CN1994934A - Method for processing cyanogens-containing waste water using chemical precipitation and gamma ray irradiation - Google Patents
Method for processing cyanogens-containing waste water using chemical precipitation and gamma ray irradiation Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 43
- 239000002351 wastewater Substances 0.000 title claims abstract description 42
- 230000005251 gamma ray Effects 0.000 title claims abstract description 17
- 238000009388 chemical precipitation Methods 0.000 title claims description 5
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims abstract description 73
- 150000003751 zinc Chemical class 0.000 claims abstract description 21
- 239000000126 substance Substances 0.000 claims abstract description 13
- 238000004064 recycling Methods 0.000 claims abstract description 5
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims description 49
- 238000001556 precipitation Methods 0.000 claims description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 18
- 239000002244 precipitate Substances 0.000 claims description 16
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 16
- 239000011701 zinc Substances 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 12
- 229960001763 zinc sulfate Drugs 0.000 claims description 12
- 238000006731 degradation reaction Methods 0.000 claims description 11
- 230000015556 catabolic process Effects 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 239000002002 slurry Substances 0.000 claims description 8
- 239000012716 precipitator Substances 0.000 claims description 7
- 238000010521 absorption reaction Methods 0.000 claims description 4
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 4
- 238000007664 blowing Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 239000004246 zinc acetate Substances 0.000 claims description 4
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 3
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 3
- 239000004571 lime Substances 0.000 claims description 3
- 230000001678 irradiating effect Effects 0.000 claims description 2
- 238000005259 measurement Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000013049 sediment Substances 0.000 abstract 1
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 13
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 12
- 229910052737 gold Inorganic materials 0.000 description 12
- 239000010931 gold Substances 0.000 description 12
- 239000010949 copper Substances 0.000 description 9
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 8
- 239000011686 zinc sulphate Substances 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 6
- 230000000593 degrading effect Effects 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 4
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 4
- 238000005119 centrifugation Methods 0.000 description 4
- DOBRDRYODQBAMW-UHFFFAOYSA-N copper(i) cyanide Chemical compound [Cu+].N#[C-] DOBRDRYODQBAMW-UHFFFAOYSA-N 0.000 description 4
- 125000004093 cyano group Chemical group *C#N 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 238000002386 leaching Methods 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000007832 Na2SO4 Substances 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- MNWBNISUBARLIT-UHFFFAOYSA-N sodium cyanide Chemical compound [Na+].N#[C-] MNWBNISUBARLIT-UHFFFAOYSA-N 0.000 description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
- 239000004471 Glycine Substances 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- UXKUODQYLDZXDL-UHFFFAOYSA-N fulminic acid Chemical compound [O-][N+]#C UXKUODQYLDZXDL-UHFFFAOYSA-N 0.000 description 2
- 230000020477 pH reduction Effects 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 238000003608 radiolysis reaction Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- VGTPCRGMBIAPIM-UHFFFAOYSA-M sodium thiocyanate Chemical compound [Na+].[S-]C#N VGTPCRGMBIAPIM-UHFFFAOYSA-M 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- -1 thiocyanate radicals Chemical class 0.000 description 2
- 235000009529 zinc sulphate Nutrition 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
- 229910001369 Brass Inorganic materials 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- NAVJNPDLSKEXSP-UHFFFAOYSA-N Fe(CN)2 Chemical class N#C[Fe]C#N NAVJNPDLSKEXSP-UHFFFAOYSA-N 0.000 description 1
- OJDHPAQEFDMEMC-UHFFFAOYSA-N N#C[Cu]C#N Chemical class N#C[Cu]C#N OJDHPAQEFDMEMC-UHFFFAOYSA-N 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 229910001779 copper mineral Inorganic materials 0.000 description 1
- LEKPFOXEZRZPGW-UHFFFAOYSA-N copper;dicyanide Chemical compound [Cu+2].N#[C-].N#[C-] LEKPFOXEZRZPGW-UHFFFAOYSA-N 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 1
- QPJDMGCKMHUXFD-UHFFFAOYSA-N cyanogen chloride Chemical compound ClC#N QPJDMGCKMHUXFD-UHFFFAOYSA-N 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- 238000001784 detoxification Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- MXZVHYUSLJAVOE-UHFFFAOYSA-N gold(3+);tricyanide Chemical compound [Au+3].N#[C-].N#[C-].N#[C-] MXZVHYUSLJAVOE-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 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
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000005025 nuclear technology Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000000247 postprecipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 210000004911 serous fluid Anatomy 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 231100001234 toxic pollutant Toxicity 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- GTLDTDOJJJZVBW-UHFFFAOYSA-N zinc cyanide Chemical compound [Zn+2].N#[C-].N#[C-] GTLDTDOJJJZVBW-UHFFFAOYSA-N 0.000 description 1
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- Removal Of Specific Substances (AREA)
- Physical Water Treatments (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The invention discloses a disposing method of cyanic waste water through chemical sediment-gamma-ray radiating method, which comprises the following steps: combining zinc salt sediment and gamma-ray decomposing cyanide method; adding zinc salt in the cyanic waste water; sedimenting and recycling most of cyanide; decomposing residual cyanide through gamma-ray to make waste water reach draining standard.
Description
Technical Field
The invention belongs to the field of nuclear technology and environmental protection. In particular to a method for treating cyanide-containing wastewater by a chemical precipitation-gamma-ray irradiation method for recovering cyanide from cyanide-containing wastewater to treat the cyanide-containing wastewater.
Background
Cyaniding gold leaching is a method commonly used in gold smelteries to extract gold and silver. The gold leaching cyanidation waste water (cyanidation barren liquor) is not only highly toxic, but also has a large water content, and a medium-scale cyanidation plant produces about 400m per day3And (4) barren liquor. The treatment of the cyanide barren solution is related to the sustainable development of gold extraction enterprises. The barren solution generally contains total cyanogen CNt0.5-8.0 g/L; 0.4-2.4 g/L of copper; 0.2-2.0 g/L of zinc and a small amount of gold and silver. Some gold concentrates are associated with a considerable amount of copper minerals, the copper content of corresponding barren solution is as high as 8-10 g/L, and the total cyanogen is as high as 15-22 g/L. At present, no ideal method exists for treating barren liquor. Most gold smelteries circulate cyanide barren solution in a closed cycle or recycle cyanide barren solution after acidification, precipitation, copper removal and neutralization, so that cyanide in the cyanide barren solution is utilized, but the leaching rate of gold is seriously influenced by impurity accumulation caused by long-time circulation; on the other hand, the lean liquor circulation causes an imbalance in the amount of water, and a part of the wastewater must be discharged. Therefore, a part of the cyanide barren solution needs to be taken out for treatment.
Current methods for treating cyanide-containing wastewater generally involve destroying cyanide species and recovering cyanide species, but suffer from one or more of these disadvantages. The low-concentration cyanide-containing wastewater is generally treated by a destruction method, such as a chlorine gas and sodium hypochlorite oxidation method, a large amount of chlorine is remained in the water after the treatment by the method, and CNCl extremely toxic gas can be generated to cause secondary pollution; inco (air-SO)2Oxidation) method and hydrogen peroxide oxidation method have no removing effect on thiocyanate, copper salt is used as a catalyst, nonferrous metal is consumed, and the cost is high; the biodegradation process has strict requirements on the cyanide concentration, the pH value and the temperature of the wastewater. All destructive methods are purely consumable. The cyanide-containing wastewater with medium and high concentration is generally treated by a recovery method. These methods include: (1) in a traditional acidification method, the total cyanogen concentration of the treated wastewater is generally CNt 5-20 mg/L and cannot reach the discharge standard (CNt0.5mg/L); (2) ZnSO4Precipitation method. The treated wastewater CNt 20-40 mg/L does not reach the discharge standard. (3) The ion exchange resin adsorption can make the waste water reach the discharge standard, but the resin elution and regeneration operations are complex, and the resin is expensive.
Disclosure of Invention
The invention aims to provide a method for treating cyanide-containing wastewater by a chemical precipitation-gamma-ray irradiation method for recovering cyanide from cyanide-containing wastewater to treat cyanide-containing wastewater. The method is characterized in that a zinc salt precipitation and gamma ray irradiation cyanide degradation process is adopted to treat the cyanide barren solution, and the specific process steps are as follows:
1) using cyanide barren solution as feed liquid;
2) adding a precipitator zinc salt into the cyanide barren solution for precipitation reaction;
3) centrifuging the mixture to separate a clear solution and a precipitate, and filtering the precipitate Zn (CN)2；
4) In Zn (CN)2Adding about 50% (volume ratio) cyanide-containing waste water into the precipitate to make slurry, adding 50% concentrated sulfuric acid, acidifying to pH 2, and aerating and blowing off generated HCN; the liquid after stripping is zinc sulfate solution, lime Ca (OH)2Adjusting the pH value to be more than 7, and returning to be used as a precipitator for recycling;
5) with 10% NaOH solution or 10% Ca (OH)2Absorbing HCN liquid in the steps 3 and 4 by using slurry;
6) irradiating the chemical precipitation solution by gamma-ray to further degrade cyanide,
the zinc salt is Zn2+And CNtThe molar ratio is 0.61-1.5, and the pH is 6.0-8.0.
And the stripping conditions comprise that the pH value of the solution is 0.35, the temperature is 40-50 ℃, the time is 1h, the gas-liquid ratio is 1000, and the gas is filled for 35 minutes.
The precipitator zinc salt is zinc sulfate or zinc acetate.
The gamma-ray is formed by Co60The central bore was found to measure 4.9 GY/s.
The gamma ray absorption measurement is 125 kGY-1010 kGY, and the degradation rate G (CNt) is 0.07-0.14.
The precipitation reaction occurs at a pH greater than or equal to 7 so that no HCN escapes from the solution.
The invention has the following obvious advantages:
1. the new process of zinc salt precipitation and gamma ray cyanide degradation is adopted to treat the cyanide barren solution, which not only can recover most valuable elements of cyanogen and the like, but also can ensure that the effluent reaches the discharge standard (total cyanogen is 0.5mg/L), thereby having economic benefit and environmental benefit.
2. The high-energy ray has high efficiency for treating the cyanide-containing wastewater, can treat various toxic pollutants simultaneously, does not produce secondary pollution, and is a novel wastewater treatment technology with high efficiency and high cleanliness.
3. The new process for degrading cyanide by using zinc salt precipitation and gamma rays has strong adaptability to waste water, and can treat gold ore cyanide barren solution, cyanide brass electroplating waste water, cyanide copper electroplating waste water, solid sodium cyanide production waste water and the like.
Drawings
FIG. 1 is a process flow chart of degradation treatment of cyanide-containing wastewater by chemical precipitation-gamma-ray irradiation.
Detailed Description
The invention provides a method for treating cyanide-containing wastewater by a chemical precipitation-gamma-ray irradiation method, which is used for recovering cyanide from cyanide-containing wastewater to treat the cyanide-containing wastewater. The cyanide barren solution is treated by adopting the process of degrading cyanide by zinc salt precipitation and gamma ray irradiation, so that most of valuable elements, such as cyanogen and the like, can be recovered, and the effluent can reach the discharge standard (total cyanogen is 0.5mg/L), thereby having economic benefit and environmental benefit. The basic principle is explained as follows:
adding a precipitator zinc salt such as zinc sulfate into cyanide-containing wastewater, converting cyanide ions into zinc cyanide precipitates, and reacting iron-cyanide complexes and copper-cyanide complexes with zinc sulfate to generate precipitates:
2NaCN+ZnSO4＝Zn(CN)2↓+Na2SO4
Na2Cu(CN)3+ZnSO4＝Zn(CN)2↓+CuCN↓+Na2SO4
Na4Fe(CN)6+2ZnSO4＝Zn2Fe(CN)6↓+Na2SO4
the above reaction occurs at a pH greater than or equal to 7 so that almost no HCN escapes from the solution. The precipitate is then added to H2SO4Acidification, Zn (CN)4 2-And (3) decomposing to release HCN:
Zn(CN)2+H2SO4＝2HCN↑+ZnSO4wherein the sulfuric acid is concentrated sulfuric acid which is not diluted by water.
Acidifying to pH 2 and aerating the HCN produced by stripping, absorbing the hydrogen cyanide gas with sodium hydroxide solution:
HCN+NaOH＝H2O+NaCN
high-concentration sodium cyanide is generated and returned to a cyanide gold leaching system for use. Filtering or centrifugally separating the serous fluid after blowing off HCN to separate acid-insoluble precipitate CuCN and Zn2Fe(CN)6Clear solution of ZnSO4Solution of ZnSO4The solution can be returned to precipitate the cyanide in the next batch of cyanide-containing wastewater, and the cyanide can be recycled.
Most of cyanide can be removed by precipitation with zinc salt, wherein the total cyanide precipitation rate is more than or equal to 94 percent, the copper precipitation rate is more than or equal to 95 percent, and the iron precipitation rate is more than or equal to 94 percent; but few thiocyanate radicals are precipitated, the waste water after the zinc salt precipitation treatment can not reach the discharge standard, some free cyanogen, complex cyanogen, thiocyanate and even some organic matters are remained, and certain toxicity is still remained. The invention combines a new environment-friendly technology, namely a gamma-ray irradiation method, to carry out deep detoxification treatment. The basic principle is that a large amount of e is generated when the wastewater is irradiated by gamma-raysaqFree radicals (hydrated electrons), H, OH and the like which have extremely strong activity and can initiate chain reaction, have strong oxidation and decomposition effects on residual cyanide, thiocyanide, organic substances and the like, and can also be reduction reaction to oxidize or reduce the cyanide and the like into nontoxic N2And CO2Or low-toxicity products such as cyanate, formamide and glycine. The radiolysis reaction of cyanide may have the following reaction mechanism:
H+HCN→H2CN
HCN+eaq -→HCN-
HCN-+H+→H2CN
HCN-+·CONH2→HCONH2+CN-
2·CONH2→HCNO+HCONH2
·CONH2+H2CN→HCNO+H2CNH
it can be seen that the radiolysis reaction is complex, in which glycine may hydrate electrons to form HCN-And then produced by polymerization, hydrolysis and the like.
The degradation mechanism of the metal-cyanide complex is: metal-cyano complexes with CN-Equilibrium between ions, CN-After the ions are degraded in the above manner, the equilibrium is constantly shifted to the right, thereby degrading the metal-cyanide complex. For example:
Cu(CN)4 3-_Cu(CN)3 2-+CN-
the degradation of thiocyanate is SCN-Oxidized by OH free radical to form CN-Ions then CN-The ions are degraded in the manner described above.
Therefore, under a certain irradiation metering condition, cyanide can be quickly and effectively degraded, so that the total cyanide concentration of the effluent reaches the discharge standard.
Example 1
The feed liquid is a real cyaniding barren solution of a gold ore in Hebei, and comprises the following components: CNt0.770g/L, Cu0.030g/LZn0.246g/L, CN-0.560g/L，SCN-0.141g/L, Fe0.029g/L, pH 11.9. the process flow is shown in figure 1.
Most of the cyanogen was first removed and recovered by precipitation with zinc sulphate.
Adding zinc salt such as zinc sulfate or zinc acetate into cyanide barren solution, and addingn 2+Quickly react with OH in barren solution-、CN-Zinc cyanide complex ion, copper cyanide complex ion, [ Fe (CN)]6]4-The cyanide reacts as described above to produce a white flocculent precipitate. These reactions proceed rapidly and are essentially completed with proper stirring for 1-3 min. Then, the supernatant and the precipitate were separated by centrifugation with a centrifuge. The best dosage of zinc salt is Zn2+And CNtA pH of 6.5 to 8.0 at a molar ratio of 1.5, wherein the residual cyanogen concentration is maintained at about 40ppm, the cyanogen precipitation rate is 94.7%, iron is 1.8mg/L, and thiocyanate radicals are present at about 40ppm150mg/L。
Zn (CN) separated by centrifugation2Adding about 50% (volume ratio) cyanogen-containing waste water into the precipitate to make slurry, adding 50% concentrated sulfuric acid and aerating to blow off HCN, using 10% NaOH solution or 10% Ca (OH)2The slurry absorbs HCN. The stripping conditions are that the pH value of the solution is 0.35, the temperature is 40-50 ℃, the time is 1h, the gas-liquid ratio is 1000, the total cyanogen concentration can be reduced from 7340mg/L to 26.1mg/L after the gas is filled for 35 minutes, and the stripping rate reaches 99.64%.
The solution after stripping is zinc sulfate solution, and lime is used for adjusting the pH value to a preset value and returning the solution as a precipitator for recycling. The zinc sulfate solution can be reused for many times.
Finally using gamma-ray (Co)60Central bore metering 4.9GY/s) was irradiated on the post-chemical precipitation liquor to further degrade cyanide. The order of increasing difficulty in degrading a single contaminant is: NaCN is more than Zn-CN and more than Cu-CN and more than NaSCN. The result of the degradation by irradiation shows that the gamma ray absorption metric for degrading the cyanided barren solution containing 26mg/L of total cyanogen is 125kGY, and the degradation amount G (CNt) is 0.07. After the lean solution is subjected to zinc salt precipitation and cyanogen removal, the lean solution contains 150mg/L thiocyanate, and the thiocyanate can be degraded by 69% by metering 125 kGy.
Example 2
The feed liquid is a real cyaniding barren solution of a gold ore in Shandong, and comprises the following components: CNt8.38g/L, Cu2.40g/L, Zn1.88g/L, CN-4.3g/L, Fe0.94g/L, pH 12.5. The processing flow is shown in figure 1.
Most of the cyanogen was first removed and recovered by precipitation with zinc sulphate.
Adding zinc salt such as zinc sulfate or zinc acetate into cyanide barren solution, and addingn 2+Quickly react with OH in barren solution-、CN-Zinc cyanide complex ion, copper cyanide complex ion, [ Fe (CN)]6]4-The cyanide reacts as described above to produce a white flocculent precipitate. These reactions proceed rapidly and are essentially complete with appropriate stirring for 1-3 min. The supernatant and the precipitate are then separated by filtration or centrifugation.
The results show that the optimum amount of zinc salt is Zn2+And CNtThe molar ratio is 0.61, the pH is 6.0-8.0, the residual cyanogen concentration is about 421ppm, and the cyanogen precipitation rate is 95%; the iron precipitation rate was 92%, the copper precipitation rate was 93.5%, the residual concentration copper was 66mg/L, and iron was 75 mg/L.
Zn (CN) separated by centrifugation2Adding 50% (volume ratio) barren solution into the precipitate to make slurry, adding concentrated sulfuric acid or 50% dilute sulfuric acid, aerating and blowing off HCN, using 10% NaOH solution or 10% Ca (OH)2The slurry absorbs HCN. The total cyanogen concentration can be reduced from 26029mg/L to 82mg/L under the conditions that the pH value of the solution is 0.2, the temperature is 40-50 ℃ and the gas-liquid ratio is 360 for 1 hour, and the total cyanogen stripping rate reaches 99.7 percent. The solution after stripping is zinc sulfate solution and limeAdjusting pH to 2-4, and returning to be used as precipitant for recycling. The zinc sulfate solution can be reused for many times.
Then using gamma-rays (Co)60Central bore 4.9GY/s) was irradiated on the post-chemical precipitation liquor to further degrade cyanide. The order of increasing difficulty in degrading a single contaminant is: NaCN is more than Zn-CN and more than Cu-CN and more than NaSCN. The result of the degradation by irradiation showed that the gamma ray absorption of the post-precipitation solution containing 421mg/L of total cyanogen was 1010kGY, and the degradation amount g (cnt) was 0.14.
Claims (7)
1. A chemical precipitation-gamma-ray irradiation method for treating cyanide-containing wastewater is characterized in that zinc salt precipitation and gamma-ray irradiation are adopted to degrade cyanide to treat cyanide barren solution, and the specific process steps are as follows:
1) using cyanide barren solution as feed liquid;
2) adding a precipitator zinc salt into the cyanide barren solution for precipitation reaction;
3) centrifuging the mixture to separate a clear solution and a precipitate, and filtering the precipitate Zn (CN)2；
4) In Zn (CN)2Adding about 50% (volume ratio) cyanide-containing waste water into the precipitate to make slurry, adding 50% concentrated sulfuric acid, acidifying to pH 2, and aerating and blowing off the generated HCN; the liquid after stripping is zinc sulfate solution, lime Ca (OH)2Adjusting the pH value to be more than 7, and returning to be used as a precipitator for recycling;
5) with 10% NaOH solution or 10% Ca (OH)2Absorbing HCN liquid in the steps 3 and 4 by using slurry;
6) irradiating the chemical precipitation solution by gamma-ray to further degrade cyanide.
2. The method for treating cyanide-containing wastewater by chemical precipitation-gamma-ray irradiation according to claim 1, wherein the zinc salt is Zn2+And CNtThe molar ratio is 0.61-1.5, and the pH is 6.0-8.0.
3. The method for treating cyanide-containing wastewater by using the chemical precipitation-gamma-ray irradiation method according to claim 1, wherein the stripping condition comprises that the pH value of the solution is 0.35, the temperature is 40-50 ℃, the time is 1h, the gas-liquid ratio is 1000, and the gas is filled for 35 minutes.
4. The method for treating cyanide-containing wastewater by chemical precipitation-gamma-ray irradiation according to claim 1, wherein the precipitant zinc salt is zinc sulfate or zinc acetate.
5. The method for treating cyanide-containing wastewater by chemical precipitation-gamma-ray irradiation according to claim 1, wherein the gamma-ray is Co-based60The central bore was found to measure 4.9 GY/s.
6. The method for treating cyanide-containing wastewater by chemical precipitation-gamma-ray irradiation according to claim 1, wherein the gamma-ray absorption measurement is 125 kGY-1010 kGY, and the degradation yield G (CNt) is 0.07-0.14.
7. The method of claim 1, wherein the precipitation reaction is carried out at a pH of 7 or higher, so that no HCN is released from the solution.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102491487A (en) * | 2011-11-29 | 2012-06-13 | 华东理工大学 | Depth processing method of cyanogen-containing waste water |
| CN104291356A (en) * | 2014-09-10 | 2015-01-21 | 杭州青化社化工有限公司 | Preparation method of zinc cyanide |
| CN104900295A (en) * | 2015-05-28 | 2015-09-09 | 官爱平 | Irradiation apparatus and method for fluid processing |
| CN106977029A (en) * | 2017-05-17 | 2017-07-25 | 哈工大新材料智能装备技术研究院（招远）有限公司 | A kind of cyaniding gold extraction waste water processing being combined based on soundization and cyclic utilization system |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103304052A (en) * | 2013-05-28 | 2013-09-18 | 西安建筑科技大学 | Treatment method of gold extraction cyaniding wastewater containing copper and iron ions with high concentration |
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2006
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102491487A (en) * | 2011-11-29 | 2012-06-13 | 华东理工大学 | Depth processing method of cyanogen-containing waste water |
| CN102491487B (en) * | 2011-11-29 | 2014-04-16 | 华东理工大学 | Depth processing method of cyanogen-containing waste water |
| CN104291356A (en) * | 2014-09-10 | 2015-01-21 | 杭州青化社化工有限公司 | Preparation method of zinc cyanide |
| CN104900295A (en) * | 2015-05-28 | 2015-09-09 | 官爱平 | Irradiation apparatus and method for fluid processing |
| CN106977029A (en) * | 2017-05-17 | 2017-07-25 | 哈工大新材料智能装备技术研究院（招远）有限公司 | A kind of cyaniding gold extraction waste water processing being combined based on soundization and cyclic utilization system |
| CN106977029B (en) * | 2017-05-17 | 2022-11-04 | 重庆哈工拓普科技有限公司 | Cyanide gold extraction wastewater treatment and cyclic utilization system based on sonochemistry is compound |
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