CN109502811A - The flocculation sedimentation purification method of Thiocyanate ion in a kind of cyanide wastewater - Google Patents
The flocculation sedimentation purification method of Thiocyanate ion in a kind of cyanide wastewater Download PDFInfo
- Publication number
- CN109502811A CN109502811A CN201811483901.5A CN201811483901A CN109502811A CN 109502811 A CN109502811 A CN 109502811A CN 201811483901 A CN201811483901 A CN 201811483901A CN 109502811 A CN109502811 A CN 109502811A
- Authority
- CN
- China
- Prior art keywords
- cyanide
- thiocyanate ion
- flocculation sedimentation
- purification method
- cyanide 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.)
- Pending
Links
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
- 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
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
-
- 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
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F2001/007—Processes including a sedimentation step
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
- C02F2101/18—Cyanides
Abstract
The present invention relates to a kind of flocculation sedimentation purification methods of Thiocyanate ion in cyanide wastewater.It is studied by the purification process to various concentration cyanide wastewater, it is determined that the technological parameters such as solution ph, ferric sulfate, bodied ferric sulfate dosage；First acidified processing recovery of cyanide, cyanide then remaining using ferric sulphate precipitate filtering removal remove Thiocyanate ion using bodied ferric sulfate flocculation sedimentation after filtrate addition milk of lime adjusts pH to cyanide wastewater.The method solves Thiocyanate ion in gold cyaniding smelting wastewater and accumulates; cause lean solution can not normal reuse; and then the problem of influencing normal smelting process, it ensure that gold Cyanide Leaching and subsequent adsorbtion, replace being normally carried out for process, effectively improve smelting recovery.
Description
Technical field
The present invention relates to the precipitation and purification methods of thiocyanate ion in cyanide wastewater, belong to technology for treating industrial waste water neck
Domain.
Background technique
Currently, gold mainly uses hydrometallurgical processes directly to refine from gold sulphide ores, only small part is by pyrogenic process smelting
It is obtained in refining non-ferrous metal byproduct.Cyaniding and leaching process due to production cost is low, the rate of recovery is high, to the adaptable of ore
Etc. advantages, be the main method of current golden production and leading position will be occupied within considerable time.
Although having many advantages using extraction of gold by cyanidation, which can generate a large amount of de- golden lean solutions in process of production.
It is recycled although can be returned by lean solution and leach process, due to containing sulfide mineral, Cyanide Leaching in gold mine mostly
In the process, sulfide mineral can react with cyanide, and final element sulphur can be existed in solution with the formation of thiocyanate, and with
It takes off the recycling of gold lean solution and constantly accumulates.The presence of a large amount of Thiocyanate ions can reduce the leaching of gold in Cyanide Leaching liquid
Rate, in addition, the presence of thiocyanate can reduce golden adsorption rate and adsorption capacity and cause resin when using resin absorption technique
" poisoning " shortens its service life.Therefore, research and development effectively remove the technique of the Thiocyanate ion in cyanide wastewater, for gold
It is particularly important for industry.
Acidization is otherwise known as and is acidified volatilization-alkali absorption method (AVR).The technique is that industrial application is more wide at present
General Treatment of cyanogen-contained wastewater makes to dissociate in waste water the basic principle is that alkali is added in sulfuric acid and protected into cyanide wastewater
Cyanide and the hydrolysis containing cyanide complex generate HCN, while metal ion is gone by forming cyanide or rhodanate precipitating
It removes；Its process can be indicated with following equation:
CuCN+SCN-→CuSCN↓+CN- (3)
The HCN generated after acidification is absorbed after air stripping using sodium hydroxide solution, and the Cymag of generation returns
Leaching metal working sequence is reused；It is recycled after remaining on the concentrated filtering of the sediment in water；Processed waste water is using in lime and residual
Acid is discharged into Tailings Dam natural degradation or direct Returning process.When using the process, the thiocyanate radical in cyanide wastewater is final
Precipitating is generated in the form of CuSCN；But in Cyanide Leaching lean solution, the content of thiocyanate radical is much higher than the amount of copper ion, even if adopting
Thiocyanate radical can not still be completely removed with acidification technique；So the lean solution thiocyanic acid after being recycled for multiple times, in solution again
Root can build up to higher concentration.
When using the oxidative degradation process Treatment of Cyanide-containing Wastewater such as alkaline chlorination process, the cyanide in waste water is oxidized to cyanic acid
Salt, then further oxidation generates CO2And nitrogen, to achieve the purpose that purify sewage.The process can use following equation table
Show:
ClO-+H2O+CN-→CNCl+2OH- (4)
CNCl+2OH-→CNO-+Cl-+H2O (5)
2CNO-+3ClO-+H2O→2CO2↑+N2↑+2OH-+3Cl- (6)
In actual production, to guarantee that the complete oxidation of cyanide is deviate from, the additive amount of oxidant is usually theory in production
1.5~2 times of amount, therefore cause the technique reagent consumption amount larger, processing cost is higher.Further, since thiocyanate radical is steady
It is qualitative to be much higher than cyanide, such as it is aoxidized, it is necessary to increase dosing, cause that the production cost increases；To limit
Application of the oxidation technology in thiocyanate wastewater treatment.
Summary of the invention
The technical problem to be solved by the invention is to provide thiocyanates in a kind of simple, efficiently, inexpensive cyanide wastewater
The flocculation sedimentation purification method of ion.
Technical scheme is as follows:
The flocculation sedimentation purification method of Thiocyanate ion in a kind of cyanide wastewater, it is characterised in that according to the following steps into
Row:
1) concentrated sulfuric acid, is added in cyanide wastewater and adjusts pH value to 2-3；
2), after acidifying solution filtering, excess soluble molysite is added into filtrate for free cyanogen to be removed in depth, is sufficiently stirred
After filter；
3) milk of lime, is added in filtrate and adjusts pH value to 5-9, stirring, is added bodied ferric sulfate or poly-ferric chloride is inhaled
Attached thiocyanate ion；
4) abandoned mine powder, is added and stirs further flocculating setting；
5) it is filtered after, settling.
Soluble ferric iron salt preferable amount is 1~2 times of free sodium cyanide gross mass in step 2).
In step 3) bodied ferric sulfate or poly-ferric chloride preferable amount be thiocyanate gross mass in waste water 0.65~
1.28 again.
The preferred control method that useless mineral powder amount is added in step 4) is: stirring flocculating setting to solution red disappears.
Soluble ferric iron salt is preferably ferric sulfate.
Liquid passes through aeration stripping, carrier gas regenerating sodium cyanide after lye adsorbs after step 1) acidification.
The present invention is dropped using bodied ferric sulfate absorption, flocculation, precipitating removal thiocyanate radical to purify Cyanide Leaching liquid
Influence of the low lean solution reuse to smelting process.
Bodied ferric sulfate is a kind of inorganic polymer flocculant haveing excellent performance, and molecular structure is huge, and adsorption capacity is strong,
It has been widely used in industrial waste water purifying process field.The present invention utilizes SCN?And Fe3+Stable complex can be formed, is led to
Chain macromolecule bodied ferric sulfate is crossed to adsorb it；It is free by the removal of the methods of acidification aeration and molysite complexing simultaneously
Cyanogen, to avoid CN?With SCN?Competitive Adsorption occurs on polyaluminum sulfate iron molecule, to reduce the dosage of bodied ferric sulfate and mention
The removal rate of high thiocyanate radical；Finally SCN has been adsorbed using the assistance of abandoned mine powder?Bodied ferric sulfate flocculating setting, realize precipitating
Remove the purpose of thiocyanate radical.
The present invention is by a large number of experiments to factors such as ferric sulfate dosage, pH value, bodied ferric sulfate and miberal powder dosages to sulphur cyanogen
Acid group removal effect has carried out detailed investigation, it is determined that best agentia condition；After the process, thiocyanic acid in waste water
Root removal rate can reach 70% or more.Present invention process is simple, reagent consumption is few, equipment investment is low is suitable for popularization and application.
Compared with the existing technology, the present invention omits acidification-regenerating sodium cyanide process, directly carries out deep removal free cyanogen
Processing.
Specific embodiment
Embodiment 1
The de- golden lean solution 2L of Cyanide Leaching is weighed, thiocyanate radical concentration is 4.23g/L in liquid, and the concentrated sulfuric acid is added and adjusts solution
PH value is 2.5 or so, aeration stripping 1h, carrier gas regenerating sodium cyanide after lye adsorbs.Liquid filters to take filtrate 1.5L after acidification,
Solid sulphuric acid iron 12g is added, is filtered after stirring 30min.Taking filtrate 1L that milk of lime is added to adjust pH value is 7.5 or so, adds 6g solid
Body bodied ferric sulfate, is added the abandoned mine powder 300g that -400 mesh account for 80% or more after being sufficiently stirred, stirring flocculating setting is red to solution
Decoloration completes treatment process after filtering.Thiocyanate radical concentration is 0.68g/L in tail washings after processing, and theoretical removal rate reaches
83.9%.
Embodiment 2
The de- golden lean solution 2L of Cyanide Leaching is weighed, thiocyanate radical concentration is 5.81g/L in liquid, and concentrated sulfuric acid adjustment solution is added
PH value is 2.2 or so, aeration stripping 1h, carrier gas regenerating sodium cyanide after lye adsorbs.Liquid filters to take filtrate 1.5L after acidification,
Solid sulphuric acid iron 15g is added, is filtered after stirring 30min.Taking filtrate 1L that milk of lime is added to adjust pH value is 8.3 or so, adds 8g solid
Body bodied ferric sulfate, is added the abandoned mine powder 400g that -400 mesh account for 80% or more after being sufficiently stirred, stirring flocculating setting is red to solution
Decoloration completes treatment process after filtering.Thiocyanate radical concentration is 0.77g/L in tail washings after processing, and theoretical removal rate reaches
86.7%.
Claims (7)
1. the flocculation sedimentation purification method of Thiocyanate ion in a kind of cyanide wastewater, it is characterised in that follow the steps below:
1) concentrated sulfuric acid, is added in cyanide wastewater and adjusts pH value to 2-3；
2), after acidifying solution filtering, excess soluble molysite is added into filtrate and is used to that free cyanogen to be removed in depth, mistake after being sufficiently stirred
Filter；
3) milk of lime, is added in filtrate and adjusts pH value to 5-9, stirring, is added bodied ferric sulfate or poly-ferric chloride adsorbs sulphur
Cyanic acid ion；
4) abandoned mine powder, is added and stirs further flocculating setting；
5) it is filtered after, settling.
2. the flocculation sedimentation purification method of Thiocyanate ion in cyanide wastewater according to claim 1, it is characterised in that: step
It is rapid 2) in soluble ferric iron salt dosage be 1 ~ 2 times of free sodium cyanide gross mass.
3. the flocculation sedimentation purification method of Thiocyanate ion in cyanide wastewater according to claim 1, it is characterised in that: step
It is rapid 3) in bodied ferric sulfate or poly-ferric chloride dosage be 0.65 ~ 1.28 times of thiocyanate gross mass in waste water.
4. the flocculation sedimentation purification method of Thiocyanate ion in cyanide wastewater according to claim 1, it is characterised in that step
The rapid control method that useless mineral powder amount 4) is added is: stirring flocculating setting to solution red disappears.
5. the flocculation sedimentation purification method of Thiocyanate ion in cyanide wastewater according to claim 1 or 2 or 3 or 4, special
Sign is: soluble ferric iron salt is ferric sulfate.
6. the flocculation sedimentation purification method of Thiocyanate ion in cyanide wastewater according to claim 1 or 2 or 3 or 4, special
Sign is: liquid passes through aeration stripping, carrier gas regenerating sodium cyanide after lye adsorbs after step 1) acidification.
7. the flocculation sedimentation purification method of Thiocyanate ion in cyanide wastewater according to claim 5, it is characterised in that: step
Liquid passes through aeration stripping, carrier gas regenerating sodium cyanide after lye adsorbs after rapid 1) acidification.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811483901.5A CN109502811A (en) | 2018-12-06 | 2018-12-06 | The flocculation sedimentation purification method of Thiocyanate ion in a kind of cyanide wastewater |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811483901.5A CN109502811A (en) | 2018-12-06 | 2018-12-06 | The flocculation sedimentation purification method of Thiocyanate ion in a kind of cyanide wastewater |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109502811A true CN109502811A (en) | 2019-03-22 |
Family
ID=65752926
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811483901.5A Pending CN109502811A (en) | 2018-12-06 | 2018-12-06 | The flocculation sedimentation purification method of Thiocyanate ion in a kind of cyanide wastewater |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109502811A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110104829A (en) * | 2019-05-16 | 2019-08-09 | 山东金创金银冶炼有限公司 | A kind of processing method of cyanide containing wastewater |
| CN110902878A (en) * | 2019-11-28 | 2020-03-24 | 德州众和环保装备制造有限公司 | Method for reducing hardness of wastewater |
| CN112028309A (en) * | 2020-08-22 | 2020-12-04 | 长春黄金研究院有限公司 | Method for resource recovery of high-concentration cyanide-containing wastewater and treatment of intermediate product |
| CN112125320A (en) * | 2019-06-25 | 2020-12-25 | 湖南能也科技发展有限公司 | Method for desalting water from barren liquor or barren liquor generated in gold extraction process by cyanidation |
| CN112337963A (en) * | 2020-11-05 | 2021-02-09 | 中国石油化工股份有限公司 | Method and device for removing soil cyanide |
| CN113041542A (en) * | 2021-02-10 | 2021-06-29 | 河南科技大学 | Method for removing cyanide in gold smelting red slag by washing method |
| CN114377646A (en) * | 2022-03-02 | 2022-04-22 | 新疆有色金属研究所 | Process for purifying sulfur ions in water by tailing modified adsorption-based method |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1382641A (en) * | 2002-05-28 | 2002-12-04 | 萍乡钢铁有限责任公司 | Process for decyanadating water used to wash ammonia and naphthalene in pretreatment of coking by iron salt method |
| CN104876361A (en) * | 2015-05-14 | 2015-09-02 | 北京矿冶研究总院 | Method for comprehensively recovering cyanide-containing wastewater |
| CN105776765A (en) * | 2016-04-29 | 2016-07-20 | 广东新大禹环境科技股份有限公司 | Cyanide-containing wastewater treatment method |
| CN105776675A (en) * | 2016-05-31 | 2016-07-20 | 武汉钢铁股份有限公司 | Device and method for desulfuration and decyanation treatment of waste liquid generated in vacuum potassium carbonate desulfurization process |
| CN106977015A (en) * | 2017-04-30 | 2017-07-25 | 长春黄金研究院 | A kind of sulphur-bearing ore Cyanided gold tailings slurry harmless treatment and tail washings purification method |
-
2018
- 2018-12-06 CN CN201811483901.5A patent/CN109502811A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1382641A (en) * | 2002-05-28 | 2002-12-04 | 萍乡钢铁有限责任公司 | Process for decyanadating water used to wash ammonia and naphthalene in pretreatment of coking by iron salt method |
| CN104876361A (en) * | 2015-05-14 | 2015-09-02 | 北京矿冶研究总院 | Method for comprehensively recovering cyanide-containing wastewater |
| CN105776765A (en) * | 2016-04-29 | 2016-07-20 | 广东新大禹环境科技股份有限公司 | Cyanide-containing wastewater treatment method |
| CN105776675A (en) * | 2016-05-31 | 2016-07-20 | 武汉钢铁股份有限公司 | Device and method for desulfuration and decyanation treatment of waste liquid generated in vacuum potassium carbonate desulfurization process |
| CN106977015A (en) * | 2017-04-30 | 2017-07-25 | 长春黄金研究院 | A kind of sulphur-bearing ore Cyanided gold tailings slurry harmless treatment and tail washings purification method |
Non-Patent Citations (1)
| Title |
|---|
| 孙文武等主编: "《金属矿山环境保护与安全》", 31 July 2012, 冶金工业出版社 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110104829A (en) * | 2019-05-16 | 2019-08-09 | 山东金创金银冶炼有限公司 | A kind of processing method of cyanide containing wastewater |
| CN112125320A (en) * | 2019-06-25 | 2020-12-25 | 湖南能也科技发展有限公司 | Method for desalting water from barren liquor or barren liquor generated in gold extraction process by cyanidation |
| CN110902878A (en) * | 2019-11-28 | 2020-03-24 | 德州众和环保装备制造有限公司 | Method for reducing hardness of wastewater |
| CN112028309A (en) * | 2020-08-22 | 2020-12-04 | 长春黄金研究院有限公司 | Method for resource recovery of high-concentration cyanide-containing wastewater and treatment of intermediate product |
| CN112337963A (en) * | 2020-11-05 | 2021-02-09 | 中国石油化工股份有限公司 | Method and device for removing soil cyanide |
| CN113041542A (en) * | 2021-02-10 | 2021-06-29 | 河南科技大学 | Method for removing cyanide in gold smelting red slag by washing method |
| CN114377646A (en) * | 2022-03-02 | 2022-04-22 | 新疆有色金属研究所 | Process for purifying sulfur ions in water by tailing modified adsorption-based method |
| CN114377646B (en) * | 2022-03-02 | 2024-01-09 | 新疆有色金属研究所 | Technology for purifying sulfur ions in water by tailing modified adsorption base method |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109502811A (en) | The flocculation sedimentation purification method of Thiocyanate ion in a kind of cyanide wastewater | |
| CN103086548B (en) | Harmless comprehensive treatment method for cyanide-containing tailing pulp | |
| WO2014194664A1 (en) | Method for treating wastewater containing cyanides, thiocyanides and heavy metals | |
| CN104773863A (en) | Deep purification process for thallium-containing waste water | |
| CN103924102B (en) | Method for removing antimony from refractory gold ore and preparing cubic crystal sodium pyroantimonate | |
| CN102923874B (en) | Method for processing wastewater containing heavy metal ions | |
| CN106977015A (en) | A kind of sulphur-bearing ore Cyanided gold tailings slurry harmless treatment and tail washings purification method | |
| CN109264920A (en) | A kind of processing method of beneficiation wastewater zero-emission | |
| CN113088702B (en) | Method for recovering valuable elements from acid leaching solution of roasting slag of gold-containing sulfur concentrate | |
| Figueroa et al. | Recovery of gold and silver and removal of copper, zinc and lead ions in pregnant and barren cyanide solutions | |
| CN104787933B (en) | Treatment method for gold-smelting cyanide-containing wastewater | |
| CN102925899A (en) | Method for refining copper chloride etching waste liquor | |
| CA2647965C (en) | Nickel sulphide precipitation processes | |
| CN111847702B (en) | Method for treating cyanide-containing high-concentration ammonium sulfite wastewater | |
| CN111018212B (en) | Method for removing arsenic and chlorine from waste acid wastewater of metallurgical enterprise | |
| WO2023070556A1 (en) | Method for removing thallium from leach liquor of ash of lead smelting bottom-blown converter | |
| CN103007588B (en) | The method of the ammonium sulfate liquor purification that a kind of sintering flue gas ammonia method desulfurizing technique produces | |
| JP6597349B2 (en) | Blast furnace wastewater treatment method | |
| CN110668550B (en) | Gold concentrate non-cyanide beneficiation tailing liquid recycling treatment method | |
| CN112142070A (en) | Method for separating and recycling valuable metals in cyanide-containing wastewater | |
| JP6555182B2 (en) | Wastewater treatment method | |
| CN113816534B (en) | Process for deep impurity removal and resource recovery of gold smelting wastewater | |
| CN214141868U (en) | Harmless treatment system for gold smelting cyanide-and heavy metal-containing wastewater | |
| RU2340687C1 (en) | Method for neutralisation against residual cyanide of liquid phase of tail pulps after sorption of nonferrous metals | |
| CN214612692U (en) | System for recovering valuable elements from acid leaching solution of roasting slag of gold-containing sulfur concentrate |
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 | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20190322 |