CN102701334A - Method for treating cyanide and ammonia nitrogen in gold smelting wastewater through electrocatalytic oxidation process - Google Patents
Method for treating cyanide and ammonia nitrogen in gold smelting wastewater through electrocatalytic oxidation process Download PDFInfo
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- CN102701334A CN102701334A CN2012101992166A CN201210199216A CN102701334A CN 102701334 A CN102701334 A CN 102701334A CN 2012101992166 A CN2012101992166 A CN 2012101992166A CN 201210199216 A CN201210199216 A CN 201210199216A CN 102701334 A CN102701334 A CN 102701334A
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- waste water
- ammonia nitrogen
- prussiate
- catalytic oxidation
- gold smelting
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- 238000000034 method Methods 0.000 title claims description 56
- 239000002351 wastewater Substances 0.000 title claims description 56
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 title claims description 33
- 238000007254 oxidation reaction Methods 0.000 title claims description 33
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 title claims description 27
- 230000003647 oxidation Effects 0.000 title claims description 25
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 title claims description 20
- 239000010931 gold Substances 0.000 title claims description 20
- 229910052737 gold Inorganic materials 0.000 title claims description 20
- 238000003723 Smelting Methods 0.000 title claims description 18
- 230000003197 catalytic effect Effects 0.000 claims description 18
- 238000005868 electrolysis reaction Methods 0.000 claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- JMANVNJQNLATNU-UHFFFAOYSA-N glycolonitrile Natural products N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 235000011941 Tilia x europaea Nutrition 0.000 description 3
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 description 3
- 238000005660 chlorination reaction Methods 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- -1 cyanogen compound Chemical class 0.000 description 3
- 239000004571 lime Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- TWHASHYLEGKHEX-UHFFFAOYSA-N [N].N.N#CC#N Chemical compound [N].N.N#CC#N TWHASHYLEGKHEX-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 241000251468 Actinopterygii Species 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 241000192700 Cyanobacteria Species 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 241001062472 Stokellia anisodon Species 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 230000009615 deamination Effects 0.000 description 1
- 238000006481 deamination reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
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Abstract
The invention relates to a method for treating cyanide and ammonia nitrogen in gold smelting wastewater through an electrocatalytic oxidation process. The content of total cyanide and the content of ammonia nitrogen in the wastewater which is treated by adopting the method can satisfy the requirements that the content of total cyanide is less than or equal to 0.5mg/L and the content of ammonia nitrogen is less than or equal to 15mg/L in Class I discharge standards of Integrated Wastewater Discharge Standard (GB8978-1996). At the same time, the method has the characteristics of simple process flow, investment saving, small occupied area, no secondary pollution and the like.
Description
One. technical field
The present invention relates to a kind of method of removing prussiate and ammonia nitrogen in the waste water, relate in particular to the method for removing prussiate and ammonia nitrogen in the gold smelting waste water.
Two. background technology
At present, be starting material to carry golden charcoal, desorb, electrodeposition, purifying technique are produced gold and are obtained comparatively widespread use at home, nearly nearly 30 families of domestic this type of gold smelting factory, the pan amount accounts for national more than 30% of output of mineral products gold.Gold smelting factory will produce high salinity and contain the cyanogen ammonia nitrogen waste water in putting forward golden process, and prussiate and ammonia nitrogen concentration all are lower than 800mg/L.Prussiate belongs to highly toxic substance, and CN-can combine with ferricytochrome enzyme in the human body, generates cyanocytochromeoxidase and loses the propagation function of oxygen, causes histanoxia in vivo and suffocates; Ammonia nitrogen is one of principal pollutant of water body, can cause body eutrophication, and waterplant such as pasture and water and blue-green algae are bred in a large number, and the dissolved oxygen in the luxus consumption water forces hydrobiont such as fish dead because of anoxic.Therefore, before discharging, must carry out processing up to standard to containing the cyanogen ammonia nitrogen waste water, there is strict control criterion in China to above-mentioned discharge of wastewater." integrated wastewater discharge standard " (GB8978-1996) requires in the first discharge standard: total cyanogen compound≤0.5mg/L, ammonia nitrogen≤15mg/L.
China is started in the sixties to the improvement of cyanide wastewater; Existing so far 20 several different methods mainly contain acidization, half acidization, chlorination, Yin Kefa, hydrogen peroxide oxidation process, biological oxidation process, natural degradation method, ozone oxidation method and combination process thereof.The method of handling ammonia nitrogen waste water has a lot, present common have blow-off method, chemical precipitation method, break point chlorination, biological deamination method, ion exchange method, absorption method and combination process thereof.Then often adopt chlorination, blow-off method or combination process to handle for prussiate and ammonia nitrogen in the gold smelting waste water; But adopt aforesaid method still to have many problems technically and economically,, floor space high like facility investment and working cost greatly, effluent quality is poor, secondary pollution etc. is arranged; Also do not have at present a kind ofly can to take into account that flow process is simple, reduced investment, floor space is little and the treatment process of non-secondary pollution.For this reason, prussiate and ammonia nitrogen how economical, that remove in the waste water effectively become one of processing gold smelting waste water problem demanding prompt solution.
Three. summary of the invention
To the problems referred to above, the present invention provides a kind of method of utilizing the catalytic oxidation method to handle prussiate and ammonia nitrogen in the gold smelting waste water, have that the efficient of removal is high, flow process simply, reduced investment, floor space is little and advantage such as non-secondary pollution.
Technical scheme of the present invention is following:
The first step: if the waste water ph that needs to handle less than 6 or greater than 12, then adds alkali in waste water or waste water ph to 6～12 are regulated in acid, wherein, alkali includes but not limited to lime, sheet alkali, yellow soda ash, sodium hydrogencarbonate, and lime and sheet alkali are preferred for regulating the pH value; Acid includes but not limited to sulfuric acid, hydrochloric acid, phosphoric acid, and sulfuric acid is preferred for regulating the pH value.
Second step: if chlorine ion concentration is less than 2g/L in the said waste water; Then in waste water, add villaumite and regulate in the waste water chlorine ion concentration greater than more than the 2g/L; Wherein, villaumite includes but not limited to sodium-chlor, iron(ic)chloride, aluminum chloride, and sodium-chlor is preferred for regulating chlorine ion concentration.
The 3rd step: said waste water is introduced in the electrocatalysis oxidation reaction device,, removed prussiate and ammonia nitrogen in the waste water through the catalytic oxidation method to the electrifying electrodes in the reactor drum.Main technologic parameters is following in the catalytic oxidation process: polar plate spacing 0.5cm ~ 10cm, current density 10mA/cm2 ~ 100mA/cm2, electrolysis voltage 2V ~ 20V.Electrolysis time is confirmed by prussiate in the waste water and ammonia nitrogen concentration, generally is controlled at 30min ~ 360min.
The ultimate principle of this process method is following:
Electro-catalytic oxidation technology is to utilize direct oxidation and the indirect oxidation of electrode to be used for oxidative degradation prussiate and ammonia nitrogen, makes its oxygenolysis become carbonic acid gas and nitrogen, and its reaction mechanism can be represented with following reaction formula.
The direct oxidation reaction:
CN-+2OH--2e→CNO-+H2O
2CNO-+4OH--6e→2CO2↑+N2↑+2H2O
2NH3+6OH--6e→N2↑+6H2O
The indirect oxidation reaction:
2Cl-→Cl2+2e-
Cl2+H2O→HClO+HCl
2CN-+5HClO+2H+→2CO2↑+N2↑+5HCl+H2O
2NH3+3HClO→N2↑+3HCl+3H2O
2NH4++2OH-+3HClO→N2↑+3HCl+5H2O
The present invention has following advantage and beneficial effect:
The present invention proposes a kind of method of utilizing the catalytic oxidation method to handle prussiate and ammonia nitrogen in the gold smelting waste water, the total cyanogen of waste water, the ammonia nitrogen according to the present invention after the processing can reach " integrated wastewater discharge standard " (GB8978-1996) requirement of the total cyanogen compound≤0.5mg/L of defined, ammonia nitrogen≤15mg/L in the first discharge standard.Simultaneously, this method has that flow process is simple, reduced investment, floor space is little and characteristics such as non-secondary pollution.
Four. description of drawings
Fig. 1 is that the present invention utilizes the catalytic oxidation method to handle the schematic flow sheet of the method for prussiate and ammonia nitrogen in the gold smelting waste water.
Five. embodiment
Below in conjunction with accompanying drawing 1 and embodiment the present invention is done further detailed description.
Embodiment 1
Adopt the method for utilizing the catalytic oxidation method to handle prussiate and ammonia nitrogen in the gold smelting waste water disclosed by the invention; Handle Fujian gold smelting factory purification waste water, raw water quality is: pH3.46, CNT40.52mg/L, NH3-N310.30mg/L, Cl 11.41g/L.Get 1L waste water and regulate pH value to 7.50 with lime earlier; Then said waste water is introduced in the electrocatalysis oxidation reaction device; To the electrifying electrodes in the reactor drum, main technologic parameters is following in the catalytic oxidation process: polar plate spacing 2cm, current density 26.6mA/cm2, electrolysis voltage 5V.Behind the electrolysis time 90min, the water outlet concentration of cyanide is that 0.12mg/L, water outlet ammonia nitrogen concentration are 5.50mg/L, and total cyanogen and ammonia nitrogen all reach " integrated wastewater discharge standard " (GB8978-1996) first discharge standard.
Embodiment 2
Adopt the method for utilizing the catalytic oxidation method to handle prussiate and ammonia nitrogen in the gold smelting waste water disclosed by the invention; Handle Fujian gold smelting factory electrolysis wastewater, raw water quality is: pH12.58, CNT155.32mg/L, NH3-N643.18mg/L, Cl 0g/L.Get 1L waste water earlier with sulphur acid for adjusting pH value to 9.50; Add a certain amount of sodium-chlor then; Make that cl concn reaches 10.00g/L in the waste water; At last said waste water is introduced in the electrocatalysis oxidation reaction device, to the electrifying electrodes in the reactor drum, main technologic parameters is following in the catalytic oxidation process: polar plate spacing 2cm, current density 26.6mA/cm2, electrolysis voltage 5V.Behind the electrolysis time 150min, the water outlet concentration of cyanide is that 0.20mg/L, water outlet ammonia nitrogen concentration are 6.51mg/L, and total cyanogen and ammonia nitrogen all reach " integrated wastewater discharge standard " (GB8978-1996) first discharge standard.
Embodiment 3
Adopt the method for utilizing the catalytic oxidation method to handle prussiate and ammonia nitrogen in the gold smelting waste water disclosed by the invention; Handle Fujian gold smelting factory and smelt comprehensive wastewater, raw water quality is: pH6.75, CNT46.66mg/L, NH3-N357.42mg/L, Cl 15.70g/L.1L waste water is introduced in the electrocatalysis oxidation reaction device, and to the electrifying electrodes in the reactor drum, main technologic parameters is following in the catalytic oxidation process: polar plate spacing 2cm, current density 26.6mA/cm2, electrolysis voltage 5V.Behind the electrolysis time 90min, the water outlet concentration of cyanide is that 0.14mg/L, water outlet ammonia nitrogen concentration are 5.00mg/L, and total cyanogen and ammonia nitrogen all reach " integrated wastewater discharge standard " (GB8978-1996) first discharge standard.
Claims (2)
1. utilize the catalytic oxidation method to handle the method for prussiate and ammonia nitrogen in the gold smelting waste water, it is characterized in that: the first step: if the waste water ph that needs to handle, then adds alkali or acid adjusting waste water ph to 6 ~ 12 less than 6 or greater than 12 in waste water; Second step: said waste water is introduced in the electrocatalysis oxidation reaction device; To the electrifying electrodes in the reactor drum; Remove prussiate and ammonia nitrogen in the waste water through the catalytic oxidation method; Main technologic parameters is following in the catalytic oxidation process: polar plate spacing 0.5cm ~ 10cm, current density 10mA/cm2 ~ 100mA/cm2, electrolysis voltage 2V ~ 20V, electrolysis time is confirmed by prussiate in the waste water and ammonia nitrogen concentration, generally is controlled at 30min ~ 360min.
2. according to the described method of utilizing the catalytic oxidation method to handle prussiate and ammonia nitrogen in the gold smelting waste water of right 1; It is characterized in that: the first step:, then in waste water, add villaumite and regulate in the waste water chlorine ion concentration greater than more than the 2g/L if chlorine ion concentration is less than 2g/L in the said waste water; Second step: said waste water is introduced in the electrocatalysis oxidation reaction device; To the electrifying electrodes in the reactor drum; Remove prussiate and ammonia nitrogen in the waste water through the catalytic oxidation method; Main technologic parameters is following in the catalytic oxidation process: polar plate spacing 0.5cm ~ 10cm, current density 10mA/cm2 ~ 100mA/cm2, electrolysis voltage 2V ~ 20V, electrolysis time is confirmed by prussiate in the waste water and ammonia nitrogen concentration, generally is controlled at 30min ~ 360min.
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| CN2012101992166A CN102701334A (en) | 2012-06-15 | 2012-06-15 | Method for treating cyanide and ammonia nitrogen in gold smelting wastewater through electrocatalytic oxidation process |
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| CN2012101992166A CN102701334A (en) | 2012-06-15 | 2012-06-15 | Method for treating cyanide and ammonia nitrogen in gold smelting wastewater through electrocatalytic oxidation process |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103896373A (en) * | 2014-02-28 | 2014-07-02 | 重庆大学 | Method for treating ammonia nitrogen in electrolytic manganese wastewater |
| CN104341063A (en) * | 2013-07-29 | 2015-02-11 | 黄明科 | Efficient treatment technology for electroplating sewage |
| CN107176760A (en) * | 2017-06-26 | 2017-09-19 | 中电环保股份有限公司 | A kind of high salt advance for the treatment of process of cyanide-bearing effluent and processing system |
| CN108101163A (en) * | 2017-12-21 | 2018-06-01 | 衢州华友钴新材料有限公司 | It is a kind of that valuable metal is recycled from industrial wastewater and drops ammonia nitrogen and the method for COD |
| CN110040886A (en) * | 2019-05-09 | 2019-07-23 | 浙江巨化技术中心有限公司 | A kind of utilization method of sodium sulfate wastewater |
| CN115504582A (en) * | 2022-11-09 | 2022-12-23 | 中船第九设计研究院工程有限公司 | Wastewater hardness removing device for gold smelting |
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2012
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Patent Citations (3)
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|---|---|---|---|---|
| CN1057245A (en) * | 1990-03-15 | 1991-12-25 | 杨新玉 | Purifier for cyanogen removal reaches the technological process for purifying of removing prussiate from waste liquid |
| JP2005246109A (en) * | 2004-03-01 | 2005-09-15 | Sumitomo Metal Mining Co Ltd | Cyanide-containing wastewater treatment method containing ammonia nitrogen |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104341063A (en) * | 2013-07-29 | 2015-02-11 | 黄明科 | Efficient treatment technology for electroplating sewage |
| CN103896373A (en) * | 2014-02-28 | 2014-07-02 | 重庆大学 | Method for treating ammonia nitrogen in electrolytic manganese wastewater |
| CN103896373B (en) * | 2014-02-28 | 2015-12-09 | 重庆大学 | A kind of method processing ammonia nitrogen in Electrolytic Manganese Wastewater |
| CN107176760A (en) * | 2017-06-26 | 2017-09-19 | 中电环保股份有限公司 | A kind of high salt advance for the treatment of process of cyanide-bearing effluent and processing system |
| CN108101163A (en) * | 2017-12-21 | 2018-06-01 | 衢州华友钴新材料有限公司 | It is a kind of that valuable metal is recycled from industrial wastewater and drops ammonia nitrogen and the method for COD |
| CN108101163B (en) * | 2017-12-21 | 2020-11-03 | 衢州华友钴新材料有限公司 | Method for recovering valuable metals and reducing ammonia nitrogen and COD (chemical oxygen demand) from industrial wastewater |
| CN110040886A (en) * | 2019-05-09 | 2019-07-23 | 浙江巨化技术中心有限公司 | A kind of utilization method of sodium sulfate wastewater |
| CN115504582A (en) * | 2022-11-09 | 2022-12-23 | 中船第九设计研究院工程有限公司 | Wastewater hardness removing device for gold smelting |
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Application publication date: 20121003 |