CN114933352A - Treatment method of cyanide-containing wastewater - Google Patents
Treatment method of cyanide-containing wastewater Download PDFInfo
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- CN114933352A CN114933352A CN202210383416.0A CN202210383416A CN114933352A CN 114933352 A CN114933352 A CN 114933352A CN 202210383416 A CN202210383416 A CN 202210383416A CN 114933352 A CN114933352 A CN 114933352A
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- cyanide
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- copper salt
- containing wastewater
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- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 239000002351 wastewater Substances 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 35
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims abstract description 52
- 150000001879 copper Chemical class 0.000 claims abstract description 30
- 239000010949 copper Substances 0.000 claims abstract description 30
- 239000011259 mixed solution Substances 0.000 claims abstract description 24
- 239000003814 drug Substances 0.000 claims abstract description 23
- 229910052802 copper Inorganic materials 0.000 claims abstract description 19
- 239000000243 solution Substances 0.000 claims abstract description 19
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000007788 liquid Substances 0.000 claims abstract description 18
- 239000000706 filtrate Substances 0.000 claims abstract description 15
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 14
- 238000000926 separation method Methods 0.000 claims abstract description 14
- 239000002244 precipitate Substances 0.000 claims abstract description 12
- 238000001556 precipitation Methods 0.000 claims abstract description 10
- LEKPFOXEZRZPGW-UHFFFAOYSA-N copper;dicyanide Chemical compound [Cu+2].N#[C-].N#[C-] LEKPFOXEZRZPGW-UHFFFAOYSA-N 0.000 claims abstract description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 238000003723 Smelting Methods 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 229940116318 copper carbonate Drugs 0.000 claims description 6
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 6
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 238000004062 sedimentation Methods 0.000 claims description 5
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 5
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 5
- 239000013522 chelant Substances 0.000 claims description 4
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 4
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 4
- 238000003825 pressing Methods 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 3
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 3
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 claims description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 3
- 239000004571 lime Substances 0.000 claims description 3
- 239000011736 potassium bicarbonate Substances 0.000 claims description 3
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 3
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 235000011181 potassium carbonates Nutrition 0.000 claims description 3
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 3
- 235000011118 potassium hydroxide Nutrition 0.000 claims description 3
- 239000012266 salt solution Substances 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 235000017550 sodium carbonate Nutrition 0.000 claims description 3
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 3
- LITQZINTSYBKIU-UHFFFAOYSA-F tetracopper;hexahydroxide;sulfate Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Cu+2].[Cu+2].[Cu+2].[Cu+2].[O-]S([O-])(=O)=O LITQZINTSYBKIU-UHFFFAOYSA-F 0.000 claims description 3
- 238000003672 processing method Methods 0.000 claims description 2
- 229920005989 resin Polymers 0.000 claims description 2
- 239000011347 resin Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 description 8
- 230000008901 benefit Effects 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 239000003513 alkali Substances 0.000 description 5
- -1 and meanwhile Chemical compound 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 231100000331 toxic Toxicity 0.000 description 3
- 230000002588 toxic effect Effects 0.000 description 3
- 238000004065 wastewater treatment Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- OJDHPAQEFDMEMC-UHFFFAOYSA-N N#C[Cu]C#N Chemical class N#C[Cu]C#N OJDHPAQEFDMEMC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- OSVXSBDYLRYLIG-UHFFFAOYSA-N dioxidochlorine(.) Chemical compound O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 description 2
- 150000004692 metal hydroxides Chemical class 0.000 description 2
- 229910052976 metal sulfide Inorganic materials 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 230000020477 pH reduction Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000004155 Chlorine dioxide Substances 0.000 description 1
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 1
- 239000005750 Copper hydroxide Substances 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- 238000012271 agricultural production Methods 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 229920001429 chelating resin Polymers 0.000 description 1
- 238000003843 chloralkali process Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 235000019398 chlorine dioxide Nutrition 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 229910001956 copper hydroxide Inorganic materials 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- PANJMBIFGCKWBY-UHFFFAOYSA-N iron tricyanide Chemical compound N#C[Fe](C#N)C#N PANJMBIFGCKWBY-UHFFFAOYSA-N 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
-
- 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
- C02F1/5209—Regulation methods for flocculation or precipitation
-
- 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
- C02F2101/16—Nitrogen compounds, e.g. ammonia
- C02F2101/18—Cyanides
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Removal Of Specific Substances (AREA)
Abstract
The invention discloses a method for treating cyanide-containing wastewater, which comprises the following steps: adding soluble copper salt into cyanide-containing wastewater to obtain a first mixed solution; carrying out solid-liquid separation on the first mixed solution to obtain a cyanide copper salt-containing precipitate and a filtrate; adding a first medicament and a second medicament into the filtrate in sequence for precipitation treatment to obtain a second mixed solution; carrying out solid-liquid separation on the second mixed solution to obtain a solution from which cyanogen and heavy metals are removed; the heavy metal comprises copper. By adopting the method, the cyanogen removal efficiency of the cyanide-containing wastewater can be improved, and the cost is reduced.
Description
Technical Field
The invention relates to the field of wastewater treatment, in particular to a method for treating cyanide-containing wastewater.
Background
The cyanide-containing wastewater is mainly from industrial production such as ore dressing, non-ferrous metal smelting, metal processing, coking, electroplating, electronics, chemical industry, leather making, instruments and the like, and the cyano is a chemical substance with strong complexing capability, so that the wastewater in the industries not only contains simple cyanide, but also contains metal cyanide complex, thiocyanate and the like, and has great harm to regional environment quality, industrial and agricultural production, human health and the like due to the extremely high toxicity, and the problem of harmless treatment of the cyanide-containing wastewater is very important from the perspective of environmental engineering and biosafety.
At present, the cyanide-containing wastewater treatment methods mainly include physical and chemical methods such as activated carbon adsorption, electrolysis, acidification stripping, sulfur dioxide-oxidation, chlor-alkali, iron oxidation, ion exchange, chlorine dioxide and the like. Among them, the chlor-alkali process is currently the most widely used process, which can completely oxidize cyanide to cyanate and finally decompose cyanide to CO 2 And N 2 However, this process, and similar oxidation processes such as hydrogen peroxide and ozone processes, are limited by the following aspects: not destroying stable metal cyanide complexes, e.g. ferrocyanide complexes (Fe (CN)) 6 4- ) And iron cyanide complex (Fe (CN)) 6 3- ) (ii) a ② maintaining a high pH; and thirdly, the reaction is non-selective, the amount of chemicals consuming chlorine and caustic alkali is large, and especially when high-concentration cyanide-containing wastewater is treated, a large amount of bleaching water needs to be added, the wastewater yield is large, and the subsequent treatment cost is high. And other methods such as an electrolysis method, an acidification stripping method, an ion exchange method and the like also have the problems of high production safety risk, low removal efficiency, high one-time investment, complex equipment, high process requirement conditions, high running cost and the like. Therefore, development and search of new processes are urgently needed for the treatment of high-concentration cyanide-containing wastewater.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a cyanide-containing wastewater treatment method, which can effectively remove cyanide-containing compounds in high-concentration cyanide-containing wastewater with a removal rate of more than 99.9 percent and overcomes the defects of high cost, high control parameter requirement, unstable treatment efficiency and the like in the prior art.
In order to achieve the above object, the technical scheme of the invention is as follows:
in one aspect of the present invention, the present invention provides a method for treating high-concentration cyanide-containing wastewater, comprising the steps of:
adding soluble copper salt into cyanide-containing wastewater to obtain a first mixed solution;
carrying out solid-liquid separation on the first mixed solution to obtain a cyanide copper salt-containing precipitate and a filtrate;
adding a first medicament and a second medicament into the filtrate in sequence for precipitation treatment to obtain a second mixed solution;
carrying out solid-liquid separation on the second mixed solution to obtain a solution from which cyanogen and heavy metals are removed; the heavy metal comprises copper.
According to the embodiment of the invention, the cyanogen content of the cyanogen-containing wastewater is not less than 2 mg/L.
According to an embodiment of the present invention, the cyanide-containing wastewater includes one or more of cyanide, metal cyanide complex and thiocyanate.
According to the embodiment of the invention, the soluble copper salt is a substance which contains copper element and is soluble in water, and the copper content of the water solution is more than 0.1g/L, and the soluble copper salt comprises one or more of copper sulfate, copper chloride, copper nitrate, copper carbonate, basic copper chloride, basic copper sulfate and basic copper carbonate;
the copper content of the soluble copper salt is 2-5 times of the cyanogen content of the cyanogen-containing wastewater.
According to an embodiment of the invention, the soluble copper salt is a soluble copper salt solid or a soluble copper salt solution.
According to the embodiment of the invention, the pH value of the first mixed solution is 6-8, and the reaction time of the cyanogen-containing wastewater and the soluble copper salt is 30 min.
According to the embodiment of the invention, the solid-liquid separation mode is filter pressing or centrifugal standing sedimentation.
According to an embodiment of the invention, the first agent is a base, the first agent comprising one or more of sodium hydroxide, potassium hydroxide, lime, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate; the second medicament is a DTCR series medicament, and the second medicament comprises one or more of sodium sulfide and liquid amino dithioformic acid type chelate resin derivatives;
the pH value of the second mixed solution is 7-10, and the reaction time of the filtrate, the first medicament and the second medicament is 30 min.
According to an embodiment of the invention, CN is present in the solution for removing cyanogen and heavy metals - Is less than 2mg/L, Cu 2+ The content of (A) is less than 5 mg/L.
According to an embodiment of the present invention, the processing method further includes:
and smelting the cyanide-containing copper salt precipitate through a smelting furnace, so that copper is obtained after cyanide in the cyanide-containing copper salt precipitate is oxidized and decomposed.
Compared with the prior art, the method has the following advantages:
(1) the method can simultaneously react CN - 、SCN - 、Fe(CN) 6 3- The cyanide-containing anions are removed from the wastewater, the removal efficiency is high, and the reaction time is short; the process is simple, and the precipitation can be completed in a conventional device; no toxic and harmful gas is generated in the reaction process, and the production safety coefficient is high; the precipitated cyanide-containing copper salt enters a smelting furnace to recover copper, and meanwhile, cyanogen is thoroughly oxidized and decomposed at high temperature, so that thorough harmless treatment is realized, and the environment-friendly benefit is good;
(2) the method has the advantages of advanced process, common adopted medicaments, low price, safe and reliable process operation, obvious economic benefit, environmental benefit and social benefit and provides a new idea for treating the high-concentration cyanide-containing wastewater.
Drawings
FIG. 1 is a schematic flow chart of a method for treating cyanide-containing wastewater provided by the embodiment of the application;
FIG. 2 is a schematic diagram illustrating a method for treating cyanide-containing wastewater according to an embodiment of the present disclosure.
Detailed Description
In order to make the technical problems, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail in the following preferred embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
In one aspect of the present invention, referring to fig. 1, fig. 1 is a schematic flow chart of a method for treating cyanide-containing wastewater, which includes:
s100: adding soluble copper salt into cyanide-containing wastewater to obtain a first mixed solution;
according to the specific embodiment of the invention, the cyanogen content of the cyanogen-containing wastewater is not less than 2 mg/L.
According to a specific embodiment of the present invention, the cyanide-containing wastewater comprises one or more of cyanide, metal cyanide complex and thiocyanate.
According to a specific embodiment of the invention, the soluble copper salt is a substance containing copper element and having solubility in water and copper content in water solution of more than 0.1g/L, and the soluble copper salt comprises one or more of copper sulfate, copper chloride, copper nitrate, copper carbonate, basic copper chloride, basic copper sulfate and basic copper carbonate;
the copper content of the soluble copper salt is 2-5 times (calculated by molar ratio) of the cyanogen content of the cyanogen-containing wastewater.
According to a specific embodiment of the invention, the soluble copper salt is a soluble copper salt solid or a soluble copper salt solution.
According to the specific embodiment of the invention, soluble copper salt is added into cyanide-containing wastewater to generate a series of precipitation reactions, so that various cyanide-containing compounds such as cyanide, metal cyanide complex, thiocyanate and the like can be removed simultaneously, and the defects that the stable metal cyanide complex cannot be effectively destroyed in the prior art and the like are overcome. The relevant reaction principle is as follows:
Cu 2+ +2CN - ＝Cu(CN) 2
Cu 2+ +2SCN - ＝Cu(SCN) 2
nCu 2+ +2[Me(CN) 6 ] n- ＝Cu n [Me(CN) 6 ] 2
according to a specific embodiment of the invention, the pH of the first mixed solution is 6-8. The pH value of the reaction is strictly controlled in the reaction process. When the pH value is too low, the cyanogen-containing compound in the solution can generate toxic cyanogen-containing gas when meeting acid; too high a pH value accelerates the acidic hydrolysis of copper ions in the solution to form copper hydroxide precipitate, which affects the binding of copper ions with cyanide-containing anions.
S200: carrying out solid-liquid separation on the first mixed solution to obtain a cyanide copper salt-containing precipitate and a filtrate;
s300: sequentially adding a first medicament and a second medicament into the filtrate for precipitation treatment to obtain a second mixed solution;
according to a specific embodiment of the present invention, the first agent is a base, and the first agent includes one or more of sodium hydroxide, potassium hydroxide, lime, sodium carbonate, potassium carbonate, sodium bicarbonate, and potassium bicarbonate; the second medicament is DTCR series medicament, and the second medicament comprises one or more of sodium sulfide and liquid amino dithioformic acid type chelating resin derivatives.
According to the specific embodiment of the invention, the pH of the second mixed solution is 7-10. The reaction mainly utilizes the fact that sulfur ions are easy to combine with heavy metal ions to generate metal sulfide precipitate with low solubility, or adds DTCR series medicaments to Hg in the wastewater 2+ 、Cd 2+ 、Cu 2 +、Pb 2+ 、Mn 2+ 、Ni 2+ 、Zn 2+ 、Cr 3+ And the heavy metal ions react rapidly to generate insoluble chelate salt, and then the chelate salt is subjected to filter pressing separation and precipitation, so that the heavy metal ions in the waste liquid are effectively removed. In the reaction process, the pH value of the solution is adjusted by using the compound alkali, so that the phenomenon that the added sodium sulfide generates toxic hydrogen sulfide gas when meeting acid due to the over-low pH value is avoided.
S400: carrying out solid-liquid separation on the second mixed solution to obtain a solution from which cyanogen and heavy metals are removed; the heavy metal comprises copper;
according to the specific embodiment of the invention, the solid-liquid separation mode is filter pressing or centrifugal standing sedimentation.
According to a particular embodiment of the invention, CN is present in the solution for removing cyanogen and heavy metals - Is less than 2mg/L, Cu 2+ Of (1) containsThe amount is less than 5 mg/L.
Referring to fig. 2, fig. 2 is an exemplary schematic diagram of a method for treating cyanide-containing wastewater according to an embodiment of the present disclosure. Taking 1.23kg of cyanide-containing wastewater of a certain printed circuit board manufacturing enterprise, analyzing the total cyanide content in the raw material liquid to 6454.4mg/L, COD cr The content of 43920mg/L, pH is 7.3-8.6.
Firstly, adding a proper amount of compound alkali into cyanide-containing wastewater, adjusting the pH of the solution to 6-8, then adding 228.42g of self-made copper sulfate solid (soluble copper salt) in a factory, fully reacting for 30min, and after complete precipitation, carrying out centrifugal standing and sedimentation (solid-liquid separation) on the mixed solution to obtain 1.37kg of centrifugal filtrate and 84.56g of filter residue. Wherein, the filter residue is sediment containing copper cyanide salt, the copper cyanide salt enters a smelting furnace to recover copper, and meanwhile, the high-temperature oxidative decomposition of cyanide is realized to achieve thorough harmless treatment; the filtrate was analyzed: the total cyanogen content is 1.1mg/L, the removal rate reaches 99.9 percent, and the COD is cr The content is reduced to 14448mg/L, which indicates that the cyanide-containing waste water contains organic cyanide and can react with Cu 2+ Binding resulted in precipitation.
Adding a proper amount of compound alkali (a first agent) into the filtrate, adjusting the pH of the solution to 7-10, and generating precipitates in the solution. In order to further remove metal ions in the solution, a proper amount of sodium sulfide (second agent) is continuously added, the mixture is fully reacted for 30min, and after the precipitation is completed, the mixed solution is subjected to centrifugal standing and sedimentation (solid-liquid separation) to obtain centrifugal filtrate and filter residue. Wherein the filter residue is a metal hydroxide and sulfide precipitate, and the metal hydroxide can enter a smelting furnace to realize the recovery of copper; the filtrate was analyzed: total cyanogen content of 1.1mg/L, Cu 2+ The content of (B) was 3.6 mg/L.
While the principles and embodiments of the present invention have been described, it should be understood by those skilled in the art that the above embodiments are not intended to limit the present invention in any way, and all technical solutions obtained by using equivalent substitution or equivalent exchange methods fall within the scope of the present invention.
Claims (10)
1. A method for treating cyanide-containing wastewater is characterized by comprising the following steps:
adding soluble copper salt into cyanide-containing wastewater to obtain a first mixed solution;
carrying out solid-liquid separation on the first mixed solution to obtain a cyanide copper salt-containing precipitate and a filtrate;
adding a first medicament and a second medicament into the filtrate in sequence for precipitation treatment to obtain a second mixed solution;
carrying out solid-liquid separation on the second mixed solution to obtain a solution from which cyanogen and heavy metals are removed; the heavy metal comprises copper.
2. The treatment method according to claim 1, wherein the cyanogen content of the cyanogen-containing wastewater is not less than 2 mg/L.
3. The treatment method according to claim 1, wherein the cyanide-containing wastewater comprises one or more of cyanide, a metal cyanide complex and thiocyanate.
4. The treatment method according to claim 1, wherein the soluble copper salt is a substance containing copper element and having solubility in water and copper content in water solution of more than 0.1g/L, and the soluble copper salt comprises one or more of copper sulfate, copper chloride, copper nitrate, copper carbonate, basic copper chloride, basic copper sulfate and basic copper carbonate;
the copper content of the soluble copper salt is 2-5 times of the cyanogen content of the cyanogen-containing wastewater.
5. The treatment method according to claim 1, wherein the soluble copper salt is a soluble copper salt solid or a soluble copper salt solution.
6. The treatment method according to claim 1, wherein the pH of the first mixed solution is 6 to 8, and the reaction time of the cyanide-containing wastewater and the soluble copper salt is 30 min.
7. The treatment method according to claim 1, wherein the solid-liquid separation mode is filter pressing or centrifugal standing sedimentation.
8. The process of claim 1, wherein the first agent is a base, the first agent comprising one or more of sodium hydroxide, potassium hydroxide, lime, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate; the second medicament is a DTCR series medicament, and the second medicament comprises one or more of sodium sulfide and liquid amino dithioformic acid type chelate resin derivatives;
the pH value of the second mixed solution is 7-10, and the reaction time of the filtrate, the first medicament and the second medicament is 30 min.
9. The treatment process according to claim 1, wherein CN in the solution for removing cyanogen and heavy metals - Is less than 2mg/L, Cu 2+ The content of (A) is less than 5 mg/L.
10. The processing method of claim 1, further comprising:
and smelting the cyanide-containing copper salt precipitate through a smelting furnace, so that copper is obtained after cyanide in the cyanide-containing copper salt precipitate is oxidized and decomposed.
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| CN117843109A (en) * | 2024-03-06 | 2024-04-09 | 山东黄金矿业科技有限公司选冶实验室分公司 | Method for treating cyanide-containing wastewater by curing copper salt precipitation with concentrated sulfuric acid |
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| CN117843109A (en) * | 2024-03-06 | 2024-04-09 | 山东黄金矿业科技有限公司选冶实验室分公司 | Method for treating cyanide-containing wastewater by curing copper salt precipitation with concentrated sulfuric acid |
| CN117843109B (en) * | 2024-03-06 | 2024-05-10 | 山东黄金矿业科技有限公司选冶实验室分公司 | Method for treating cyanide-containing wastewater by curing copper salt precipitation with concentrated sulfuric acid |
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