CN108862714A - A kind of chemical precipitation-gas floatation process removes cyanogen and Treatment of cyanogen-contained wastewater - Google Patents
A kind of chemical precipitation-gas floatation process removes cyanogen and Treatment of cyanogen-contained wastewater Download PDFInfo
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- 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
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- 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
- C02F1/24—Treatment of water, waste water, or sewage by flotation
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- 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
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- 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
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
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- 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
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- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
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- 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
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/16—Nature of the water, waste water, sewage or sludge to be treated from metallurgical processes, i.e. from the production, refining or treatment of metals, e.g. galvanic wastes
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2301/00—General aspects of water treatment
- C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
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Abstract
The invention discloses a kind of chemical precipitation-gas floatation processes to remove cyanogen and Treatment of cyanogen-contained wastewater, including chemical precipitation-air bearing, hydrogen peroxide advanced oxidation and coagulation-settlement process combination.PH value of waste water is adjusted to 6-7 first, soluble zinc salt and collecting agent are successively added under stirring, generates deposit, then dissolved air flotation；PH value of waste water is adjusted to 9-11, hydrogen peroxide is added and advanced oxidation is carried out to Pollutants in Wastewater, finally utilize suspended particulate substance remaining in coagulant sedimentation removal waste water.The methods of chemical precipitation, advanced oxidation and coagulant precipitation are combined together by this method according to cyanide wastewater feature, carry out advanced treating to cyanide wastewater, cyanogen, heavy metal and COD are significantly reduced after processing.The present invention has the advantages that valuable metal and cyanogen, corrosive medium be not high, system is stable in recoverable wastewater, without secondary pollution, management is simple, is easy to implement industrial application, is suitable for the industries cyanide wastewater such as gold mine, plating and coking.Treated, and waste water can be used as the recycling of recycled water return system or qualified discharge.
Description
Technical field
The present invention relates to a kind of processing method except cyanogen and cyanide wastewater, especially a kind of chemical precipitation-gas floatation process removal
Cyanogen and Treatment of cyanogen-contained wastewater, belong to technical field of waste water processing.
Background technique
Extraction of gold by cyanidation is current main Gold Extracting Methods, and the 80% of world's gold output is using this according to statistics
Technique obtains.Cyanidation gold-extracted to generate a large amount of cyanide wastewater, this kind of waste water is in addition to containing cyanogen and its derivative, also containing a certain amount of
The heavy metal ion such as copper, zinc, lead.So the emphasis of these wastewater treatments is not only to reduce cyanogen concentration, while being also required to heavy metal
Concentration is up to standard.No matter that index exceeding standard, can all cause greatly to destroy to ecological environment.Cyanogen is contained for special high concentration
Waste water（CN-1000 mg/L -2000mg/L of concentration）, commonly used technology is acidification recycling HCN at present, after recycling in waste water
Cyanogen concentration can be down to 5-50mg/L, need to be further processed.This method can recycle a certain amount of copper ashes, but the rate of recovery simultaneously
It is insufficient.Solvent extraction is also applied to processing extra heavy concentration cyanide wastewater, and principle is in amine extractant extraction water
The metals cyanogen complex ion such as copper, zinc is contained a large amount of free cyanogens in treated water, therefore can be recycled with return system, is taken this
Realize lean solution complete alternation.Solvent extraction opens a way processing system in application, since solvent loss is larger in waste water, operating cost
Height, therefore the example of practical application is less.For CN-Concentration is the general high cyanide containing wastewater of 300mg/L-700mg/L, specially
Sharp " a kind of high concentration cyanide wastewater processing method "（CN 102515388 B）It is sub- to disclose acidification-precipitation method removal cyaniding
Then copper makes Cyanide in Waste Water reach discharge standard with three sections of Pomolio-Celdecor process.This method PH values are required 3 hereinafter, corrosivity is strong,
Operation control requires high.As it can be seen that for general high cyanide containing wastewater, if it is possible to the mild solution environmental in neutral range
In recycling metal ion and cyanogen as much as possible, can not only reduce the processing load of follow-up link, but also can produce certain warp
Ji benefit, sustainable development and gold environmental mining protection to gold industry are of great significance.
Cyanide electroplating is one of most common plating, is mainly used for zinc-plated, lead plating, copper facing etc., can be produced during these
Raw a large amount of cyanide wastewater.Every liter of total cyanogen concentration of this kind of waste water is up to hundreds of milligrams.In addition to free cyanogen, copper is also contained in waste water
The complex ions such as cyanogen, zinc cyanogen, silver-colored cyanogen.Therefore the main Con trolling index of electroplating cyanic waste water is cyanogen and various heavy metal ion.It is molten
The methods of agent extraction, acidification recycling limit it in the lesser electroplating wastewater of the scale of construction since complex process, control requirement are high
Application in processing.The broken cyanides such as ozone high grade oxidation, Yin Kefa, chlor-alkali method can not recycle cyanogen and metal in waste water.
Generally, coking cyanide wastewater first has to by recycling operation area, including desulfurization workshop section, relieving haperacidity workshop section etc., by this
Cyanogen concentration will be greatly reduced in water after a little operations.Amount containing cyanogen is usually between 8mg/L~20mg/L in draining outside environmentally friendly process,
If the methods of the application acidification recycling of this part cyanogen or solvent extraction recycling, economically unreasonable.If using method for oxidation
Direct broken cyanide then needs the reaction time long, and oxidant demand is big.
Summary of the invention
Technical problem：The cyanide wastewater that the purpose of the present invention is smelt, be electroplated for gold mine and the industries such as coking generate, mesh
The recycling of HCN existing for pre-treating method is insufficient, and equipment and control require the deficiencies of high, provides a kind of chemical precipitation-gas floatation process and removes
Cyanogen and Treatment of cyanogen-contained wastewater.
Technical solution：A kind of chemical precipitation-gas floatation process of the present invention removes cyanogen and Treatment of cyanogen-contained wastewater, including walks as follows
Suddenly：
（1）In pretreatment reaction pond, cyanide wastewater is stirred with 300 revs/min, according to on-line checking cyanide wastewater
PH value is slowly added dilute sulfuric acid in whipping process into cyanide wastewater, adjusts pH value to 6-7；
（2）In the case where continuing stirring, soluble zinc salt is added into cyanide wastewater, after completely dissolution, then into cyanide wastewater
Metal cyanogen complex ion collecting agent is added, cyanide wastewater reaction is made to generate flocculent deposit；
（3）The cyanide wastewater that reaction generates flocculent deposit is imported in air-flotation separation equipment and carries out air bearing, the froth pulp of floating
For the deposit of the complex ion of cyanogen containing metal；
（4）The remaining underflow waste water of dissolved air flotation is imported into oxidation pond, lye is added by pH value of waste water and is adjusted to 9-11, then add
Enter hydrogen peroxide further progress oxidation processes, the processing time is 60-180min；
（5）Cyanide wastewater after oxidation is imported into coagulation reaction tank, is successively added under 175 revs/min of revolving speed stirrings solidifying
Poly- agent and flocculant carry out coagulating, and waste water enters sedimentation basin standing sedimentation 15-120min after coagulation；
（6）Supernatant liquid after precipitating returns to recycling or qualified discharge in the technological process of production.
The soluble zinc salt is zinc sulfate, zinc nitrate, zinc chloride or zinc carbonate.
The metal cyanogen complex ion collecting agent is quaternary ammonium salt substance.
The soluble zinc salt dosage determines by the cyanogen content that dissociates in waste water, soluble zinc salt and free cyanogen molar ratio
It is 1：3.
The dosage of the metal cyanogen complex ion collecting agent is determined according to metal cyanogen complex ion content in waste water；According to every
Ton waste water 100g metal cyanogen complex ion collecting agent adds, and flocculent deposit tests underwater gold category cyanogen complex ion residual volume after being formed, such as
Fruit is higher than processing requirement, continues to add collecting agent, until at or below processing requirement.
The air-flotation separation equipment is mining flotation device, flotation column or water process airfloat equipment.
The lye is sodium hydroxide solution or milk of lime.
The hydrogen peroxide dosage is determined according to cyanogen remaining in waste water and COD；First add 3g/m3Dioxygen
Water oxidized waste water measures wherein remaining cyanogen and COD, gradually increases hydrogen peroxide dosage, until at or below place
Reason requires.
The flocculating agent is polymer-inorganic salt flocculating agent, additive amount 5-10g/m3；The flocculant is polypropylene
Amide, additive amount 1-3g/m3。
Beneficial effect：By adopting the above-described technical solution, the present invention is using chemical precipitation-gas floatation process removal cyanogen and contains cyanogen
Waste water effectively removes the cyanogen and its derivative in cyanide wastewater using zinc salt and quaternary ammonium salt as collecting agent, recycling metal from
Son reduces the pollutional load of subsequent oxidation processing.Hydrogen peroxide can aoxidize the organic matter in water body, keep COD up to standard.This method
High cyanide containing wastewater can be not only handled, but also is also applied for middle low cyanide wastewater processing, collecting agent used is cheap,
Remarkable in economical benefits.Compared with other cyanogen recycle and remove the method for cyanogen, solution environmental is mild, and corrosive medium is weak, quickly high
Effect, it is easy to operate, it is convenient for management, there is wide applicability in the art.
Specific embodiment
A kind of chemical precipitation-gas floatation process of the present invention removes cyanogen and Treatment of cyanogen-contained wastewater, and specific step is as follows：
（1）In pretreatment reaction pond, cyanide wastewater is stirred with 300 revs/min, according to the pH value of waste water, is being stirred
Dilute sulfuric acid is slowly added into cyanide wastewater in the process, adjusts pH value to 6-7；
（2）In the case where continuing stirring, soluble zinc salt is added into cyanide wastewater, after completely dissolution, then into cyanide wastewater
Metal cyanogen complex ion collecting agent is added, cyanide wastewater reaction is made to generate flocculent deposit；
The soluble zinc salt is zinc sulfate, zinc nitrate, zinc chloride or zinc carbonate；Soluble zinc salt dosage is by waste water
Free cyanogen content determines that soluble zinc salt and free cyanogen molar ratio are 1：3.
The metal cyanogen complex ion collecting agent is quaternary ammonium salt substance.The metal cyanogen complex ion collecting agent adds
Amount is determined according to metal cyanogen complex ion content in waste water；It is added according to waste water 100g metal cyanogen complex ion collecting agent per ton, it is cotton-shaped
Precipitating tests underwater gold category cyanogen complex ion residual volume after being formed, if being higher than processing requirement, continues to add collecting agent, until reaching
Or it is lower than processing requirement.
（3）The cyanide wastewater that reaction generates flocculent deposit is imported in air-flotation separation equipment and carries out air bearing, the foam of floating
Product is the deposit of the complex ion of cyanogen containing metal；
The air-flotation separation equipment is mining flotation device, flotation column or water process airfloat equipment.
（4）The remaining underflow waste water of dissolved air flotation is imported into oxidation pond, lye is added by pH value of waste water and is adjusted to 9-11, then
It adds into hydrogen peroxide further progress oxidation processes, the processing time is 60-180min；
The lye is sodium hydroxide solution or milk of lime.
The hydrogen peroxide dosage is determined according to cyanogen remaining in waste water and COD；First add 3g/m3Dioxygen
Water oxidized waste water measures wherein remaining cyanogen and COD, gradually increases hydrogen peroxide dosage, until at or below place
Reason requires.
（5）Cyanide wastewater after oxidation is imported into coagulation reaction tank, is successively thrown under 175 revs/min of revolving speed stirrings
Flocculating agent and flocculant is added to carry out coagulating, waste water enters sedimentation basin standing sedimentation 15-120min after coagulation；The cohesion
Agent is polymer-inorganic salt flocculating agent, additive amount 5-10g/m3；The flocculant is polyacrylamide, additive amount 1-3g/
m3。
（6）Supernatant liquid after precipitating returns to recycling or qualified discharge in the technological process of production.
Below with reference to embodiment, the present invention is further illustrated：
Embodiment 1,
Certain gold ore cyanide wastewater, pH value 11, total cyanogen 3588.1mg/L, additionally containing a small amount of copper, zinc, gold, silver etc.
Ion.Total cyanogen requires to be less than 0.5mg/L after processing, and COD is less than 30mg/L.
（1）In pretreatment reaction pond, on-line checking pH value of waste water, with 300 revs/min of stirring waste water, in whipping process
It is slowly added dilute sulfuric acid and adjusts pH value of waste water to 6.1；
（2）Continue stirring, first adds zinc nitrate and octadecyltrimethylammonium chloride in backward waste water, dosage is respectively
2.31 kg/m3And 3.12kg/m3, reaction, which generates, to be precipitated；
（3）Waste water is imported in mining flotation device, air flotation, froth pulp is the deposit of the complex ion of cyanogen containing metal；
（4）The remaining underflow waste water of dissolved air flotation imports oxidation pond, adjusts pH value of waste water to 9.3 using milk of lime, adds 10%
Hydrogen peroxide 10g/ m3, reaction time 60min；
（5）Waste water is imported into coagulation reaction tank, successively adds aluminium polychloride 5g/m in the case where 175 revs/min of revolving speeds stir3And wadding
Solidifying 1 g/m of agent polyacrylamide3Coagulating is carried out, waste water enters sedimentation basin standing sedimentation 15min after coagulation；
（6）Supernatant liquid after precipitating reaches processing requirement, returns to the technological process of production.
Embodiment 2,
Certain electroplating cyanic waste water, pH value 10, total cyanogen 150mg/L, chromium 150mg/L.Total cyanogen requires to be less than after processing
0.5mg/L, COD are less than 50mg/L, and total chromium is less than 0.1 mg/L.
（1）On-line checking pH value of waste water is slowly added dilute sulfuric acid in whipping process and adjusts pH value of waste water to 6.9；
（2）Continue stirring, dodecyl trimethyl ammonium chloride, dosage 2.48kg/m are added into waste water3, reaction production
Raw precipitating；
（3）Waste water is imported in mine flotation column, air flotation, froth pulp is the deposit containing cyanogen.
（4）The remaining underflow waste water of dissolved air flotation imports oxidation pond, adjusts pH value of waste water to 10.7 using sodium hydroxide,
Add 15% hydrogen peroxide 7g/ m3, reaction time 180min；
（5）Waste water is imported into coagulation reaction tank, aluminium polychloride 10g/m is successively added under stirring3、With flocculant polyacrylamide
3 g/m3Coagulating is carried out, waste water enters sedimentation basin standing sedimentation 120min after coagulation；
（6）Supernatant liquid qualified discharge after precipitating.
Embodiment 3,
Certain coking cyanide wastewater, pH value 10, total cyanogen 20mg/L, COD 12000mg/L.Total cyanogen requires to be less than after processing
0.5mg/L, COD are less than 300mg/L.
（1）On-line checking pH value of waste water is slowly added dilute sulfuric acid in whipping process and adjusts pH value of waste water to 6.5；
（2）Continue stirring, first adds double octadecyltrimethylammonium chloride, dosage 1.13kg/m in backward waste water3,
Reaction generates precipitating；
（3）Waste water is imported in airfloat equipment, air flotation, froth pulp is the deposit containing cyanogen；
（4）The remaining underflow waste water of dissolved air flotation imports oxidation pond, adjusts pH value of waste water to 10.5 using sodium hydroxide, adds
15% hydrogen peroxide 10g/ m3, reaction time 120min；
（5）Waste water is imported into coagulation reaction tank, aluminium polychloride 7.4g/m is successively added under stirring3、With flocculant polyacrylamide
1.5 g/m of amine3, waste water enters sedimentation basin standing sedimentation 30min after coagulation；
（6）Supernatant liquid after precipitating is discharged into subsequent biochemical processing links.
Claims (10)
1. a kind of chemical precipitation-gas floatation process removes cyanogen and Treatment of cyanogen-contained wastewater, which is characterized in that include the following steps：
(1) in pretreatment reaction pond, with 300 revs/min of stirring cyanide wastewater, in whipping process slowly into cyanide wastewater
Dilute sulfuric acid is added, adjusts pH value to 6-7；
(2) in the case where continuing stirring, soluble zinc salt is added into cyanide wastewater, after completely dissolution, then into cyanide wastewater
Metal cyanogen complex ion collecting agent is added, cyanide wastewater reaction is made to generate flocculent deposit；
(3) cyanide wastewater containing flocculent deposit is imported in air-flotation separation equipment and carries out air bearing, the froth pulp of floating is containing gold
Belong to the deposit of cyanogen complex ion；
(4) the remaining underflow waste water of dissolved air flotation is imported into oxidation pond, adds lye for pH value of waste water and be adjusted to 9-11, then adds
Enter hydrogen peroxide further progress oxidation processes, the processing time is 60-180min；
(5) cyanide wastewater after oxidation is imported into coagulation reaction tank, is successively added under 175 revs/min of revolving speed stirrings solidifying
Poly- agent and flocculant carry out coagulating, and waste water enters sedimentation basin standing sedimentation 15-120min after coagulation；
(6) the supernatant liquid after precipitating returns to recycling or qualified discharge in the technological process of production.
2. a kind of chemical precipitation-gas floatation process according to claim 1 removes cyanogen and Treatment of cyanogen-contained wastewater, feature exists
In：The soluble zinc salt is zinc sulfate, zinc nitrate, zinc chloride or zinc carbonate.
3. a kind of chemical precipitation-gas floatation process according to claim 1 removes cyanogen and Treatment of cyanogen-contained wastewater, feature exists
In：The metal cyanogen complex ion collecting agent is quaternary ammonium salt substance.
4. a kind of chemical precipitation-gas floatation process according to claims 1 and 2 removes cyanogen and Treatment of cyanogen-contained wastewater, feature
It is：The soluble zinc salt dosage determines that soluble zinc salt is with free cyanogen molar ratio by the cyanogen content that dissociates in waste water
1：3.
5. removing cyanogen and Treatment of cyanogen-contained wastewater, feature with a kind of chemical precipitation-gas floatation process described in 3 according to claim 1
It is：The dosage of the metal cyanogen complex ion collecting agent is determined according to metal cyanogen complex ion content in waste water；According to per ton
Waste water 100g metal cyanogen complex ion collecting agent adds, and flocculent deposit tests underwater gold category cyanogen complex ion residual volume after being formed, if
Higher than processing requirement, continue to add collecting agent, until at or below processing requirement.
6. a kind of chemical precipitation-gas floatation process according to claim 1 removes cyanogen and Treatment of cyanogen-contained wastewater, feature exists
In：The air-flotation separation equipment is mining flotation device, flotation column or water process airfloat equipment.
7. a kind of chemical precipitation-gas floatation process according to claim 1 removes cyanogen and Treatment of cyanogen-contained wastewater, feature exists
In：The lye is sodium hydroxide solution or milk of lime.
8. a kind of chemical precipitation-gas floatation process according to claim 1 removes cyanogen and Treatment of cyanogen-contained wastewater, feature exists
In：The hydrogen peroxide dosage is determined according to cyanogen remaining in waste water and COD.First add 3g/m3Hydrogen peroxide oxidation
Waste water measures wherein remaining cyanogen and COD, gradually increases hydrogen peroxide dosage, until wanting at or below processing
It asks.
9. a kind of chemical precipitation-gas floatation process according to claim 1 removes cyanogen and Treatment of cyanogen-contained wastewater, feature exists
In：The flocculating agent is polymer-inorganic salt flocculating agent, additive amount 5-10g/m3。
10. a kind of chemical precipitation-gas floatation process according to claim 1 removes cyanogen and Treatment of cyanogen-contained wastewater, feature exists
In：The flocculant is polyacrylamide, additive amount 1-3g/m3。
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| CN115583766A (en) * | 2022-11-04 | 2023-01-10 | 中国科学院过程工程研究所 | Method for treating cyanide-containing wastewater |
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