CN109534369B (en) | Membrane integrated lithium chloride preparation equipment and method thereof | |
| CN112159005A (en) | Treatment process and treatment system for aluminum processing anode waste liquid | |
| CN115676856B (en) | Method and system for extracting lithium from salt lake | |
| CN109055748B (en) | Defluorination chlorine agent and preparation method thereof and method for defluorination chlorine using same | |
| CN107662929B (en) | Sodium chloride and sodium sulfate separation concentration elutriation process and system in strong brine zero emission | |
| CN215089715U (en) | Fly ash water washing system and fly ash treatment system containing same | |
| CN101713025B (en) | Method for wet separation of mixed solution containing nickel and zinc |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: A method for resource treatment of smelting waste acid wastewater Effective date of registration: 20211215 Granted publication date: 20210226 Pledgee: China Everbright Bank Co.,Ltd. Changsha Wanjiali road sub branch Pledgor: CHANGSHA HASKY ENVIRONMENTAL PROTECTION TECHNOLOGY DEVELOPMENT Co.,Ltd. Registration number: Y2021430000092 |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| PC01 | Cancellation of the registration of the contract for pledge of patent right |
Date of cancellation: 20230104 Granted publication date: 20210226 Pledgee: China Everbright Bank Co.,Ltd. Changsha Wanjiali road sub branch Pledgor: CHANGSHA HASKY ENVIRONMENTAL PROTECTION TECHNOLOGY DEVELOPMENT Co.,Ltd. Registration number: Y2021430000092 |
|
| PC01 | Cancellation of the registration of the contract for pledge of patent right | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: A method of resource treatment of smelting waste acid wastewater Effective date of registration: 20230116 Granted publication date: 20210226 Pledgee: China Everbright Bank Co.,Ltd. Changsha Wanjiali road sub branch Pledgor: CHANGSHA HASKY ENVIRONMENTAL PROTECTION TECHNOLOGY DEVELOPMENT Co.,Ltd. Registration number: Y2023430000004 |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| PC01 | Cancellation of the registration of the contract for pledge of patent right |
Granted publication date: 20210226 Pledgee: China Everbright Bank Co.,Ltd. Changsha Wanjiali road sub branch Pledgor: CHANGSHA HASKY ENVIRONMENTAL PROTECTION TECHNOLOGY DEVELOPMENT Co.,Ltd. Registration number: Y2023430000004 |
|
| PC01 | Cancellation of the registration of the contract for pledge of patent right | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: A method for resource utilization treatment of smelting acid wastewater Granted publication date: 20210226 Pledgee: China Everbright Bank Co.,Ltd. Changsha Wanjiali road sub branch Pledgor: CHANGSHA HASKY ENVIRONMENTAL PROTECTION TECHNOLOGY DEVELOPMENT Co.,Ltd. Registration number: Y2024980009862 |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right |