CN102502994A - Method and system for treating cyanide-containing wastewater at low concentration - Google Patents
Method and system for treating cyanide-containing wastewater at low concentration Download PDFInfo
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- CN102502994A CN102502994A CN2011103512898A CN201110351289A CN102502994A CN 102502994 A CN102502994 A CN 102502994A CN 2011103512898 A CN2011103512898 A CN 2011103512898A CN 201110351289 A CN201110351289 A CN 201110351289A CN 102502994 A CN102502994 A CN 102502994A
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Abstract
The invention discloses a system and a method for treating cyanide-containing wastewater at low concentration. The method mainly comprises the following steps of: pre-treating the cyanide-containing wastewater at low concentration to remove large solid pollutant particles from the cyanide-containing wastewater at low concentration; performing membrane treatment to remove most cyanide ions, treating effluent obtained after treatment by the conventional NaClO oxidation method and other methods, and then discharging effluent which reaches the standard; and performing catalytic wet oxidation on concentrated liquor produced after the membrane treatment, and discharging the treated concentrated liquor which reaches the standard. The system mainly comprises a grating, a membrane treatment system, and catalytic wet oxidation treatment equipment. The invention has the advantages that: the cyanide-containing wastewater at low concentration is subjected to membrane treatment and then is treated by the conventional NaClO oxidation method, and effluent which reaches the standard is discharged, so the treatment difficulty and cost of a discharge and treatment system are reduced; and the concentrated liquor is subjected to catalytic wet oxidation, and the effluent obtained after treatment can reach the direct discharging standard, or can be recycled as clear water.
Description
Technical field
The present invention relates to a kind of wastewater treatment method, more precisely, relate to a kind of treatment Methods of Cyanide Wastewater of lower concentration, the invention still further relates to a kind of system that uses this processing method.
Background technology
Cyanide wastewater is the bigger trade effluent of a kind of toxicity, and is unstable in water, is decomposed into inorganic cyanogen and organic cyanogen easily, is the hypertoxicity material, and the people eats and can cause acute poisoning.Prussiate is 0.18g to the human body lethal quantity, and Potssium Cyanide is 0.12g, and prussiate is 0.01-0.1mg/L to the deadly mass concentration of fish in the water body.Cyanide wastewater mainly comes from industries such as plating, coal gas, coking, metallurgy, metal processing, chemical fibre, plastics, agricultural chemicals, chemical industry.These industry produce cyanide wastewater and can cause very big pollution to environment, all are a kind of serious threats to the life of human beings'health and livestock, fish.
The treatment process commonly used of cyanide wastewater has: alkaline chlorination process, pressurizing hydrolysis, electrolytic process, biochemical process, sulphur dioxide-air oxidation style, hydrogen peroxide oxidation process, natural purification method, acidifying absorption method etc.; These treatment processs are handled the problem that all exists on using to cyanide wastewater, and secondary pollutant discharges as having in long processing period, the treating processes, more treatment effect instability and the prussiate of causing of influence factor removed halfway situation.The catalytic wet oxidation method grows up on the wet air oxidation basis.The treatment process that in wet air oxidation, adds catalyzer is referred to as the catalytic wet oxidation method, is called for short the CWO method.The catalytic wet oxidation method is meant at high temperature (200～280 ℃), high pressure (under 2～8MPa); With oxygen rich gas or oxygen is catalyzer; Utilize the katalysis of catalyzer; Respiratory reaction in the quickening waste water between organism and oxygenant makes the organism in the waste water and contains poisonous substances such as N, S to be oxidized to CO2, N2, SO2, H2O, reaches the purpose of purification.To the chemical oxygen level of height or contain the various industrial organic waste waters of the compound that biochemical process can not degrade, no longer need carry out aftertreatment, only can reach emission standard through primary treatment.But the investment of this method is huge, and the treatment time is long, a lot of enterprises, the factory great amount of cost of being unwilling for this reason to spend.
Summary of the invention
The present invention is in order to solve the problem that exists in the prior art; A kind of lower concentration treatment Methods of Cyanide Wastewater is provided; Membrane sepn and two modern techniquies of CWO are carried out rational combination, optimization, solved the subsequent disposal of reverse osmosis concentrated liquid, reduced the treatment scale of catalytic wet oxidation simultaneously; Thereby reduced investment, obtained good treatment effect.
For realizing above-mentioned purpose, technical scheme of the present invention is: a kind of lower concentration treatment Methods of Cyanide Wastewater comprises the steps:
(1) the lower concentration cyanide wastewater is carried out pre-treatment, remove the macrobead solid pollutant in the lower concentration cyanide wastewater;
(2) above-mentioned pretreated lower concentration cyanide wastewater is carried out film and handle, produce liquid concentrator and see through clear water;
(3) liquid concentrator is carried out CWO and handle, discharging or recycling;
(4) the said clear water that sees through is handled discharging or recycling with the NaClO method for oxidation.
Preferably: the pre-treatment in the said step (1) gets into equalizing tank then through grid filtration, and stirring and transferring pH simultaneously is 7.5～8.5.
Preferably: the film in the said step (2) is handled and is comprised preprocessing system, first step reverse osmosis membrane processing system and second stage reverse osmosis membrane processing system successively; Preprocessing system comprises sand filtration and filter element filtering; Sand filtration adopts silica sand to filter; Filter core aperture in the filter element filtering is 2～5 μ m, and the waste water after the filtration filters through the two steps ro film processing system.
Preferably: said first step reverse osmosis membrane and second stage reverse osmosis membrane are selected high pollution-resistant membrane for use.
Preferably: the CWO in the said step (3) is handled and is: liquid concentrator boosts to 3.8～4.0Mpa through boosting pump; With oxidizing gas thorough mixing with pressure; After the gas-liquid material temperature is promoted to 220～240 ℃; In the entering reaction tower, pollution substance is decomposed into CO by exhaustive oxidation under the effect of catalyzer
2, H
2O, the reaction times is 1.4～1.6h, and the reaction water outlet is carried out the heat exchange postcooling through the liquid concentrator with the system of entering, and temperature is reduced to 30～50 ℃, carries out gas-liquid separation again and handles.
Preferably: said oxidizing gas is air or purity oxygen.
Preferably: said catalyzer is that titanium oxide is carrier ruthenium base active catalyst.
Preferably: in CWO was handled, the material of the equipment of the part that contacts with the gas-liquid raw material adopted the titanium material.
The present invention also provides a kind of system that is applicable to above-mentioned lower concentration cyanide wastewater treatment process, comprising:
Pre-processing device comprises grid and equalizing tank;
Film processing system; It comprises preprocessing system, first step reverse osmosis membrane processing system and second stage reverse osmosis membrane processing system; Preprocessing system comprises sand filtration and filter element filtering, and silica sand is adopted in sand filtration, and the filter core aperture of filter element filtering is 2～5 μ m; Liquid through first, second grade reverse osmosis membrane processing system is to see through clear water, and the liquid through first, second grade reverse osmosis membrane processing system is not liquid concentrator;
Be used to handle the CWO treatment system of liquid concentrator, said liquid concentrator is broken down into gaseous substance and water in the CWO treatment facility.
Beneficial effect of the present invention is, the advantage of lower concentration advance of treatment process of cyanide-bearing effluent of the present invention: the lower concentration cyanide wastewater is removed macrobead solid pollutant in the sewage through grid earlier, the normal effectively operation of protection subsequent processing device, and the equipment that prevents stops up; Equalizing tank plays the effect that homogeneous is all measured, and prevents because the excessive unsettled situation of treatment effect that causes of change of water quality amplitude; Water outlet after the lower concentration cyanide wastewater is handled through film, cyanogen content reduces by 99%, and methods such as the NaClO oxidation of available routine are handled back up to standard discharging; The liquid concentrator that two steps ro is handled is handled through CWO again, can reach direct emission standards fully after the processing, can do the rinse water reuse, realizes the recycling of resource; The water inlet preheating of CWO treatment system adopts water inlet and its system to go out the mode of hydrothermal exchange, makes full use of heat, has energy-conservation characteristics; The CWO treatment system is higher than under the situation of 30000mg/L in water inlet COD concentration, and the heat energy that exothermic heat of reaction produces not only can be kept the operation of CWO system, and can have the surplus heat to produce.In sum, the present invention has realized innoxious, the recycling treatment of lower concentration cyanide wastewater.
Description of drawings
Fig. 1 shows the schematic flow sheet of lower concentration cyanide wastewater treatment process of the present invention and system.
Embodiment
Further specify below in conjunction with the accompanying drawing specific embodiments of the invention.
As shown in Figure 1, a kind of lower concentration treatment Methods of Cyanide Wastewater of the present invention comprises the steps:
(1) the lower concentration cyanide wastewater is entered into pretreatment system through lift pump, pretreatment system comprises grid and equalizing tank.Remove in the sewage greater than the macrobead solid pollutant of 1mm with grid, the water outlet behind the grid flows in the equalizing tank, is provided with whipping appts in the equalizing tank, and rotating speed is at 40-60 rev/min, under the stirring action of cyanide wastewater in equalizing tank, and water quality and water yield homogenizing; Simultaneously, in equalizing tank with pH regulator to 7.5～8.5 of cyanide wastewater.
The lower concentration cyanide wastewater that (2) will mix up the pH value enters into sand filtration equipment through lift pump and filters; The silica sand material is adopted in sand filtration, and the filtration water outlet of sand filtration gets into the filter element filtering system, and the filter core aperture is 2～5 μ m; Water outlet behind the filter element filtering gets into the reverse osmosis membrane processing system through HPP; What reverse osmosis membrane adopted is high antipollution ultra-filtration membrane, and the cyanogen pollutent through 99% in the waste water of two steps ro film treatment facility is removed, and the concentrate recirculation of second stage reverse osmosis membrane processing to first-stage reverse osmosis film front end carries out secondary filtration; Liquid concentrator before the first-stage reverse osmosis film film is the final liquid concentrator in the film processing system, gets into concentration basin and stores; The liquid that sees through of two-pass reverse osmosis film is called through clear water, after the conventional NaClO method for oxidation of process is handled, and back up to standard discharging or recycling.
(3) liquid concentrator in the concentration basin carries out the CWO processing; Its operation is carried out in CWO treatment facility (system), and its idiographic flow is following: earlier the liquid concentrator in the concentration basin is delivered to homogeneous groove (not shown) through lift pump, the homogeneous troughed belt has the jacking-type whisking appliance; Get into boosting pump through the liquid concentrator of regulating homogeneous and boost to 3.8～4.0Mpa; Mix with oxidizing gas from the uniform pressure of air compressor machine then, the volume ratio of gas-liquid raw material under standard state is 110: 1～130: 1, is warming up to 220～240 ℃ through preheater and well heater again; Getting into reactive system reacts; Reactive system mainly is made up of placed in-line two reactor drums, and liquid concentrator at first gets into the void tower reactor drum, and then gets into the heating agent reactor drum that catalyzer is housed; Pollutent in the liquid concentrator is broken down into products such as carbonic acid gas, water and nitrogen in reactor drum, the reaction times is 1.4～1.6h.Catalytic oxidation is thermopositive reaction, and the part that reactor wall, preheater, well heater etc. contact with reaction liquid all adopts metal titanium as liner, prevents the infringement of severe corrosive pollutent to equipment; Temperature is that 220～240 ℃ reaction product gets into preheater and raw wastewater and carries out heat exchange and be cooled to about 130～170 ℃; Treated again watercooler further is cooled to 30～50 ℃ of entering gas-liquid separators; Isolated gas phase directly enters atmosphere, and liquid phase gets into the in line or reuse of clear water storage tank as treating water.
In the lower concentration of the present invention treatment of cyanide waste water side, wherein: in the said step (1), if the pH value of lower concentration cyanide wastewater between 7.5～8.5, then need not regulated the pH operation.
In the lower concentration of the present invention treatment of cyanide waste water side, wherein: in the said step (3), oxidizing gas can be air or purity oxygen.
In the lower concentration of the present invention treatment of cyanide waste water side, wherein: in the said step (3), catalyzer is that titanium oxide is carrier ruthenium base active catalyst.
Embodiment
The lower concentration cyanide wastewater is handled and is adopted aforesaid method of the present invention and system, and the designing treatment Total Water is 1000t/d, and every day was by operation design continuously in 24 hours.Film processing unit flooding velocity is 1000m
3/ d; Catalytic wet oxidation processing unit flooding velocity is 41.7m
3/ h;
The test result of influent quality and effluent quality is shown in table 1 and table 2:
Table 1 lower concentration cyanide wastewater influent quality (unit: mg/l; PH value non-dimensional)
Table 2 lower concentration cyanide wastewater water quality of processed water (unit: mg/l; PH value non-dimensional)
The result proves, adopts the effluent quality after the inventive method is handled to reach " integrated wastewater discharge standard " (GB8978-1996) secondary discharge standard of middle regulation.
Membrane treatment process section design variable:
The reverse osmosis membrane processing system of 1000t/d membrane treatment process adopts the two steps ro film processing system, and the part operating parameter is shown in table 3, table 4:
Table 3 first step reverse osmosis membrane processing system design parameters
Table 4 second stage reverse osmosis membrane processing system design parameters
The clearance situation is shown in table 5, table 6:
The removal effect of table 5 film processing unit
Table 6 catalytic wet oxidation processing unit clearance
Beneficial effect:
Adopt method and system of the present invention can handle 36.5 ten thousand tons of lower concentration cyanide wastewater every year; Clear up COD (CODcr): 5439 tons/year; Clear up five-day BOD (BOD5): 1356 tons/year, clear up ammonia nitrogen (NH3-N): 839 tons/year, clear up prussiate: 292 tons/year.
Claims (9)
1. a lower concentration treatment Methods of Cyanide Wastewater comprises the steps:
(1) the lower concentration cyanide wastewater is carried out pre-treatment, remove the macrobead solid pollutant in the lower concentration cyanide wastewater;
(2) above-mentioned pretreated lower concentration cyanide wastewater is carried out film and handle, produce liquid concentrator and see through clear water;
(3) liquid concentrator is carried out CWO and handle, discharging or recycling;
(4) the said clear water that sees through is handled discharging or recycling with the NaClO method for oxidation.
2. lower concentration treatment Methods of Cyanide Wastewater according to claim 1 is characterized in that: the pre-treatment in the said step (1) gets into equalizing tank then through grid filtration, and stirring and transferring pH simultaneously is 7.5～8.5.
3. lower concentration treatment Methods of Cyanide Wastewater according to claim 1; It is characterized in that: the film in the said step (2) is handled and is comprised preprocessing system, first step reverse osmosis membrane processing system and second stage reverse osmosis membrane processing system successively; Preprocessing system comprises sand filtration and filter element filtering; Sand filtration adopts silica sand to filter, and the filter core aperture in the filter element filtering is 2～5 μ m, and the waste water after the filtration filters through the two steps ro film processing system.
4. lower concentration treatment Methods of Cyanide Wastewater according to claim 3 is characterized in that: said first step reverse osmosis membrane and second stage reverse osmosis membrane are selected high pollution-resistant membrane for use.
5. lower concentration treatment Methods of Cyanide Wastewater according to claim 1; It is characterized in that: the CWO in the said step (3) is handled and is: liquid concentrator boosts to 3.8～4.0Mpa through boosting pump; With oxidizing gas thorough mixing with pressure; After the gas-liquid material temperature is promoted to 220～240 ℃, get in the reaction tower, pollution substance is decomposed into CO by exhaustive oxidation under the effect of catalyzer
2, H
2O, the reaction times is 1.4～1.6h, and the reaction water outlet is carried out the heat exchange postcooling through the liquid concentrator with the system of entering, and temperature is reduced to 30～50 ℃, carries out gas-liquid separation again and handles.
6. lower concentration treatment Methods of Cyanide Wastewater according to claim 5 is characterized in that: said oxidizing gas is air or purity oxygen.
7. lower concentration treatment Methods of Cyanide Wastewater according to claim 5 is characterized in that: said catalyzer is that titanium oxide is carrier ruthenium base active catalyst.
8. lower concentration treatment Methods of Cyanide Wastewater according to claim 5 is characterized in that: in CWO was handled, the material of the equipment of the part that contacts with the gas-liquid raw material adopted the titanium material.
9. lower concentration treatment of cyanide waste water system comprises:
Pre-processing device comprises grid and equalizing tank;
Film processing system; It comprises preprocessing system, first step reverse osmosis membrane processing system and second stage reverse osmosis membrane processing system; Preprocessing system comprises sand filtration and filter element filtering, and silica sand is adopted in sand filtration, and the filter core aperture of filter element filtering is 2～5 μ m; Liquid through first, second grade reverse osmosis membrane processing system is to see through clear water, and the liquid through first, second grade reverse osmosis membrane processing system is not liquid concentrator;
Be used to handle the CWO treatment system of liquid concentrator, said liquid concentrator is broken down into gaseous substance and water in the CWO treatment facility.
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| CN102728350A (en) * | 2012-07-10 | 2012-10-17 | 北京纬纶华业环保科技股份有限公司 | Catalyst for treating industrial waste water by catalytic wet air oxidation (CWAO) |
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| CN104193123A (en) * | 2014-09-29 | 2014-12-10 | 长春黄金研究院 | Gold mine cyanide-containing wastewater system treating method |
| CN104193058A (en) * | 2014-09-27 | 2014-12-10 | 长春黄金研究院 | Gold mine cyanide-containing wastewater comprehensive treating method |
| CN104193040A (en) * | 2014-09-18 | 2014-12-10 | 长春黄金研究院 | Comprehensive treatment method for cyanide-containing wastewater of gold mines |
| CN104862495A (en) * | 2015-06-05 | 2015-08-26 | 长春黄金研究院 | Clean production method for gold extraction by cyanidation |
| CN105399261A (en) * | 2015-12-12 | 2016-03-16 | 常州大学 | Treating method for low-concentration electroplating cyanide-containing waste water |
| CN108249629A (en) * | 2018-03-06 | 2018-07-06 | 安徽三江水务工程有限公司 | A kind for the treatment of of Perfume Wastewater pretreatment system |
| CN108367955A (en) * | 2015-09-04 | 2018-08-03 | 蒂森克虏伯工业解决方案股份公司 | Method for handling the industrial wastewater containing organic compound |
| CN112777718A (en) * | 2020-12-18 | 2021-05-11 | 滨化集团股份有限公司 | Treatment method of high-salinity wastewater |
| CN114890597A (en) * | 2022-04-20 | 2022-08-12 | 江苏安绿新能源科技有限公司 | Comprehensive treatment system for oily wastewater |
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| CN102728350A (en) * | 2012-07-10 | 2012-10-17 | 北京纬纶华业环保科技股份有限公司 | Catalyst for treating industrial waste water by catalytic wet air oxidation (CWAO) |
| CN104176884B (en) * | 2014-09-01 | 2015-11-18 | 长春黄金研究院 | A kind of cyanide wastewater integrated conduct method |
| CN104176884A (en) * | 2014-09-01 | 2014-12-03 | 长春黄金研究院 | Cyanide-containing wastewater comprehensive treatment method |
| CN104193040B (en) * | 2014-09-18 | 2016-03-02 | 长春黄金研究院 | A kind of gold mine cyanide wastewater integrated conduct method |
| CN104193040A (en) * | 2014-09-18 | 2014-12-10 | 长春黄金研究院 | Comprehensive treatment method for cyanide-containing wastewater of gold mines |
| CN104193058A (en) * | 2014-09-27 | 2014-12-10 | 长春黄金研究院 | Gold mine cyanide-containing wastewater comprehensive treating method |
| CN104193058B (en) * | 2014-09-27 | 2016-01-20 | 长春黄金研究院 | A kind of gold mine cyanide wastewater comprehensive processing method |
| CN104193123A (en) * | 2014-09-29 | 2014-12-10 | 长春黄金研究院 | Gold mine cyanide-containing wastewater system treating method |
| CN104193123B (en) * | 2014-09-29 | 2016-05-18 | 长春黄金研究院 | A kind of gold mine cyanide wastewater system processing method |
| CN104862495A (en) * | 2015-06-05 | 2015-08-26 | 长春黄金研究院 | Clean production method for gold extraction by cyanidation |
| CN108367955A (en) * | 2015-09-04 | 2018-08-03 | 蒂森克虏伯工业解决方案股份公司 | Method for handling the industrial wastewater containing organic compound |
| CN108367955B (en) * | 2015-09-04 | 2022-03-04 | 蒂森克虏伯工业解决方案股份公司 | Method for treating industrial waste water containing organic compounds |
| CN105399261A (en) * | 2015-12-12 | 2016-03-16 | 常州大学 | Treating method for low-concentration electroplating cyanide-containing waste water |
| CN108249629A (en) * | 2018-03-06 | 2018-07-06 | 安徽三江水务工程有限公司 | A kind for the treatment of of Perfume Wastewater pretreatment system |
| CN112777718A (en) * | 2020-12-18 | 2021-05-11 | 滨化集团股份有限公司 | Treatment method of high-salinity wastewater |
| CN114890597A (en) * | 2022-04-20 | 2022-08-12 | 江苏安绿新能源科技有限公司 | Comprehensive treatment system for oily wastewater |
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Application publication date: 20120620 Assignee: LIANG YONGJUN Assignor: Beijing Biotechina Environment Corp.Ltd. Contract record no.: 2015990000403 Denomination of invention: Method and system for treating cyanide-containing wastewater at low concentration Granted publication date: 20140716 License type: Exclusive License Record date: 20150602 |
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Effective date of registration: 20180604 Address after: 102200 Room 201, building 139, South earth road, Xichang, Changping District, Beijing. Patentee after: LIANG YONGJUN Address before: 100083 room 1906, block A, Cai Zhi International Building, 18 Zhongguancun East Road, Haidian District, Beijing. Patentee before: Beijing Biotechina Environment Corp.Ltd. |