CN106315908B - Deep treatment method and device for cold rolling oily wastewater - Google Patents
Deep treatment method and device for cold rolling oily wastewater Download PDFInfo
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Abstract
The invention provides a method and a device for deeply treating cold rolling oily wastewater, wherein the method comprises the following steps: cold-rolled oily biochemical effluent enters a multi-media filter, passes through a ceramsite packing area and a grain slag packing area in the multi-media filter, and then enters an intermediate water tank, wastewater in the intermediate water tank enters an ozone catalytic tower through a secondary water inlet pump, and diatomite catalyst packing is filled in the ozone catalytic tower; ozone generated by the ozone generator enters from the bottom of the ozone catalytic tower and is diffused to the whole ozone catalytic tower through the ozone diffuser, and the cold-rolled oily wastewater reaches the standard and is discharged after being subjected to gas-liquid mixing in the ozone catalytic tower and catalytic oxidation through the diatomite catalyst. The method and the system provided by the invention have the advantages of stable treatment effect, low production and operation cost, simple and convenient operation and high automation degree. The invention belongs to an environment-friendly steel green production system.
Description
Technical Field
The invention belongs to the technical field of water treatment, and particularly relates to a method and a device for deeply treating cold rolling oily wastewater.
Background
The steel industry is a high-energy-consumption, high-resource and high-pollution industry, and the water resource consumption of the steel industry is huge and accounts for about 14 percent of the water consumption of the national industry.
The national development and improvement committee of 7 months in 2005 issued "iron and steel industry development policy", put forward higher targets and more specific requirements for the development of circular economy, energy and resource conservation and sustainable development road of the iron and steel industry, and under the condition of global resource shortage, low energy consumption, low pollution and low emission become the needs of social development.
The cold rolling waste water mainly comes from oil depot drainage of various units such as a rolling mill unit, a grinding roller room, a strip steel degreasing unit and the like. The cold rolling waste water after conventional treatment can meet the national environmental protection discharge requirement.
The environmental protection department executes a new discharge standard for water pollution in the iron and steel industry (GB 13456) from 1 month and 1 day 2015, and the requirements for various water quality indexes which reach the discharge standard in the new standard are called as 'most severe history'. The new standards stipulate that the COD emission value must be lower than 30 mg/L. Therefore, the COD of the cold rolling wastewater discharged is reduced to below 30mg/L from 60-100 mg/L at present, which is a core problem to be solved at present.
Chinese patent "a treatment process of wastewater containing alkali and oil" (CN101684025A) discloses a treatment process of wastewater containing alkali and oil. The process comprises the steps of firstly carrying out neutralization treatment on the alkali-containing and oil-containing wastewater, then sequentially carrying out inclined plate precipitation, paper tape filtration and ultrafiltration treatment, and finally discharging. The technology is only a treatment process of alkali-containing and oil-containing wastewater, and does not consider the advanced treatment of alkali-containing and oil-containing wastewater and the requirement of meeting the discharge standard of water pollution in the steel industry (GB 13456-2012). The invention discloses an anaerobic-aerobic combined biological treatment method for oily wastewater of a cold rolling mill (CN 101481195A). The anaerobic treatment and the aerobic treatment are carried out on the oily wastewater, and all parameters are strictly controlled, so that the concentrations of oil and COD in the cold rolling dilute alkali oily wastewater after secondary treatment reach the primary discharge standard of Integrated wastewater discharge Standard (GB 101481195A-1996), and the method is simple and convenient to operate, stable to operate, good in biodegradability and low in operation cost. The technology adopts a biological technology to ensure that the water quality index in the cold rolling oily wastewater reaches the old discharge standard, and does not need to consider the treatment technology of the oily wastewater reaching the discharge standard of pollutants for water in the steel industry (GB 13456-2012). Chinese patent "a treatment process of dilute emulsified oily wastewater" (CN101684025A) discloses a treatment process of dilute emulsified oily wastewater. The effluent of the dilute emulsified oily wastewater is subjected to uniform aeration adjustment, primary pH adjustment, secondary pH adjustment, coagulation, air flotation, cooling, biological contact oxidation, flocculation precipitation and partial sludge backflow, and then is discharged or recycled after reaching the standard. The technology is only a technology for discharging the dilute emulsified oily wastewater after reaching the standard, and does not relate to a technical scheme of advanced treatment.
However, no mature advanced treatment process for cold rolling oily wastewater exists at home and abroad, so the patent provides a system process for the advanced treatment of the cold rolling oily wastewater, realizes the green treatment of the cold rolling wastewater and reduces the COD discharge of ton steel.
Therefore, the research on the deep treatment of the cold-rolling oily wastewater is enhanced, a targeted treatment scheme is formulated, a production process for further efficiently removing COD in the wastewater is explored, and the method has important significance for realizing the sustainable development and energy conservation and emission reduction of enterprises.
Disclosure of Invention
The first purpose of the invention is to provide a method for deeply treating cold rolling oily wastewater.
The second purpose of the invention is to provide a deep treatment device for cold rolling oily wastewater.
According to the invention, an economic and efficient advanced wastewater treatment process is developed according to the water quality and water quantity conditions of cold rolling oily wastewater, so that the wastewater is discharged up to the standard, the removal efficiency of organic matters in industrial wastewater is improved, and the COD discharge amount of ton steel wastewater is reduced. The deep treatment process for the cold rolling oily wastewater has the advantages of stable treatment effect, low production and operation cost, simple and convenient operation and high automation degree.
The technical scheme of the invention is as follows:
the advanced treatment method of the cold rolling oily wastewater is characterized by comprising the following steps:
cold-rolled oily biochemical effluent enters a multi-media filter, passes through a ceramsite packing area and a grain slag packing area in the multi-media filter, and then enters an intermediate water tank, wastewater in the intermediate water tank enters an ozone catalytic tower through a secondary water inlet pump, and diatomite catalyst packing is filled in the ozone catalytic tower; ozone generated by an ozone generator enters from the bottom of an ozone catalytic tower and is diffused to the whole ozone catalytic tower through an ozone diffuser, the wastewater is subjected to gas-liquid mixing in the ozone catalytic tower and catalytic oxidation through a diatomite catalyst, and the cold-rolled oily wastewater reaches the standard and is discharged;
the diatomite catalyst is prepared by the following steps:
(1) cleaning of the carrier: selecting diatomite with the particle size of 5-25 mm, cleaning the diatomite with a sulfuric acid solution, cleaning the diatomite with distilled water, drying the diatomite for 3-5 hours at 105-110 ℃, and cooling the diatomite for later use;
(2) preparing a solution: preparing a solution, calculating by metal elements, mixing a nickel nitrate solution with the concentration of 5-10%, a manganese nitrate solution with the concentration of 3-8% and a ceric ammonium nitrate solution with the concentration of 1-4%, and adding 2-5 mg/L hydroxylamine hydrochloride into the mixed solution to form an impregnation solution;
(3) shaking and mixing: soaking the diatomite prepared in the step (1) in the dipping solution, shaking for 5-10 hours in a constant-temperature shaking box at 35-55 ℃ at a speed of 120-160 rpm, taking out, and airing;
(4) and (3) high-temperature sintering: and (4) roasting the aired diatomite in the step (3) at the constant temperature of 210 ℃ for 2-3 hours, then continuously heating to 610 ℃, roasting at the constant temperature for 3-5 hours, and naturally cooling to obtain the diatomite catalyst.
According to the deep treatment method of the cold-rolling oily wastewater, the retention time of the cold-rolling oily wastewater in the catalytic tower is 20-70 minutes, the packing density of the diatomite catalyst is 120-330 g/L, and the volume of the diatomite catalyst accounts for 55-75% of the volume of the whole catalytic tower.
According to the deep treatment method of the cold rolling oily wastewater, the diatomite catalyst preferably has a load metal rate of 9-17% by mass, a porosity of 83-90% and a specific surface area of 53-65 m2/g。
According to the advanced treatment method of the cold rolling oily wastewater, the diatomite is preferably mainly SiO2：85～92％；Al2O3：2～5％；CaO：1～2％；Fe2O3: 1-1.5%; MgO: 0.5-1% of impurities and 0.5-5% of impurities; the uniformity of the diatomite is 86% -97%.
According to the advanced treatment method of the cold rolling oily wastewater, the mixing is preferably performed according to the volume ratio of the nickel nitrate solution, the manganese nitrate solution and the ceric ammonium nitrate solution of 1: (1-5): (1 to 6), preferably 1: (2-5): (3-6) preparing a mixed solution.
According to the advanced treatment method of the cold rolling oily wastewater, the high-temperature sintering process is preferably carried out in the preparation of the diatomite catalyst: and (2) drying the diatomite in a blast heating box at the temperature of 120 ℃ for 2-5 hours, then putting the diatomite in a high-temperature furnace with nitrogen as protective gas, heating to 210 ℃ at the speed of 5-10 ℃/min, roasting at constant temperature for 2-3 hours, then continuously heating to 610 ℃ at the speed of 10-20 ℃/min, roasting at constant temperature for 3-5 hours, and then naturally cooling to obtain the diatomite catalyst.
According to the deep treatment method of the cold rolling oily wastewater, the aperture of the water distributor in the multi-media filter is preferably 25-75 mm.
According to the deep treatment method of the cold-rolling oily wastewater, the volume ratio of the ceramsite filling area to the grain slag filling area in the multi-media filter is preferably 1: 5-8; the ceramsite has the particle size of 2-10 mm, the porosity of 40-65%, the density of 300-500 kg/m3 and the compressive strength of more than or equal to 1.5 MPa; the chemical components of the granulated slag are mainly CaO: 36-47%; SiO 22：27～45％；Al2O3: 3 to 21 percent; FeO: 0.5-4.5%; the grain size of the grain slag is 3-20 mm, and the uniformity is 85% -98%.
The diatomite catalyst provided by the invention can convert ozone into hydroxyl free radicals more easily, and can decompose refractory organic matters in water more easily.
According to the advanced treatment method of the cold rolling oily wastewater, the quality of the cold rolling oily wastewater after the treatment method is as follows: the PH value is 6-9, the COD is 11-27 mg/L, the suspended matters are 10-35 mg/L, the conductivity is 2500-7500 mu s/cm, the chloride ions are 630-1670 mg/L, and the effluent quality reaches the new national discharge standard.
The invention also provides a device for applying the advanced treatment method of the cold rolling oily wastewater, which comprises a primary water inlet pump 1, a multi-medium filter 3, an intermediate water tank 11, a secondary water inlet pump 12, an ozone catalytic tower 14 and a drainage pump 21 which are sequentially connected through pipelines; a water distributor 4 is arranged at the inner bottom of the multi-media filter 3, and a ceramsite filling area 5 and a grain slag filling area 6 are arranged at the upper part of the water distributor 4; a back flush water inlet 9 and a back flush water outlet 10 are arranged at the upper side and the lower side of the multi-media filter 3; an ozone diffuser 18 is arranged at the bottom of the ozone catalytic tower 14, the ozone diffuser 18 is connected with an ozone generator 16, an ozone catalyst 15 is filled in the ozone catalytic tower 14, and an ozone outlet 19 of an ozone quencher is arranged at the top of the ozone catalytic tower 14.
Detailed description of the invention:
the invention relates to a deep treatment process system for cold-rolled oily wastewater, which comprises a primary water inlet pump, a filter water inlet, a multi-media filter, a water distributor, a ceramsite filler zone, a grain slag filler zone, a filter water outlet, a backwashing pump, a backwashing water inlet, a backwashing water outlet, an intermediate water tank, a secondary water inlet pump, a catalytic tower water inlet, an ozone catalytic tower, a diatomite ozone catalyst, an ozone generator, an ozone pipeline and air inlet, an ozone diffuser, an ozone quencher and air outlet, a catalytic tower water outlet and a drainage pump.
The invention adopts biochemical effluent of cold rolling oily wastewater, and the water quality is as follows: the pH is 6-9, the COD is 45-87 mg/L, the suspended matter is 210-450 mg/L, the conductivity is 2500-7500 mu s/cm, and the chloride ion is 630-1670 mg/L.
Cold-rolled oily biochemical effluent enters a multi-media filter from a water inlet of the filter through a primary water inlet pump from a pipeline, the aperture of a water distributor in the filter is 25-75 mm, and then the cold-rolled oily biochemical effluent passes through a ceramsite filler area and a grain slag filler area. The volume ratio of the ceramsite filling area to the grain slag filling area is 1: 5 to 8.
The main functions of the ceramsite filling area are to remove large particulate matters in the cold rolling oily wastewater and prevent the loss of the upper layer filter material. The grain size of the ceramsite is 2 mm-10 mm, the surface of the ceramsite is rough and hard, and the ceramsite is provided with a plurality of micropores and is gray black. The porosity is 40-65%, the density is 300-500 kg/m3, and the compressive strength is not less than 1.5 MPa.
Then the wastewater enters a grain slag filling area. The water slag in the water slag layer is molten slag from a blast furnace during blast furnace iron making, and granular solid residues are generated after water quenching. The grain slag filling area has the main function of removing suspended matters and impurities in the cold rolling oily wastewater. Further, the chemical components of the granulated slag are CaO: 36-47%; SiO 22：27～45％；Al2O3: 3 to 21 percent; FeO: 0.5 to 4.5 percent. The grain size of the grain slag is 3-20 mm, and the uniformity is 85% -98%.
After passing through the two filler areas, suspended matters and impurities in the cold-rolling oily wastewater are effectively removed, and then the cold-rolling oily wastewater enters the intermediate water tank through the water outlet of the filter.
The retention time of the cold rolling oily wastewater in the multi-medium filter is 20-55 minutes, and the back washing period of the multi-medium filter is 8-24 hours. During backwashing, clean water enters a backwashing water inlet of the filter from the backwashing pump and flows out of a backwashing water outlet, and the whole backwashing time is 5-10 min.
And the wastewater in the middle water tank enters the catalytic tower from a water inlet at the upper part of the catalytic tower through a secondary water inlet pump, and catalyst filler is filled in the catalytic tower. The air source of the ozone generator is pure oxygen, the generated ozone enters from the bottom of the catalytic tower through the ozone pipeline and the air inlet, is diffused to the whole catalytic reaction tower through the ozone diffuser, and finally the ozone which is not utilized is eliminated by the ozone quencher and is safely discharged through the air outlet. The whole catalytic tower reactor is cylindrical and belongs to a gas-liquid countercurrent structure. The retention time of the cold rolling oily wastewater in the catalytic tower is 20-70 minutes, the packing density of the catalyst is 120-330 g/L, and the volume of the catalyst accounts for 55-75% of the volume of the whole catalytic tower.
The invention aims at the water quality characteristics of cold rolling oily wastewater and prepares the high-efficiency COD removal catalyst. Preparation of the catalyst:
preparation of a diatomite catalyst: a) screening of diatomite: the diatomite mainly contains SiO2：85～92％；Al2O3：2～5％；CaO：1～2％；Fe2O3: 1-1.5%; MgO: 0.5-1% and 0.5% of impurities-5%. The particle size of the diatomite is 5-25 mm, and the uniformity is 86-97%. b) Cleaning of the carrier: selecting diatomite with corresponding particle size, washing the diatomite with 2-5% sulfuric acid solution for 5 times, then washing the diatomite with distilled water for 5 times, then drying the diatomite in a 105-110 ℃ blast drying oven for 3-5 hours, and cooling the diatomite for later use. c) Preparing a solution: preparing a nickel nitrate solution with the concentration of 5-10% (calculated by metal elements), a manganese nitrate solution with the concentration of 3-8% and a ceric ammonium nitrate solution with the concentration of 1-4%, wherein the volume ratio of the three solutions is 1: 1: 1 preparing a mixed solution, and adding 2-5 mg/L hydroxylamine hydrochloride serving as a dispersing agent into the mixed solution to form an impregnation solution. d) Shaking and mixing: soaking the diatomite in the dipping solution, and oscillating for 5-10 hours in a constant-temperature oscillation box at 35-55 ℃ at the speed of 120-160 rpm; the diatomaceous earth was then removed and allowed to air dry at room temperature. e) And (3) high-temperature sintering: and (2) drying the diatomite in a blast heating box at the temperature of 120 ℃ for 2-5 hours, then putting the diatomite in a high-temperature furnace with nitrogen as protective gas, heating to 210 ℃ at the speed of 5-10 ℃/min, roasting at constant temperature for 2-3 hours, then continuously heating to 610 ℃ at the speed of 10-20 ℃/min, roasting at constant temperature for 3-5 hours, and then naturally cooling to prepare the diatomite catalyst.
Aiming at the characteristics of cold rolling oily wastewater, the prepared diatomite catalyst has 9-17% of supported metal rate, 83-90% of porosity and 53-65 m of specific surface area2/g。
After catalytic oxidation by the catalytic tower, the cold rolling oily wastewater is discharged by a drainage pump after reaching the standard.
After the treatment of the whole set of advanced treatment process flow, the cold rolling oil-containing wastewater quality is as follows: the PH value is 6-9, the COD is 11-27 mg/L, the suspended matters are 10-35 mg/L, the conductivity is 2500-7500 mu s/cm, the chloride ions are 630-1670 mg/L, and the effluent quality reaches the new national discharge standard.
According to the invention, an economic and efficient advanced wastewater treatment process is developed according to the water quality and water quantity conditions of cold rolling oily wastewater, so that the wastewater is discharged up to the standard, the removal efficiency of organic matters in industrial wastewater is improved, and the COD discharge amount of ton steel wastewater is reduced. The development of the advanced treatment process of cold rolling wastewater takes energy conservation, emission reduction and recycling as main tasks, reduces environmental pollution and actively deals with increasingly strict environmental protection regulations.
The beneficial technical effects are as follows:
the method and the system for the advanced treatment of the cold rolling oily wastewater provided by the invention have the advantages of stable treatment effect, low production and operation cost, simple and convenient operation and high automation degree. The invention belongs to an environment-friendly steel green production system.
The invention provides a technical scheme for advanced treatment of cold rolling wastewater, and solves the problem that organic pollutants in cold rolling oily wastewater exceed the standard systematically, and the cold rolling wastewater treated by the technical scheme can reach the new national emission standard.
Drawings
FIG. 1 is a schematic flow diagram of the advanced treatment process of cold rolling oily wastewater.
The treatment process mainly comprises the following steps: the device comprises a primary water inlet pump 1, a filter water inlet 2, a multi-media filter 3, a water distributor 4, a ceramsite packing area 5, a grain slag packing area 6, a filter water outlet 7, a backwashing pump 8, a backwashing water inlet 9, a backwashing water outlet 10, an intermediate water tank 11, a secondary water inlet pump 12, a catalytic tower water inlet 13, an ozone catalytic tower 14, an ozone catalyst 15, an ozone generator 16, an ozone pipeline and air inlet 17, an ozone diffuser 18, an ozone quencher and air outlet 19, a catalytic tower water outlet 20 and a drainage pump 21.
Detailed Description
In order to better understand the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples.
Example 1
The technical scheme adopted by the invention is as follows: a deep treatment process system for cold-rolled oily wastewater comprises a primary water inlet pump, a filter water inlet, a multi-media filter, a water distributor, a ceramsite packing area, a grain slag packing area, a filter water outlet, a backwashing pump, a backwashing water inlet, a backwashing water outlet, an intermediate water tank, a secondary water inlet pump, a catalytic tower water inlet, an ozone catalytic tower, a diatomite ozone catalyst, an ozone generator, an ozone pipeline and air inlet, an ozone diffuser, an ozone quencher and air outlet, a catalytic tower water outlet and a drainage pump.
The pH of the water in this example was 8.3, the COD was 82mg/L, the suspended matter was 370mg/L, the conductivity was 6100. mu.s/cm, and the chloride ion concentration was 1150 mg/L.
Cold-rolled oily biochemical effluent enters a multi-media filter from a water inlet of the filter through a first-stage water inlet pump from a pipeline, the aperture of a water distributor in the filter is 55mm, and then the cold-rolled oily biochemical effluent passes through a ceramsite packing area and a grain slag packing area. The volume ratio of the ceramsite filling area to the grain slag filling area is 1: 6.
the main functions of the ceramsite filling area are to remove large particulate matters in the cold rolling oily wastewater and prevent the loss of the upper layer filter material. The ceramsite has the particle size of 8mm, the surface is rough and hard, and a plurality of micropores are formed in the ceramsite and are gray black. Porosity of 55%, density of 450kg/m3The compressive strength is more than or equal to 1.5 MPa.
Then the wastewater enters a grain slag filling area. The water slag in the water slag layer is molten slag from a blast furnace during blast furnace iron making, and granular solid residues are generated after water quenching. The grain slag filling area has the main function of removing suspended matters and impurities in the cold rolling oily wastewater. Further, the chemical components of the granulated slag are CaO: 42%; SiO 22：40％；Al2O3: 17 percent; FeO: 1 percent. The grain size of the granulated slag was 15mm, and the uniformity was 95%.
After passing through the two filler areas, suspended matters and impurities in the cold-rolling oily wastewater are effectively removed, and then the cold-rolling oily wastewater enters the intermediate water tank through the water outlet of the filter.
The retention time of the cold-rolled oily wastewater in the multi-medium filter is 30 minutes, and the back flushing period of the multi-medium filter is 12 hours. During back washing, clean water enters a back washing water inlet of the filter from the back washing pump and flows out of a back washing water outlet, and the whole back washing time is 8 min.
And the wastewater in the middle water tank enters the catalytic tower from a water inlet at the upper part of the catalytic tower through a secondary water inlet pump, and catalyst filler is filled in the catalytic tower. The air source of the ozone generator is pure oxygen, the generated ozone enters from the bottom of the catalytic tower through the ozone pipeline and the air inlet, is diffused to the whole catalytic reaction tower through the ozone diffuser, and finally the ozone which is not utilized is eliminated by the ozone quencher and is safely discharged through the air outlet. The whole catalytic tower reactor is cylindrical and belongs to a gas-liquid countercurrent structure. The retention time of the cold rolling oily wastewater in the catalytic tower is 30 minutes, the packing density of the catalyst is 310g/L, and the volume of the catalyst accounts for 65 percent of the volume of the whole catalytic tower.
The embodiment aims at the water quality characteristics of cold rolling oily wastewater, and prepares the high-efficiency COD removal catalyst. Preparation of the catalyst:
preparation of a diatomite catalyst: a) screening of diatomite: the diatomite mainly contains SiO2：91％；Al2O3：4％；CaO：2％；Fe2O3: 1 percent; MgO: 1 percent; 1% of impurities. The particle size of the diatomaceous earth was 20mm, and the uniformity was 93%. b) Cleaning of the carrier: selecting diatomite with corresponding grain diameter, washing with 4% sulfuric acid solution for 5 times, washing with distilled water for 5 times, drying in a forced air drying oven at 110 ℃ for 3 hours, and cooling for later use. c) Preparing a solution: preparing a nickel nitrate solution with the concentration of 7 percent (calculated by metal elements), a manganese nitrate solution with the concentration of 6 percent and a ceric ammonium nitrate solution with the concentration of 3 percent, and then mixing the three solutions according to the volume ratio of 1: 1: 1, preparing a mixed solution, and adding hydroxylamine hydrochloride serving as a dispersing agent of 3mg/L into the mixed solution to form an impregnation solution. d) Shaking and mixing: soaking diatomite in the soaking solution, and shaking for 9 hours at the speed of 120 r/min in a constant-temperature shaking box at the temperature of 45 ℃; the diatomaceous earth was then removed and allowed to air dry at room temperature. e) And (3) high-temperature sintering: and (2) drying the diatomite in a blast heating box at the temperature of 120 ℃ for 3 hours, then putting the diatomite in a high-temperature furnace with nitrogen as protective gas, heating to 210 ℃ at the speed of 5 ℃/min, roasting at constant temperature for 2-3 hours, then continuously heating to 610 ℃ at the speed of 10 ℃/min, roasting at constant temperature for 3 hours, and then naturally cooling to prepare the diatomite catalyst.
Aiming at the characteristics of cold rolling oily wastewater, the prepared diatomite catalyst has the supported metal rate of 15 percent, the porosity of 87 percent and the specific surface area of 61m2/g。
After catalytic oxidation by the catalytic tower, the cold rolling oily wastewater is discharged by a drainage pump after reaching the standard.
After the treatment of the whole set of advanced treatment process flow, the cold rolling oil-containing wastewater quality is as follows: the PH is 7.6, the COD is 15mg/L, the suspended matter is 21mg/L, the conductivity is 6150 mus/cm, the chloride ion is 1200mg/L, and the effluent quality reaches the new national discharge standard.
Example 2
In order to realize the purpose of the invention, the technical scheme adopted by the invention is as follows: a deep treatment process system for cold-rolled oily wastewater comprises a primary water inlet pump, a filter water inlet, a multi-media filter, a water distributor, a ceramsite packing area, a grain slag packing area, a filter water outlet, a backwashing pump, a backwashing water inlet, a backwashing water outlet, an intermediate water tank, a secondary water inlet pump, a catalytic tower water inlet, an ozone catalytic tower, a diatomite ozone catalyst, an ozone generator, an ozone pipeline and air inlet, an ozone diffuser, an ozone quencher and air outlet, a catalytic tower water outlet and a drainage pump.
The pH of the water in this example was 6.7, the COD was 73mg/L, the suspended matter was 420mg/L, the conductivity was 3700. mu.s/cm, and the chloride ion concentration was 790 mg/L.
Cold-rolled oily biochemical effluent enters a multi-media filter from a water inlet of the filter through a first-stage water inlet pump from a pipeline, the aperture of a water distributor in the filter is 60mm, and then the cold-rolled oily biochemical effluent passes through a ceramsite packing area and a grain slag packing area. The volume ratio of the ceramsite filling area to the grain slag filling area is 1: 7.
the main functions of the ceramsite filling area are to remove large particulate matters in the cold rolling oily wastewater and prevent the loss of the upper layer filter material. The ceramsite has the particle size of 5mm, the surface is rough and hard, and a plurality of micropores are formed in the ceramsite and are gray black. The porosity was 45% and the density was 350kg/m3The compressive strength is more than or equal to 1.5 MPa.
Then the wastewater enters a grain slag filling area. The water slag in the water slag layer is molten slag from a blast furnace during blast furnace iron making, and granular solid residues are generated after water quenching. The grain slag filling area has the main function of removing suspended matters and impurities in the cold rolling oily wastewater. Further, the chemical components of the granulated slag are CaO: 45 percent; SiO 22：42％；Al2O3: 11 percent; FeO: 2 percent. The grain size of the granulated slag was 10mm, and the uniformity was 93%.
After passing through the two filler areas, suspended matters and impurities in the cold-rolling oily wastewater are effectively removed, and then the cold-rolling oily wastewater enters the intermediate water tank through the water outlet of the filter.
The retention time of the cold-rolled oily wastewater in the multi-medium filter is 40 minutes, and the back flushing period of the multi-medium filter is 8 hours. During back washing, clean water enters a back washing water inlet of the filter from the back washing pump and flows out of a back washing water outlet, and the whole back washing time is 6 min.
And the wastewater in the middle water tank enters the catalytic tower from a water inlet at the upper part of the catalytic tower through a secondary water inlet pump, and catalyst filler is filled in the catalytic tower. The air source of the ozone generator is pure oxygen, the generated ozone enters from the bottom of the catalytic tower through the ozone pipeline and the air inlet, is diffused to the whole catalytic reaction tower through the ozone diffuser, and finally the ozone which is not utilized is eliminated by the ozone quencher and is safely discharged through the air outlet. The whole catalytic tower reactor is cylindrical and belongs to a gas-liquid countercurrent structure. The retention time of the cold rolling oily wastewater in the catalytic tower is 40 minutes, the packing density of the catalyst is 260g/L, and the volume of the catalyst accounts for 70 percent of the volume of the whole catalytic tower.
The embodiment aims at the water quality characteristics of cold rolling oily wastewater, and prepares the high-efficiency COD removal catalyst. Preparation of the catalyst:
preparation of a diatomite catalyst: a) screening of diatomite: the diatomite mainly contains SiO2：89％；Al2O3：5％；CaO：1.5％；Fe2O3: 1 percent; MgO: 1 percent; 2.5 percent of impurities. The particle size of the diatomaceous earth was 10mm, the homogeneity being 95%. b) Cleaning of the carrier: selecting diatomite with corresponding grain diameter, washing with 8% sulfuric acid solution for 5 times, washing with distilled water for 5 times, drying in a 105 ℃ forced air drying oven for 4 hours, and cooling for later use. c) Preparing a solution: preparing a nickel nitrate solution with the concentration of 9 percent (calculated by metal elements), a manganese nitrate solution with the concentration of 4 percent and a ceric ammonium nitrate solution with the concentration of 2 percent, and then mixing the three solutions according to the volume ratio of 1: 1: 1, preparing a mixed solution, and adding hydroxylamine hydrochloride serving as a dispersing agent of 4mg/L into the mixed solution to form an impregnation solution. d) Shaking and mixing: soaking diatomaceous earth in the soaking solution at 140 rpm in a 50 deg.C constant temperature shaking boxShaking for 7 hours; the diatomaceous earth was then removed and allowed to air dry at room temperature. e) And (3) high-temperature sintering: and (2) drying the diatomite in a blast heating box at the temperature of 120 ℃ for 5 hours, then putting the diatomite in a high-temperature furnace with nitrogen as protective gas, heating to 210 ℃ at the speed of 8 ℃/min, roasting at constant temperature for 3 hours, then continuously heating to 610 ℃ at the speed of 15 ℃/min, roasting at constant temperature for 5 hours, and then naturally cooling to prepare the diatomite catalyst.
Aiming at the characteristics of cold rolling oily wastewater, the prepared diatomite catalyst has the supported metal rate of 13 percent, the porosity of 85 percent and the specific surface area of 59m2/g。
After catalytic oxidation by the catalytic tower, the cold rolling oily wastewater is discharged by a drainage pump after reaching the standard.
After the treatment of the whole set of advanced treatment process flow, the cold rolling oil-containing wastewater quality is as follows: the PH value is 6.9, the COD is 22mg/L, the suspended matter is 30mg/L, the conductivity is 3750 mu s/cm, the chloride ion is 810mg/L, and the effluent quality reaches the new national discharge standard.
In conclusion, the cold rolling wastewater advanced treatment system has low one-time investment; the treatment effect is stable; the production and operation cost is low; high automation degree and simple operation. The invention fully embodies the effects of energy conservation and emission reduction, and is an environment-friendly green steel production process.
Of course, those skilled in the art should recognize that the above-described embodiments are illustrative only, and not limiting, and that changes and modifications can be made within the spirit and scope of the invention as defined by the appended claims.
Claims (8)
1. The advanced treatment method of the cold rolling oily wastewater is characterized by comprising the following steps:
cold-rolled oily biochemical effluent enters a multi-media filter, passes through a ceramsite packing area and a grain slag packing area in the multi-media filter, and then enters an intermediate water tank, wastewater in the intermediate water tank enters an ozone catalytic tower through a secondary water inlet pump, and diatomite catalyst packing is filled in the ozone catalytic tower; ozone generated by an ozone generator enters from the bottom of an ozone catalytic tower and is diffused to the whole ozone catalytic tower through an ozone diffuser, the wastewater is subjected to gas-liquid mixing in the ozone catalytic tower and catalytic oxidation through a diatomite catalyst, and the cold-rolled oily wastewater reaches the standard and is discharged;
the diatomite catalyst is prepared by the following steps:
(1) cleaning of the carrier: selecting diatomite with the particle size of 5-25 mm, cleaning the diatomite with a sulfuric acid solution, cleaning the diatomite with distilled water, drying the diatomite for 3-5 hours at 105-110 ℃, and cooling the diatomite for later use;
(2) preparing a solution: preparing a solution, calculating by metal elements, mixing a nickel nitrate solution with the concentration of 5-10%, a manganese nitrate solution with the concentration of 3-8% and a ceric ammonium nitrate solution with the concentration of 1-4%, and adding 2-5 mg/L hydroxylamine hydrochloride into the mixed solution to form an impregnation solution;
(3) shaking and mixing: soaking the diatomite prepared in the step (1) in the dipping solution, shaking for 5-10 hours in a constant-temperature shaking box at 35-55 ℃ at a speed of 120-160 rpm, taking out, and airing;
(4) and (3) high-temperature sintering: roasting the aired diatomite in the step (3) at 210 ℃ for 2-3 hours at constant temperature, then continuously heating to 610 ℃, roasting at constant temperature for 3-5 hours, and naturally cooling to obtain the diatomite catalyst;
the volume ratio of the ceramsite filling area to the grain slag filling area in the multi-media filter is 1: 5-8; the ceramsite has the particle size of 2-10 mm, the porosity of 40-65%, the density of 300-500 kg/m3 and the compressive strength of more than or equal to 1.5 MPa; the chemical components of the granulated slag are mainly CaO: 36-47%; SiO 22：27～45％；Al2O3: 3 to 21 percent; FeO: 0.5-4.5%; the grain size of the granulated slag is 3-20 mm, and the uniformity is 85% -98%; the aperture of the water distributor in the multi-media filter is 25-75 mm.
2. The method for deeply treating the cold rolling oily wastewater as claimed in claim 1, wherein the residence time of the cold rolling oily wastewater in the catalytic tower is 20-70 minutes, the packing density of the diatomite catalyst is 120-330 g/L, and the volume of the diatomite catalyst accounts for 55-75% of the volume of the whole catalytic tower.
3. The advanced treatment method for cold rolling oily wastewater according to claim 1, characterized in that the diatomite catalyst has a supported metal rate of 9-17%, a porosity of 83-90%, and a specific surface area of 53-65 m2/g。
4. The advanced treatment method of cold rolling oily wastewater according to claim 1, characterized in that the diatomite component is mainly SiO2：85～92％；Al2O3：2～5％；CaO：1～2％；Fe2O3: 1-1.5%; MgO: 0.5-1% of impurities and 0.5-5% of impurities; the uniformity of the diatomite is 86% -97%.
5. The advanced treatment method of cold rolling oily wastewater according to claim 1, characterized in that in the preparation of the diatomite catalyst, the mixing is performed in such a way that the volume ratio of nickel nitrate solution, manganese nitrate solution and ceric ammonium nitrate solution is 1: (2-5): (3-6) preparing a mixed solution.
6. The advanced treatment method for cold rolling oily wastewater according to claim 1, characterized in that in the preparation of the diatomite catalyst, the high-temperature sintering: and (2) drying the diatomite in a blast heating box at the temperature of 120 ℃ for 2-5 hours, then putting the diatomite in a high-temperature furnace with nitrogen as protective gas, heating to 210 ℃ at the speed of 5-10 ℃/min, roasting at constant temperature for 2-3 hours, then continuously heating to 610 ℃ at the speed of 10-20 ℃/min, roasting at constant temperature for 3-5 hours, and then naturally cooling to obtain the diatomite catalyst.
7. The advanced treatment method of cold rolling oily wastewater according to claim 1, characterized in that the cold rolling oily wastewater after the treatment method has the following water quality: the PH value is 6-9, the COD is 11-27 mg/L, the suspended matters are 10-35 mg/L, the conductivity is 2500-7500 mu s/cm, the chloride ions are 630-1670 mg/L, and the effluent quality reaches the new national discharge standard.
8. An apparatus for applying the advanced treatment method of cold rolling oily wastewater according to any one of claims 1 to 7, which is characterized by comprising a primary water inlet pump (1), a multi-medium filter (3), an intermediate water tank (11), a secondary water inlet pump (12), an ozone catalytic tower (14) and a drainage pump (21) which are connected in sequence through pipelines; a water distributor (4) is arranged at the inner bottom of the multi-media filter (3), and a ceramsite filling zone (5) and a grain slag filling zone (6) are arranged at the upper part of the water distributor (4); a back flush water inlet (9) and a back flush water outlet (10) are arranged on the upper side and the lower side of the multi-media filter (3); the ozone catalytic tower is characterized in that an ozone diffuser (18) is arranged at the bottom of the ozone catalytic tower (14), the ozone diffuser (18) is connected with an ozone generator (16), an ozone catalyst (15) is filled in the ozone catalytic tower (14), and an ozone outlet (19) of an ozone quencher is arranged at the top of the ozone catalytic tower (14).
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| CN108328889B (en) * | 2018-02-28 | 2021-03-09 | 宝武水务科技有限公司 | Cold rolling wastewater oil residue harmless treatment system and method |
| CN111792751A (en) * | 2020-06-18 | 2020-10-20 | 神马实业股份有限公司 | Treatment method of caprolactam production wastewater |
| CN114751556A (en) * | 2022-04-26 | 2022-07-15 | 北京化工大学 | Method and device for treating oily wastewater |
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