CN110627258A - Treatment device and process for high-concentration cyanide-containing wastewater - Google Patents

Treatment device and process for high-concentration cyanide-containing wastewater Download PDF

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Publication number
CN110627258A
CN110627258A CN201911016984.1A CN201911016984A CN110627258A CN 110627258 A CN110627258 A CN 110627258A CN 201911016984 A CN201911016984 A CN 201911016984A CN 110627258 A CN110627258 A CN 110627258A
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tank
sewage
filter
gas
water
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朱洪
赵尔滨
马洪玺
杨久利
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Shanghai Lanke Petrochemical Engineering & Technology Co Ltd
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Shanghai Lanke Petrochemical Engineering & Technology Co Ltd
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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
    • C02F11/00—Treatment of sludge; Devices therefor
    • C02F11/12—Treatment of sludge; Devices therefor by de-watering, drying or thickening
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F11/00—Treatment of sludge; Devices therefor
    • C02F11/12—Treatment of sludge; Devices therefor by de-watering, drying or thickening
    • C02F11/121—Treatment of sludge; Devices therefor by de-watering, drying or thickening by mechanical de-watering
    • C02F11/122—Treatment of sludge; Devices therefor by de-watering, drying or thickening by mechanical de-watering using filter presses
    • 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
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/62—Metallic pigments or fillers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/06—Treatment with inorganic compounds
    • 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
    • C02F1/66—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
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
    • 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
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00—Use of specific compounds during water treatment
    • C02F2305/02—Specific form of oxidant
    • C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Mechanical Engineering (AREA)
  • Treatment Of Water By Oxidation Or Reduction (AREA)

Abstract

The invention discloses a treatment device for high-concentration cyanide-containing wastewater, which comprises a sewage adjusting tank, a mixer, a sedimentation tank and a sand filter which are sequentially connected along the flow direction of sewage; the sand filter is connected with an ozone treatment circulating system, the circulating system comprises an ozone catalytic oxidation reactor, a clean water tank and a clean water circulating pipeline which are sequentially connected with an outlet of the sand filter, and the clean water circulating pipeline is connected to an inlet of the sand filter; the sand filter is connected with a back flushing drainage pipeline; the sedimentation tank is connected with sludge recycling system, sludge recycling system includes sludge impoundment, pickling bath, pressure filter and dosing tank, the medicine circulating line who is connected in order with sedimentation tank bottom mud discharging port, the entry of medicine circulating line connection to blender is added. The device has simple flow, convenient operation, capability of reducing cost and stable and reliable operation. Correspondingly, the treatment process is provided, the treatment efficiency is high, and the requirements of the environment-friendly process are met.

Description

Treatment device and process for high-concentration cyanide-containing wastewater
Technical Field
The invention belongs to the technical field of wastewater treatment, and particularly relates to a treatment device and a treatment process for high-concentration cyanide-containing wastewater.
Background
In the industrial production process, cyanide is widely applied to industries such as non-ferrous metal smelting, ore dressing, metal processing, plastics, electroplating, electronics, instruments, coking, oil refining, glass, chemical engineering and the like, but a large amount of cyanide-containing waste water is generated along with the cyanide. The cyanide in the wastewater is divided into free cyanide and complex cyanide, the free cyanide is mainly alkali metal salt, such as sodium cyanide and potassium cyanide, and the complex cyanide is mainly because the cyano is a strong complexing agent and forms stable complex anion in the aqueous solution after being complexed with various metals. The cyanide-containing wastewater not only contains free cyanide, but also contains complex cyanide, so that the processing difficulty of cyanide is greatly increased, and the cyanide-containing wastewater has high toxicity, is easy to cause cancer and teratogenesis, and has great harm to the environment and human beings. Therefore, the research on the treatment method and the process of the cyanide-containing wastewater has very important significance.
Chinese patent CN207904106U discloses a cyanide-containing wastewater treatment system, which adopts sodium hypochlorite to break cyanide for pretreatment, then adopts an A/O-MBR process, and then utilizes a biological treatment method to remove cyanide. According to the method, a large amount of medicament is required to be added in the process of breaking cyanogen by using sodium hypochlorite, the dosage is large, the salt content of the treated wastewater is increased, the pretreated cyanogen-containing wastewater is even low in concentration, bacteria hardly reach high biological activity, and the biological method is easy to inactivate and unstable to operate.
Chinese patent CN106396205A discloses a method for removing heavy metals from high-concentration cyanide wastewater, which comprises the steps of electrolyzing the high-concentration cyanide wastewater by using direct current under an alkaline condition, adding hydrogen peroxide to promote the reaction speed, electrolyzing to obtain low-concentration cyanide wastewater, adjusting the pH 10-11 of the low-concentration cyanide wastewater, adding EDTA (ethylene diamine tetraacetic acid) and a catalyst for reaction, adding hydrogen peroxide into the solution obtained by the reaction for deep cyanide breaking treatment, and finally removing the heavy metals in the solution from the wastewater subjected to thorough cyanide breaking by using a ferrite method. Although the invention can process free cyanogen and complex cyanogen, the added EDTA is a stable organic substance, is difficult to degrade and is extremely difficult to process biochemically.
Therefore, the technical personnel in the field urgently need to develop a treatment device and a treatment process aiming at the high-concentration cyanide-containing wastewater, which have the advantages of simple flow, simple and convenient operation, cost reduction, high treatment efficiency, stable and reliable operation and environmental protection process requirement.
Disclosure of Invention
The invention aims to provide a treatment device and a treatment process for high-concentration cyanide-containing wastewater, which have the advantages of simple flow, convenient operation, capability of reducing cost, stable and reliable operation, high treatment efficiency and accordance with the requirements of environmental protection processes.
In order to realize one of the purposes, the invention provides a treatment device for high-concentration cyanide-containing wastewater, which adopts the following technical scheme:
a treatment device for high-concentration cyanide-containing wastewater comprises a sewage adjusting tank, a mixer, a sedimentation tank and a sand filter which are sequentially connected along the flow direction of sewage; the sand filter is connected with an ozone treatment circulating system, the circulating system comprises an ozone catalytic oxidation reactor, a clean water tank and a clean water circulating pipeline which are sequentially connected with an outlet of the sand filter, and the clean water circulating pipeline is connected to an inlet of the sand filter; the sand filter is connected with a back flushing drainage pipeline;
the sedimentation tank is connected with sludge recycling system, sludge recycling system includes sludge impoundment, pickling bath, pressure filter and dosing tank, the medicine circulating line who is connected in order with sedimentation tank bottom mud discharging port, the entry of medicine circulating line connection to blender is added.
Preferably, a back flushing drainage pipeline on the sand filter is connected to the sludge tank.
Preferably, the filter press is provided with an air inlet pipeline and a water inlet pipeline, and the bottom of the filter press is also connected with a drying box.
Further, the drying temperature is controlled to be 50-70 ℃ in the drying oven, and the drying time is 2-6 h.
Preferably, a lift pump is arranged on a connecting pipeline of the mixer and the sedimentation tank.
Preferably, a lifting pump is arranged on a connecting pipeline of the sedimentation tank and the sand filter.
Preferably, a lifting pump is arranged on a pipeline connecting the sludge tank and the pickling tank.
Preferably, a lifting pump is arranged on a connecting pipeline of the pickling tank and the filter press.
Preferably, a lift pump is arranged on the clean water circulating pipeline of the clean water tank.
Preferably, a lifting pump is arranged on a dosing circulating pipeline of the dosing tank.
Preferably, the filter material in the sand filter is selected from one or more of quartz sand, river sand, sea sand, ceramsite, anthracite, activated carbon, diatomite, manganese sand, iron sand and zeolite, and the filter material medium has a particle size of 0.2-0.5 mm and a thickness of 50-200 mm.
Furthermore, the filtering speed in the sand filter is controlled to be 5-15 m/h.
Preferably, a catalyst layer is arranged in the ozone catalytic oxidation reactor, and the catalyst layer adopts a metal supported catalyst. The active component of the catalyst is the compound of any two or more than two of transition metals of Fe, Ti, Mn, Ni, V and Co or metal oxides thereof.
Furthermore, the contact time of the sewage and the catalyst layer in the ozone catalytic oxidation reactor is controlled to be 0.5-2 hr.
The invention also aims to provide a treatment process for high-concentration cyanide-containing wastewater, which comprises the following treatment steps:
the sewage to be treated is sent to a sewage adjusting tank, the PH of the sewage is adjusted to 5-7 by adding medicines, the sewage is sent to a mixer, a ferrous solution is added into the mixer, most of free cyanide in the sewage reacts with ferrous ions to generate insoluble ferric ferrocyanide, the sewage is sent to a sedimentation tank by a lifting pump after the reaction, and then two-way treatment is carried out:
one path is as follows: the supernatant after precipitation is sent to a sand filter by a lifting pump for filtration, a small amount of suspended matters containing ferric ferrocyanide contained in the water are removed by filtration, and the solid content in the filtered water is less than 10 mg/l; a small amount of free cyanide and complex cyanide are still contained in the sewage after reaction, precipitation and filtration, and the sewage is continuously sent to an ozone catalytic oxidation reactor, a transition metal catalyst is filled in the reactor, ozone generates hydroxyl free radicals under the action of the catalyst, and the hydroxyl free radicals have no selectivity on the degradation of organic matters, so that the complex cyanide and the free cyanide in the water can be thoroughly degraded; the sewage after the catalytic oxidation treatment of the ozone enters a clean water tank for collection, part of water in the clean water tank is sent to a sand filter tank through a lifting pump to be used as backwashing water for cleaning the sand filter tank regularly, the water after the flushing is sent to a sludge tank for collection, and the other part of water is used as the treated water and is discharged from a water outlet pipe at the upper part of the clean water tank;
the other path is as follows: sludge containing ferrous cyanide and ferrous hydroxide is discharged from the bottom of the sedimentation tank, enters a sludge tank for collection, and is conveyed to a pickling tank through a lifting pump, inorganic acid is added into the pickling tank, the ferrous hydroxide in the sludge reacts with the inorganic acid through pickling to generate ferrous ions, the sludge after pickling is conveyed to a leaf filter through the lifting pump, ferric cyanide particles form a filter cake on the surface of a filter element, and the filtered filtrate is collected through a dosing tank and conveyed to a mixer through the lifting pump to be recycled as a ferrous solution raw material; and (3) after the filtration is finished, washing the filter cake with water and blowing gas to remove soluble salts, acid and water in the filter cake, then discharging the filter cake from the bottom of the filter press and conveying the filter cake to a drying box, and drying to obtain the iron blue pigment product.
Preferably, the ferrous solution is ferrous salt of ferrous sulfate or ferrous chloride.
Preferably, the sedimentation residence time in the sedimentation tank is controlled to be 0.5-2 h.
Preferably, the filtering speed in the sand filter is controlled to be 5-15 m/h.
Preferably, the ozone is O3The adding amount is adjusted according to the amount of the total cyanide, and the adding proportion is controlled to be n [ O ]3]: n (total cyanogen) is (2E to E)5): 1. wherein n represents the amount of the substance.
Preferably, the contact time of the catalyst and the sewage in the ozone catalytic oxidation reactor is controlled to be 0.5-2 hr.
Preferably, the ferrous solution is in accordance with n [ Fe ]2+]：n[CN-](2-3): the adding proportion of 1 is excessive. Wherein n represents the amount of the substance.
Preferably, the inorganic acid is sulfuric acid or hydrochloric acid, and the PH is controlled to be 1-3; the acid washing retention time is 0.5-2 h.
Preferably, the drying temperature in the drying oven is controlled to be 50-70 ℃, and the drying time is 2-6 h; drying to obtain a ferric blue product, wherein the content of the ferricyanide complex is not less than 70 wt%, the content of volatile matters is 2-6 wt%, the content of water soluble matters is not more than 2 wt%, and the acidity of the water extraction liquid is not more than 20 mL; the product conforms to ISO 2495: 1995 iron blue pigment product requirements.
The invention can bring the following beneficial effects:
(1) according to the invention, the PH of the sewage can be adjusted through the sewage adjusting tank, and the sewage enters the mixer and then is precipitated under a proper condition by adding ferrous ions, so that most of free cyanide is removed; then the sewage enters a sand filter for filtration, and then enters an ozone catalytic oxidation reactor for further removing the residual free cyanide, and particularly removing the complex cyanide in the sewage, so that the cyanide in the treated sewage is less than 0.5mg/l, and the discharge requirement of GB18918 + 2002 urban sewage treatment plant pollutant discharge standard is met.
(2) The excessive ferrous iron in the ferrous precipitation method can form ferrous hydroxide floc, and the sedimentation separation efficiency is improved.
(3) The ferrous hydroxide solution formed by pickling ferrous hydroxide can be returned to the mixed reaction tank to be used as a medicament raw material for recycling, the dosage is less, and no waste residue is generated.
(4) The treatment device for the high-concentration cyanide-containing wastewater disclosed by the invention can be used for treating high-concentration cyanide and preparing a high-purity iron blue product.
In conclusion, in the whole treatment device and process, an ozone treatment circulating system is integrated, and the stable and reliable operation of the system is ensured and water resources are saved by utilizing the treated clean water to perform backwashing on the regeneration pipeline of the sand filter; in addition, a sludge recycling circulation system is also integrally designed for sludge, so that the raw material of the ferrous solution is recycled, and meanwhile, a ferric blue pigment product can be obtained; therefore, the whole device is utilized for decyanation treatment, so that waste residues are not generated, and the device has obvious environmental protection advantage and economic advantage.
Drawings
FIG. 1 is a schematic structural diagram of a treatment device for high-concentration cyanide-containing wastewater according to the invention.
The notations in the figures have the following meanings:
1-a sewage adjusting tank; 2-a mixer; 3-a sedimentation tank;
4-a sand filter and 40-a back flushing drainage pipeline;
5-an ozone treatment circulating system, 50-an ozone catalytic oxidation reactor, 51-a clean water tank and 52-a clean water circulating pipeline;
6-sludge recycling circulation system, 60-sludge pool, 61-pickling pool, 62-filter press, 620-air inlet pipeline, 621-water inlet pipeline, 63-dosing tank, 64-dosing circulation pipeline and 65-drying box.
Detailed Description
The technical solution of the present invention will be clearly and completely described below with reference to the specific embodiments. The following examples are only for illustrating the technical solutions of the present invention more clearly, and the protection scope of the present invention is not limited thereby.
Example 1
As shown in fig. 1, the device for treating high-concentration cyanide-containing wastewater comprises a wastewater adjusting tank 1, a mixer 2 and a sedimentation tank 3 which are connected in sequence along the flow direction of wastewater;
the upper part of the sedimentation tank 3 is connected with a sand filter tank 4, the sand filter tank 4 is connected with an ozone treatment circulating system 5, the ozone treatment circulating system 5 comprises an ozone catalytic oxidation reactor 50, a clean water tank 51 and a clean water circulating pipeline 52 which are sequentially connected with the outlet of the sand filter tank 4, and the clean water circulating pipeline 52 is connected to the inlet of the sand filter tank 4; the sand filter 4 is connected with a back flushing drainage pipeline 40;
the bottom of sedimentation tank 3 is connected with mud recovery circulation system 6, mud recovery circulation system 6 includes sludge impoundment 60, pickling tank 61, pressure filter 62 and dosing tank 63, the medicine circulating line 64 of being connected in order with 3 bottom mud discharging openings of sedimentation tank, the medicine circulating line 64 that adds is connected to the entry of blender 2.
In the embodiment, the pH of the sewage can be adjusted through the sewage adjusting tank 1, and the sewage enters the mixer 2 and then is precipitated under a proper condition by adding ferrous ions, so that most of free cyanide is removed; then the sewage enters a sand filter 4 for filtration, and then enters an ozone catalytic oxidation reactor 50 for further removing residual free cyanide, and particularly removing complex cyanide in the sewage, so that the cyanide in the treated sewage is less than 0.5mg/l, and the discharge requirement of GB18918-2002 pollutant discharge standard of urban sewage treatment plants is met. In addition, in the device, an ozone treatment circulating system 5 is integrated in the system, and the sand filter 4 is backwashed and regenerated by utilizing the treated clean water from a clean water circulating pipeline 52, so that the running stability and reliability of the system are ensured, and water resources are saved; in addition, a sludge recycling and circulating system 6 is also integrally designed for sludge, so that the raw material of the ferrous solution is recycled, and meanwhile, a ferric blue pigment product can be obtained; therefore, the whole device is utilized for decyanation treatment, so that waste residues are not generated, and the device has obvious environmental protection advantage and economic advantage.
In a preferred embodiment, the backwash drain line 40 of the sand filter 4 is connected to a sludge tank 60. Therefore, the device can realize no waste slag discharge when treating waste water.
In a preferred embodiment, the filter press 62 is provided with an air inlet pipe 620 and a water inlet pipe 621, and the bottom of the filter press 62 is further connected to the drying box 65. In the embodiment, the filter cake formed after filter pressing can be washed by water and blown by gas by using the structure, so that soluble salts, acid and water in the filter cake are removed, and the iron blue product in the filter cake is further ensured to meet the product requirement. In practical application, the filter press can be a common commercially available plate and frame filter press.
As another preferred embodiment, a lift pump is arranged on a connecting pipeline of the mixer 2 and the sedimentation tank 3; and/or a lifting pump is arranged on a connecting pipeline of the sedimentation tank 3 and the sand filter tank 4; and/or a lifting pump is arranged on a pipeline connecting the sludge tank 60 and the pickling tank 61; and/or a lifting pump is arranged on a connecting pipeline of the pickling tank 61 and the filter press 62; and/or, a lift pump is arranged on the clean water circulating pipeline 52 of the clean water tank 51; and/or a lifting pump is arranged on the dosing circulating pipeline 64 of the dosing tank 63. Thereby improving the operation efficiency of the sewage.
In another preferred embodiment, the filter material in the sand filter 4 is selected from one or more of quartz sand, river sand, sea sand, ceramsite, anthracite, activated carbon, diatomite, manganese sand, iron sand and zeolite, and the filter material medium has a particle size of 0.2-0.5 mm and a thickness of 50-200 mm. Thereby ensuring the filtering effect of the sand filter 4 and improving the removing efficiency of the ozone catalytic oxidation reactor 50 to the residual cyanides.
As another preferred embodiment, a catalyst layer is disposed in the ozone catalytic oxidation reactor 50, and the catalyst layer is a metal-supported catalyst. The active component of the catalyst is the compound of any two or more than two of transition metals Fe, Ti, Mn, Ni, V and Co or transition metal oxides of Fe, Ti, Mn, Ni, V and Co. Therefore, under the action of ozone, the cyanide in a complex state and the residual free cyanide can be effectively removed; the treatment efficiency of the device for cyanide-containing wastewater is guaranteed.
Example 2
The embodiment is a treatment process for high-concentration cyanide-containing wastewater, and the following treatment steps are performed on the basis of the treatment device provided in embodiment 1:
the sewage to be treated is sent to a sewage adjusting tank, the PH of the sewage is adjusted to 5-7 by adding medicines, the sewage is sent to a mixer, a ferrous solution is added into the mixer, most of free cyanide in the sewage reacts with ferrous ions to generate insoluble ferric ferrocyanide, the sewage is sent to a sedimentation tank by a lifting pump after the reaction, and then two-way treatment is carried out:
one path is as follows: the supernatant after precipitation is sent to a sand filter by a lifting pump for filtration, a small amount of suspended matters containing ferric ferrocyanide contained in the water are removed by filtration, and the solid content in the filtered water is less than 10 mg/l; a small amount of free cyanide and complex cyanide are still contained in the sewage after reaction, precipitation and filtration, the sewage is continuously sent to an ozone catalytic oxidation reactor, a transition metal catalyst is filled in the reactor, ozone generates hydroxyl free radicals under the action of the catalyst, the hydroxyl free radicals have no selectivity on the degradation of organic matters, so that the complex cyanide and the free cyanide in the sewage can be thoroughly degraded, the sewage after the ozone catalytic oxidation treatment enters a clean water tank for collection, part of the water in the clean water tank is sent to a sand filter tank through a lifting pump to be used as backwashing water for periodically cleaning the sand filter tank, the water after the flushing is sent to a sludge tank for collection, and the other part of the water is discharged from a water outlet pipe at the upper part of the clean water tank as the treated water;
the other path is as follows: sludge containing ferrous cyanide and ferrous hydroxide is discharged from the bottom of the sedimentation tank, enters a sludge tank for collection, and is conveyed to a pickling tank through a lifting pump, inorganic acid is added into the pickling tank, the ferrous hydroxide in the sludge reacts with the inorganic acid through pickling to generate ferrous ions, feed liquid after pickling is conveyed to a leaf filter through the lifting pump, ferric cyanide particles form a filter cake on the surface of a filter element, and filtered filtrate is collected through a dosing tank and is conveyed to a mixer through the lifting pump to be used as a ferrous solution raw material for recycling; and (3) after the filtration is finished, washing the filter cake with water and blowing gas to remove soluble salts, acid and water in the filter cake, then discharging the filter cake from the bottom of the filter press and conveying the filter cake to a drying box, and drying to obtain the iron blue pigment product.
In the embodiment, most of the free cyanide is removed firstly by adding ferrous ions, and then the rest of the free cyanide, especially the complex cyanide in the sewage is removed by ozone catalytic oxidation, so that the cyanide in the sewage after treatment is less than 0.5mg/l, and the discharge requirement of GB18918 and 2002 pollutant discharge Standard of urban Sewage treatment plant is met. In addition, in the method, the backwashing regeneration of the sand filter is integrated in the system, so that the stability and the reliability of the operation of the system are ensured; in addition, a recycling process is also integrally designed for the sludge, so that the ferrous solution raw material is recycled, and meanwhile, a ferric blue pigment product can be obtained; the whole process has no waste residue, and has obvious environmental protection advantage and economic advantage.
As a preferred embodiment, the ferrous solution is a ferrous salt of ferrous sulfate or ferrous chloride, and other ferrous salts may be used in practical applications.
In order to further remove most of the free cyanide, the sedimentation time in the sedimentation tank is controlled to be 0.5-2 h, so that ferrous ions and CN-Fully reacting and precipitating. And in addition, the filtering speed is controlled to be 5-15 m/h in the sand filter 4, so that cyanide-containing suspended matters can be effectively removed, and cyanide in the treated sewage is reduced.
On the basis of removing most of the free cyanide, ozone O is treated according to the amount of the total cyanide in order to further remove the cyanide in the complex state and the residual free cyanide3The adding amount is adjusted, and the adding proportion (mol ratio) is controlled to be n [ O ]3]: n (total cyanogen) is (2-5): 1. ozone generates hydroxyl free radicals under the action of a catalyst, and the hydroxyl free radicals have no selectivity on the degradation of organic matters, so that complex cyanide and free cyanide in water can be further degraded thoroughly. And the contact time of the catalyst and the sewage in the ozone catalytic oxidation reactor is controlled to be 0.5-2 hr.
As another preferred embodiment, the ferrous solution is in accordance with n [ Fe ]2+]：n[CN-](2-3): the addition ratio (molar ratio) of 1 is excessive. The excessive addition of ferrous iron can improve the conversion efficiency of the ferric ferrocyanide on one hand, and on the other hand, the granularity of the ferric ferrocyanide generated by the reaction is nano-scale, so that the solid-liquid separation from water is difficult, therefore, the excessive addition of ferrous ions is hydrolyzed into ferrous hydroxide flocs to form larger flocs with the ferric ferrocyanide, thereby effectively promoting the solid-liquid separation, improving the sedimentation separation effect and correspondingly improving the removal efficiency of the free cyanide.
In another preferred embodiment, the inorganic acid is sulfuric acid or hydrochloric acid, and the pH is controlled to be 1-3; the acid washing retention time is 0.5-2 h. The acid pickling under proper conditions can efficiently react ferrous hydroxide in the sludge with inorganic acid to regenerate ferrous ions, so that the ferrous ions can be recycled as ferrous solution raw materials, the process is more environment-friendly, the energy is saved, the cost is reduced, and no waste residue is generated.
As another preferable embodiment, the drying temperature in the drying oven is controlled to be 50-70 ℃, and the drying time is 2-6 h; after drying, the content of the ferricyanide complex in the ferric blue product is not less than 70 wt%, the volatile matter is 2-6 wt%, the water soluble matter is not more than 2 wt%, the acidity of the water extraction liquid is not more than 20, and the product meets ISO 2495: 1995 iron blue pigment product requirements. Therefore, the method provided by the invention can be used for treating high-concentration cyanide and simultaneously preparing high-purity iron blue products, and has obvious economic benefit.
Application example 1
The total cyanide of the sewage to be treated is 125.09mg/l, wherein the free cyanide is 110.23mg/l, and the treatment process aiming at the cyanide-containing waste water with high concentration adopts the invention to carry out experimental research on the site:
delivering the sewage to be treated to a sewage adjusting tank, adjusting the pH of the sewage to be 6 by adding medicaments, delivering the sewage to a mixer, adding a ferrous sulfate solution into the mixer, and adding ferrous iron according to the proportion of n [ FeSO4]：n[CN-]2: 1 excessive throwing, most free cyanide and ferrous ion fully react and generate insoluble ferrous cyanide in the sewage, improve ferrous cyanide conversion efficiency on the one hand, on the other hand hydrolysises into ferrous hydroxide floc through throwing excessive ferrous ion, forms great floc with ferrous cyanide, and sewage is sent to the sedimentation tank through the elevator pump after the reaction, and the sediment dwell time is 2h, then carries out two routes and handles:
one path is as follows: the supernatant after precipitation is sent to a sand filter by a lifting pump for filtration, the filter medium is quartz sand, the particle size of the medium is 0.5mm, the thickness is 200mm, the filtration speed is 10m/h, and the total cyanide content of the filtered sewage is 26.92mg/l, wherein the free cyanide content is 14.68 mg/l; pumping to an ozone catalytic oxidation tank by a lifting pump, filling a catalyst in the ozone catalytic oxidation tank, wherein the contact time of sewage and the catalyst is 0.5hr, and the ratio of the ozone adding amount to the total cyanide value in water is 3: 1, the adding amount is 60mg/l of water, and the total cyanide after treatment is 0.19 mg/l; the sewage after the catalytic oxidation treatment of the ozone enters a clean water tank for collection, part of water in the clean water tank is sent to a sand filter tank through a lifting pump to be used as backwashing water for cleaning the sand filter tank regularly, the water after the flushing is sent to a sludge tank for collection, and the other part of water is used as the treated water and is discharged from a water outlet pipe at the upper part of the clean water tank;
the other path is as follows: discharging sludge containing ferrous cyanide and ferrous hydroxide from the bottom of the sedimentation tank, allowing the sludge to enter a sludge tank for collection, then conveying the sludge to a pickling tank through a lifting pump, adding sulfuric acid, controlling the pH to be 1, reacting the ferrous hydroxide in the sludge with inorganic acid through pickling to generate ferrous ions, allowing the pickling to stay for 0.5h, conveying the material liquid after pickling to a leaf filter through the lifting pump, collecting the filtered filtrate through a storage tank, conveying the filtrate to a mixer through the lifting pump, and recycling the filtrate as a ferrous solution raw material. And after filtration, washing and blowing gas to remove soluble salts, acid and water in the filter cake, discharging the filter cake from the bottom of the leaf filter, and conveying the filter cake to a drying box, wherein the drying temperature is 60 ℃, the drying time is 6 hours, the content of the iron-cyanogen complex in the dried powder is 75 wt%, the content of volatile matters is 2.5 wt%, the content of water soluble matters is 0.4 wt%, and the acidity of a water extraction solution is 15ml (the acidity of the water extraction solution refers to the dosage of titrating the filtrate of iron blue extraction by 0.01mol/l sodium hydroxide to pH 5.5), and the product meets ISO 2495: 1995 iron blue pigment product requirements.
Application example 2
The total cyanides of the sewage to be treated are 133.14mg/l, wherein the free cyanides are 114.76mg/l, and the treatment process aiming at the high-concentration cyanide-containing waste water adopts the invention to carry out experimental research on the site:
the pH of the sewage to be treated is regulated to 6.5 by a regulating tank, and the sewage enters a mixer and FeSO is added4Fully reacting, n [ FeSO4]：n[CN-]2.5: 1, pumping the mixed solution after reaction to a sedimentation tank by a lifting pump, wherein the sedimentation time is 2 hours;
after precipitation, supernatant fluid enters a sand filter through a lifting pump to be filtered, a filter medium is quartz sand, the particle size of the medium is 0.5mm, the thickness of the medium is 200mm, the filtering speed is 10m/h, and the total cyanide of filtered sewage is 28.32mg/l, wherein the free cyanide is 10.24mg/l, the supernatant fluid is sent to an ozone pool through the lifting pump, a catalyst is filled in the ozone pool, the contact time of the sewage and the catalyst is 0.75hr, and the ratio of the ozone adding amount to the total cyanide sum in water is 3: 1, the adding amount is 84mg/l of water, and the total cyanide after treatment is 0.25 mg/l; the sewage after the catalytic oxidation treatment of the ozone enters a clean water tank for collection, part of water in the clean water tank is sent to a sand filter tank through a lifting pump to be used as backwashing water for cleaning the sand filter tank regularly, the water after the flushing is sent to a sludge tank for collection, and the other part of water is used as the treated water and is discharged from a water outlet pipe at the upper part of the clean water tank;
collecting sludge at the bottom of the sedimentation tank in a sludge tank, then pumping the sludge to a pickling tank by a lifting pump, adding hydrochloric acid to control the pH to be 2, controlling the retention time of the pickling tank to be 1h, pumping the pickled material liquid to a leaf filter by the lifting pump, and collecting the filtered filtrate as FeSO by a storage tank4Using raw materials; and (3) sending a filter cake discharged from the bottom of the leaf filter to a drying tank for drying at 65 ℃ for 5 hours, wherein the content of the ferricyanide complex in the dried powder is 76 wt%, the content of volatile matters is 2.7 wt%, the content of water soluble matters is 0.6 wt%, and the acidity of a water extraction liquid is 13ml (the acidity of the water extraction liquid refers to the dosage of a filtrate obtained after ferric blue extraction is titrated by 0.01mol/l sodium hydroxide to the pH value of 5.5), and the product meets the requirements of ISO 2495: 1995 iron blue pigment product.
Application example 3
The total cyanides of the sewage to be treated are 315.33mg/l, wherein the free cyanides are 276.89mg/l, and the treatment process aiming at the high-concentration cyanide-containing waste water adopts the invention to carry out experimental research on the site:
the pH of the sewage to be treated is regulated to 6.8 by a regulating tank, and the sewage enters a mixer and FeSO is added4Fully reacting, n [ FeSO4]：n[CN-]3: 1, pumping the mixed solution after reaction to a sedimentation tank by a lifting pump, wherein the sedimentation time is 2 hours;
supernatant fluid after the precipitation enters a sand filter through a lifting pump to be filtered, a filter medium is quartz sand, the particle size of the medium is 0.5mm, the thickness is 200mm, the filtering speed is 10m/h, the total cyanide of the filtered sewage is 48.65mg/l, wherein, the free cyanide is 11.23mg/l, the supernatant fluid is sent to an ozone pool through the lifting pump, a catalyst is filled in the ozone pool, the contact time of the sewage and the catalyst is 1hr, and the ratio of the ozone adding amount to the total sum of the total cyanide in the water is 2: 1, the adding amount is 96mg/l of water, and the total cyanide after treatment is 0.37 mg/l; the sewage after the catalytic oxidation treatment of the ozone enters a clean water tank for collection, part of water in the clean water tank is sent to a sand filter tank through a lifting pump to be used as backwashing water for cleaning the sand filter tank regularly, the water after the flushing is sent to a sludge tank for collection, and the other part of water is used as the treated water and is discharged from a water outlet pipe at the upper part of the clean water tank;
collecting sludge at the bottom of the sedimentation tank in a sludge tank, pumping the sludge to a pickling tank by a lifting pump, adding sulfuric acid to control the pH to be 2.5, controlling the retention time of the pickling tank to be 1.5h, pumping the material liquid after pickling to a leaf filter by the lifting pump, and collecting the filtrate after filtering as FeSO by a storage tank4Using raw materials; and (3) conveying a filter cake discharged from the bottom of the leaf filter to a drying tank for drying at 65 ℃ for 4 hours, wherein the content of the ferricyanide complex in the dried powder is 72 wt%, the content of volatile matters is 2.9 wt%, the content of water soluble matters is 0.8 wt%, and the acidity of a water extraction liquid is 11ml (the acidity of the water extraction liquid refers to the dosage of a filtrate obtained after ferric blue extraction is titrated by 0.01mol/l sodium hydroxide to the pH value of 5.5), and the product meets the requirements of ISO 2495: 1995 iron blue pigment product.
Application example 4
The total cyanides of the sewage to be treated are 412.66mg/l, wherein the free cyanides are 389.54mg/l, and the treatment process aiming at the high-concentration cyanide-containing waste water adopts the invention to carry out experimental research on the site:
the PH of the sewage to be treated is adjusted to 7 by a regulating tank, and the sewage enters a mixer and FeSO is added4Fully reacting, n [ FeSO4]：n[CN-]2: 1, pumping the mixed solution after reaction to a sedimentation tank by a lifting pump, wherein the sedimentation time is 2 hours;
supernatant fluid after the precipitation enters a sand filter through a lifting pump to be filtered, a filter medium is quartz sand, the particle size of the medium is 0.5mm, the thickness is 200mm, the filtering speed is 10m/h, and the total cyanide of the filtered sewage is 47mg/l, wherein the free cyanide is 26.01mg/l, the supernatant fluid is conveyed to an ozone pool through the lifting pump, a catalyst is filled in the ozone pool, the contact time of the sewage and the catalyst is 1.5hr, and the ratio of the ozone adding amount to the total sum of the total cyanide in the water is 2: 1, the adding amount is 94mg/l of water, and the total cyanide after treatment is 0.41 mg/l; the sewage after the catalytic oxidation treatment of the ozone enters a clean water tank for collection, part of water in the clean water tank is sent to a sand filter tank through a lifting pump to be used as backwashing water for cleaning the sand filter tank regularly, the water after the flushing is sent to a sludge tank for collection, and the other part of water is used as the treated water and is discharged from a water outlet pipe at the upper part of the clean water tank;
collecting sludge at the bottom of the sedimentation tank in a sludge tank, pumping the sludge to a pickling tank by a lifting pump, adding sulfuric acid to control the pH to be 3, controlling the retention time of the pickling tank to be 2 hours, pumping the material liquid after pickling to a leaf filter by the lifting pump, and collecting the filtrate after filtering as FeSO by a storage tank4Using raw materials; and (3) sending a filter cake discharged from the bottom of the leaf filter to a drying tank for drying at 70 ℃, wherein the drying time is 4 hours, the content of the ferricyanide complex in the dried powder is 77 wt%, the content of volatile matters is 2.1 wt%, the content of water soluble matters is 0.6 wt%, and the acidity of the water extraction liquid is 9ml (the acidity of the water extraction liquid refers to the dosage of titrating filtrate obtained after the extraction of the ferric blue by 0.01mol/l sodium hydroxide to the pH value of 5.5), and the product meets the requirements of ISO 2495: 1995 iron blue pigment product.
Comparative example
This example is substantially the same as the processing steps of application example 4, except that:
control of n [ FeSO4]：n[CN-]1: 1; after the precipitated sewage enters a sand filter for filtration, 96.25mg/l of total cyanide in the sewage, wherein 73.13mg/l of free cyanide is pumped to an ozone tank by a lifting pump, a catalyst is filled in the ozone tank, the contact time of the sewage and the catalyst is 1.5hr, and the ratio of the ozone adding amount to the total sum of the total cyanide in the water is 2: 1, the adding amount is 192.5mg/l of water, and the total cyanide after treatment is 2.10mg/l and does not meet the discharge requirement of GB18918-2002 pollutant discharge standard of urban sewage treatment plants.
Analysis shows that the conversion efficiency of the ferrocyanide is reduced because the ferrous ions are not excessively added, and the particle size of the ferrocyanide generated by the reaction is nano-scale, so that the solid-liquid separation from water is difficult, the sedimentation separation effect is reduced, and the removal efficiency of the free cyanide is correspondingly reduced.
It should be noted that the above embodiments can be freely combined as necessary. The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (10)

1. The utility model provides a processing apparatus to high concentration cyanide wastewater which characterized in that:
comprises a sewage adjusting tank, a mixer, a sedimentation tank and a sand filter which are connected in sequence along the sewage flowing direction; the sand filter is connected with an ozone treatment circulating system, the circulating system comprises an ozone catalytic oxidation reactor, a clean water tank and a clean water circulating pipeline which are sequentially connected with an outlet of the sand filter, and the clean water circulating pipeline is connected to an inlet of the sand filter; the sand filter is connected with a back flushing drainage pipeline;
the sedimentation tank is connected with sludge recycling system, sludge recycling system includes sludge impoundment, pickling bath, pressure filter and dosing tank, the medicine circulating line who is connected in order with sedimentation tank bottom mud discharging port, the entry of medicine circulating line connection to blender is added.
2. The processing apparatus according to claim 1, characterized in that:
and a back flushing drainage pipeline on the sand filter is connected to the sludge tank.
3. The processing apparatus according to claim 1, characterized in that:
the filter press is provided with an air inlet pipeline and a water inlet pipeline, and the bottom of the filter press is also connected with a drying box.
4. The processing apparatus according to claim 1, characterized in that:
a lifting pump is arranged on a connecting pipeline of the mixer and the sedimentation tank; and/or the presence of a gas in the gas,
a lifting pump is arranged on a connecting pipeline of the sedimentation tank and the sand filter; and/or the presence of a gas in the gas,
a lifting pump is arranged on a pipeline connecting the sludge tank and the pickling tank; and/or the presence of a gas in the gas,
a lifting pump is arranged on a connecting pipeline of the pickling tank and the filter press; and/or the presence of a gas in the gas,
a lift pump is arranged on a clean water circulating pipeline of the clean water tank; and/or the presence of a gas in the gas,
and a lifting pump is arranged on a dosing circulating pipeline of the dosing tank.
5. The processing apparatus according to claim 1, characterized in that:
the filter material in the sand filter tank is selected from quartz sand, river sand, sea sand, ceramsite, anthracite, activated carbon, diatomite, manganese sand, iron sand and zeolite, and the filter material medium has the particle size of 0.2-0.5 mm and the thickness of 50-200 mm; and/or the presence of a gas in the gas,
the ozone catalytic oxidation reactor is internally provided with a catalyst layer, and the catalyst layer adopts a metal supported catalyst.
6. A treatment process for high-concentration cyanide-containing wastewater is characterized by comprising the following treatment steps:
the sewage to be treated is sent to a sewage adjusting tank, the PH of the sewage is adjusted to 5-7 by adding medicines, the sewage is sent to a mixer, a ferrous solution is added into the mixer, most of free cyanide in the sewage reacts with ferrous ions to generate insoluble ferric ferrocyanide, the sewage is sent to a sedimentation tank by a lifting pump after the reaction, and then two-way treatment is carried out:
one path is as follows: the supernatant after precipitation is sent to a sand filter by a lifting pump for filtration, a small amount of suspended matters containing ferric ferrocyanide contained in the water are removed by filtration, and the solid content in the filtered water is less than 10 mg/l; a small amount of free cyanide and complex cyanide are still contained in the sewage after reaction, precipitation and filtration, and the sewage is continuously sent to an ozone catalytic oxidation reactor, a transition metal catalyst is filled in the reactor, and the ozone generates hydroxyl free radicals under the action of the catalyst to completely degrade the complex cyanide and the free cyanide in the water; the sewage after the catalytic oxidation treatment of the ozone enters a clean water tank for collection, part of water in the clean water tank is sent to a sand filter tank through a lifting pump to be used as backwashing water for cleaning the sand filter tank regularly, the water after the flushing is sent to a sludge tank for collection, and the other part of water is used as treated water and discharged from the upper part of the clean water tank;
the other path is as follows: sludge discharged from the bottom of the sedimentation tank enters a sludge tank for collection, then is conveyed to a pickling tank through a lifting pump, inorganic acid is added into the pickling tank, ferrous hydroxide in the sludge reacts with the inorganic acid through pickling to generate ferrous ions, feed liquid after pickling is conveyed to a leaf filter through the lifting pump, ferric ferrocyanide particles form a filter cake on the surface of a filter element, and filtered filtrate is conveyed to a mixer through the lifting pump after being collected through a dosing tank and is used as a ferrous solution raw material for recycling; and after the filtration is finished, washing and blowing gas to the filter cake, then discharging the filter cake from the bottom of the filter press, conveying the filter cake to a drying box, and drying to obtain the iron blue pigment product.
7. The process of claim 6, wherein:
the ferrous solution is ferrous salt of ferrous sulfate or ferrous chloride; and/or the presence of a gas in the gas,
controlling the retention time of the sediment in the sedimentation tank to be 0.5-2 h; and/or the presence of a gas in the gas,
controlling the filtering speed in the sand filter to be 5-15 m/h; and/or the presence of a gas in the gas,
the adding proportion of the ozone catalytic oxidation reactor is controlled to be n [ O ]3]: n (total cyanogen) is (2-5): 1; and/or the presence of a gas in the gas,
the contact time of the catalyst and the sewage in the ozone catalytic oxidation reactor is controlled to be 0.5-2 hr.
8. The process of claim 6, wherein:
the ferrous solution is according to n [ Fe ]2+]：n[CN-](2-3): the adding proportion of 1 is excessive.
9. The process of claim 6, wherein:
the inorganic acid is sulfuric acid or hydrochloric acid, and the PH value is controlled to be 1-3; the acid washing retention time is 0.5-2 h.
10. The process of claim 6, wherein:
controlling the drying temperature in the drying box to be 50-70 ℃ and the drying time to be 2-6 h;
and drying to obtain the iron blue product, wherein the content of the iron cyanide complex is not less than 70 wt%, the content of volatile matters is 2-6 wt%, the content of water soluble matters is not more than 2 wt%, and the acidity of the water extraction liquid is not more than 20 ml.
CN201911016984.1A 2019-10-24 2019-10-24 Treatment device and process for high-concentration cyanide-containing wastewater Pending CN110627258A (en)

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