CN113493279A - Low-cost recycling cooperative treatment method and system for negative-hardness wastewater - Google Patents
Low-cost recycling cooperative treatment method and system for negative-hardness wastewater Download PDFInfo
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- 239000003795 chemical substances by application Substances 0.000 claims description 18
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- 235000012239 silicon dioxide Nutrition 0.000 claims description 16
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- 208000028659 discharge Diseases 0.000 claims description 7
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- 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
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
-
- 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
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
-
- 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
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/442—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/10—Nature of the water, waste water, sewage or sludge to be treated from quarries or from mining activities
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/18—Nature of the water, waste water, sewage or sludge to be treated from the purification of gaseous effluents
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Abstract
The invention provides a low-cost resource cooperative treatment method and system for negative hardness wastewater, which are characterized in that coal mine wastewater is purified, concentrated and reduced, and then is softened by using ion exchange groups in resin to obtain concentrated solution retaining bicarbonate; then, respectively mixing and reacting a part of the concentrated solution with the resin regeneration waste liquid, and precipitating calcium and magnesium ions in the resin regeneration waste liquid by using bicarbonate and sulfate radicals in the concentrated solution; and the other part of concentrated solution and the desulfurization wastewater are subjected to synergistic softening treatment and purification treatment, so that sulfate radicals and bicarbonate in the coal mine wastewater fully participate in the precipitation reaction of calcium ions in the softening treatment of the desulfurization wastewater. The invention aims to solve the problem of low single-line treatment efficiency of desulfurization wastewater and coal mine wastewater, softens the coal mine wastewater by an ion exchange method, reduces the addition of a reagent, reserves bicarbonate, and performs synergistic treatment on the coal mine wastewater, resin regeneration waste liquid and desulfurization wastewater, so that the resource recycling of sulfate radicals and bicarbonate is realized, the reagent addition cost is reduced, and the economic benefit is increased.
Description
Technical Field
The invention relates to the technical field of water treatment, in particular to a low-cost recycling cooperative treatment method and system for negative-hardness wastewater.
Background
In recent years, national environmental protection policies are increasingly strict, the investment of thermal power enterprises and coal production enterprises in the aspect of up-to-standard discharge of sewage and wastewater is continuously increased, and particularly, local governments are required to realize zero-discharge treatment of wastewater in provinces such as inner Mongolia autonomous regions and the like. Therefore, the desulfurization wastewater zero-discharge project of the thermal power enterprise is in conflict with the coal mine wastewater zero-discharge project of the coal enterprise.
For coal-electricity integrated enterprises, as power plants and coal mines are constructed closely, wastewater sources also comprise desulfurization wastewater, coal mine wastewater and the like. Calcium ions, magnesium ions and sulfate ions in the desulfurization wastewater are often higher, and bicarbonate ions and sulfate ions in the coal mine wastewater are often higher. In the past, aiming at wastewater treatment projects of various water sources, single-line treatment processes are mainly used, namely, a treatment process route is designed for wastewater, and the treatment process route does not intersect with each other. According to a conventional single-line treatment mode, a large amount of calcium hydroxide is required to be added for precipitating magnesium ions during the softening treatment of the desulfurization wastewater, and then a large amount of sodium carbonate is added for removing residual calcium ions; a large amount of hydrochloric acid or sulfuric acid is required to be added into the coal mine wastewater, and redundant bicarbonate radicals are decomposed into carbon dioxide and water; then adding proper amount of calcium hydroxide or sodium hydroxide to precipitate calcium and magnesium ions. The treatment mode leads a large amount of chloride ions or sulfate ions to be introduced into the coal mine wastewater treatment system, the salt content of the wastewater is increased, the softening effect is difficult to control, the equipment corrosion resistance level is high, the energy consumption and the chemical consumption are high, and the operation cost is high.
The single-line treatment mode usually takes the components in the wastewater as the objects of pollution treatment, additionally increases treatment facilities and medicament consumption, neglects the cooperative treatment of multiple wastewater sources, and can play the roles of self-reaction of the components in the wastewater, waste stopping and resource recycling.
The prior art has the following defects:
1. the desulfurization wastewater and coal mine wastewater single-line treatment mode enables a large amount of hydrochloric acid or sulfuric acid to be added into a coal mine wastewater treatment system to decompose bicarbonate, a large amount of chloride ions or sulfate ions are introduced into a wastewater body, the salt content of the wastewater is increased, and the corrosion resistance grade of equipment of the water treatment system is improved; the energy consumption required for overcoming osmotic pressure is increased; the adding cost of the medicament is high.
2. By adopting a single-line treatment mode, the coal mine wastewater treatment system treats the bicarbonate as a pollution factor to decompose, so that the bicarbonate in the coal mine wastewater cannot be recycled in the desulfurization wastewater treatment system.
3. A single-wire type treatment mode is adopted, carbonate and bicarbonate in a coal mine wastewater treatment system form a buffer system, redundant bicarbonate is decomposed firstly, a proper amount of calcium hydroxide or sodium hydroxide is added to precipitate calcium and magnesium ions, the reaction end point and the dosing amount are not easy to accurately control, the wastewater is not softened thoroughly, and the stable operation of a subsequent treatment system is influenced.
Therefore, a treatment mode which has low equipment cost and stable system operation and can realize the resource recycling of sodium carbonate is urgently needed.
Disclosure of Invention
The invention aims to solve the problem of low single-line treatment efficiency of desulfurization wastewater and coal mine wastewater, softens the coal mine wastewater by an ion exchange method, reduces the addition of a reagent, reserves bicarbonate, and performs synergistic treatment on the coal mine wastewater, resin regeneration waste liquid and desulfurization wastewater, so that the resource recycling of sulfate radicals and bicarbonate is realized, the reagent addition cost is reduced, and the economic benefit is increased.
The invention provides a low-cost resource cooperative treatment method for negative hardness wastewater, which comprises the following steps:
s1, purifying, concentrating and reducing the coal mine wastewater, softening the coal mine wastewater by using ion exchange groups in resin, and retaining bicarbonate to obtain a softened coal mine wastewater concentrated solution;
s2, mixing the softened coal mine wastewater concentrated solution with the desulfurization wastewater to carry out cooperative softening treatment and purification treatment, so that sulfate radicals and bicarbonate radicals in the coal mine wastewater fully participate in the precipitation reaction of calcium ions in the desulfurization wastewater softening treatment, and obtaining cooperative treatment water.
The invention relates to a low-cost recycling cooperative treatment method for negative-hardness wastewater, and as a preferable mode, the step S1 comprises the following steps:
s11, primary filtration: lifting the coal mine wastewater to a V-shaped filter tank through a lifting pump to filter colloid particles, suspended matters and part of organic matters to obtain filtered coal mine wastewater;
s12, primary concentration and decrement: after filtering, the coal mine wastewater sequentially passes through a primary self-cleaning filter and a primary ultrafiltration device to filter suspended matters, enters a primary reverse osmosis device to be concentrated to obtain coal mine wastewater after primary concentration and decrement, and the produced water is recycled;
s13, ion exchange: the coal mine wastewater after the first-stage concentration and decrement enters an ion exchanger, the ion exchanger is filled with resin, the ion exchange groups of the resin exchange calcium and magnesium ions in the coal mine wastewater after the first-stage concentration and decrement with each other to remove the calcium ions and the magnesium ions, so that the calcium ions and the magnesium ions in the coal mine wastewater are removed, the wastewater is softened, ion exchange product water and resin regeneration waste liquid are obtained, the ion exchange product water enters step S14 for treatment, and the resin regeneration waste liquid enters step S15 for treatment;
s14, secondary concentration and decrement: the ion exchange produced water is filtered by a secondary self-cleaning filter and a secondary ultrafiltration device in sequence, and then enters a secondary reverse osmosis device for concentration to obtain softened coal mine wastewater concentrated solution, and the produced water is recycled;
s15, treatment of the regenerated waste liquid: and (3) enabling the resin regeneration waste liquid and the partially softened coal mine waste water concentrated solution to enter a regeneration waste liquid treatment system, and precipitating calcium and magnesium ions in the resin regeneration waste liquid by using bicarbonate and sulfate radicals of the softened coal mine waste water concentrated solution to obtain supernatant of a regeneration waste liquid system and chemical sludge.
The invention relates to a low-cost recycling cooperative treatment method for negative-hardness wastewater, and as a preferable mode, the step S2 comprises the following steps:
s21, primary softening: enabling the desulfurization wastewater and part of softened coal mine wastewater concentrated solution to enter an inclined plate sedimentation tank for mixing, then precipitating magnesium ions, calcium ions, silicon dioxide and sulfate radicals under the action of sulfate radicals, carbonate radicals and a first reagent in the softened coal mine wastewater concentrated solution, and removing colloidal particles, suspended matters and part of organic matters to obtain primary softened and clarified produced water and chemical sludge;
s22, secondary softening: uniformly mixing the primary softened and clarified produced water with the rest softened coal mine wastewater concentrated solution in a triple box, and further precipitating calcium ions, magnesium ions and silicon dioxide by using bicarbonate, a second medicament and/or a third medicament in the softened coal mine wastewater concentrated solution to obtain secondary softened produced water and chemical sludge;
s23, filtering: and filtering the product water after the secondary softening by using a tubular ultrafiltration device to obtain the co-processed product water.
The invention discloses a low-cost recycling cooperative treatment method for negative hardness wastewater, which is a preferable mode, and the step S2 further comprises the step S24:
s24, subsequent processing: the co-processing produced water enters a nano-filtration device and/or a high-pressure reverse osmosis filtration device and/or an evaporative crystallization device for zero discharge processing, and the low-cost recycling co-processing of the negative-hardness wastewater is completed.
The invention relates to a low-cost recycling cooperative treatment method for negative-hardness wastewater, which is characterized in that S12, first-level concentration and decrement: the filtered coal mine wastewater sequentially passes through a primary self-cleaning filter and a primary ultrafiltration device to filter suspended matters and then enters a primary reverse osmosis device, the primary reverse osmosis device is concentrated to obtain primary concentrated and reduced coal mine wastewater, the produced water of the primary reverse osmosis device is recycled, the produced water of the primary ultrafiltration device is collected, the pH value is adjusted to 7.5-8.0, and then the water is conveyed to the primary reverse osmosis device through a water pump for concentration and reduction;
s14, secondary concentration and decrement: the ion exchange produced water is filtered by a secondary self-cleaning filter and a secondary ultrafiltration device in sequence, enters a secondary reverse osmosis device for concentration to obtain softened coal mine wastewater concentrated solution, is recycled, is collected, is adjusted to pH 7.5-8.0 and is conveyed to the secondary reverse osmosis device through a water pump for concentration and decrement;
in step S12, the primary ultrafiltration device uses an external pressure type ultrafiltration membrane or an immersion type ultrafiltration membrane; the first-stage reverse osmosis device uses an antipollution roll type reverse osmosis membrane, the recovery rate is 70-75%, and a scale inhibitor can be added according to the scaling tendency of calcium carbonate, magnesium carbonate, calcium sulfate, magnesium sulfate, calcium fluoride, barium sulfate and the like;
in step S13, the resin is a chelating resin, the chelating resin is a weak acid type cation exchange resin, and the ion exchanger is a forward flow acid-base regeneration mode;
in step S14, the secondary ultrafiltration device uses an external pressure type ultrafiltration membrane or an immersion type ultrafiltration membrane; the secondary reverse osmosis device uses an antipollution roll type reverse osmosis membrane, the recovery rate is 70-80%, and a scale inhibitor can be added according to the scaling tendency of calcium carbonate, magnesium carbonate, calcium sulfate, magnesium sulfate, calcium fluoride, barium sulfate and the like;
in step S15, the supernatant of the regenerated waste liquid system enters the water inlet of the inclined plate sedimentation tank.
According to the low-cost recycling cooperative treatment method for negative-hardness wastewater, as a preferred mode, in step S21, a first agent is calcium hydroxide, the molar ratio of the added calcium hydroxide to magnesium ions in an inclined plate sedimentation tank is 1-1.5, and the pH value is 10.5-12;
the ratio of the sum of the mole numbers of sulfate radicals and carbonate radicals to the mole number of calcium ions in the inclined plate sedimentation tank is 1: 1.
according to the low-cost recycling cooperative treatment method for negative-hardness wastewater, as a preferred mode, in step S22, the second agent is sodium hydroxide, and the pH value in the triple box after the sodium hydroxide is added is 11-12; the third agent is sodium carbonate;
if the produced water after the primary softening and clarification is mixed with the rest softened coal mine wastewater concentrated solution to supplement the bicarbonate is insufficient, adding sodium carbonate into the triple box to supplement the carbonate to precipitate calcium ions.
According to the low-cost recycling cooperative treatment method for negative-hardness wastewater, as a preferred mode, in step S23, effluent of a triple box is conveyed to a tubular ultrafiltration device through a circulating pump, chemical precipitation sludge, colloidal particles and suspended matters intercepted by the tubular ultrafiltration device are conveyed to a triple box through a return pipeline, and a circulating cross-flow filtration system is formed;
the filter membrane materials of the first-stage ultrafiltration device, the second-stage ultrafiltration device and the tubular ultrafiltration device are all PVDF.
The invention provides a low-cost recycling cooperative treatment system for negative hardness wastewater, which comprises a V-shaped filter tank, a primary self-cleaning filter, a primary ultrafiltration device, a primary reverse osmosis device, an ion exchanger, a secondary self-cleaning filter, a secondary ultrafiltration device, a secondary reverse osmosis device, a regenerated waste liquid treatment system, an inclined plate sedimentation tank, a three-header tank and a tubular ultrafiltration device, wherein the regenerated waste liquid treatment system, the inclined plate sedimentation tank, the three-header tank and the tubular ultrafiltration device are connected with a concentrated water outlet of the secondary reverse osmosis device in sequence;
the ion exchanger comprises an ion exchanger body, and an ion exchanger water inlet, an ion exchanger water outlet and a resin regeneration waste liquid water outlet which are arranged on the ion exchanger body, wherein the ion exchanger water inlet is connected with a concentrated water outlet of the primary reverse osmosis device, the ion exchanger water outlet is connected with a water inlet of the secondary self-cleaning filter, and the resin regeneration waste liquid water outlet is connected with a water inlet of a regeneration waste liquid treatment system;
the second-stage reverse osmosis device comprises a second-stage reverse osmosis device body, and a second-stage reverse osmosis water inlet, a second-stage reverse osmosis first concentrated water outlet, a second-stage reverse osmosis second concentrated water outlet, a second-stage reverse osmosis third concentrated water outlet and a second-stage reverse osmosis produced water outlet which are arranged on the second-stage reverse osmosis device body, wherein the second-stage reverse osmosis water inlet is connected with the water outlet of the second-stage ultrafiltration device, the second-stage reverse osmosis first concentrated water outlet is connected with the water inlet of the regenerated waste liquid treatment system, and the second-stage reverse osmosis third concentrated water outlet is connected with the water inlet of the third header;
the inclined plate sedimentation tank comprises an inclined plate sedimentation tank body and an inclined plate sedimentation tank first water inlet, an inclined plate sedimentation tank second water inlet, an inclined plate sedimentation tank third water inlet, an inclined plate sedimentation tank water outlet and an inclined plate sedimentation tank mud outlet which are arranged on the inclined plate sedimentation tank body, wherein the inclined plate sedimentation tank first water inlet is connected with a second-stage reverse osmosis second concentrated water outlet, the inclined plate sedimentation tank second water inlet is connected with a water outlet of a desulfurization waste water system, the inclined plate sedimentation tank third water inlet is connected with a supernatant outlet of a regeneration waste liquid treatment system, and the inclined plate sedimentation tank water outlet is connected with a water inlet of a triple box;
the V-shaped filter tank is used for filtering colloidal particles, suspended matters and partial organic matters of the coal mine wastewater to obtain filtered coal mine wastewater, the primary self-cleaning filter and the primary ultrafiltration device are used for filtering fine suspended matters of the filtered coal mine wastewater, the primary reverse osmosis device is used for concentrating the filtered coal mine wastewater to obtain primary concentrated reduced coal mine wastewater, the ion exchanger is used for utilizing ion exchange groups in filled resin to exchange calcium and magnesium ions of the coal mine wastewater mutually to remove the calcium and magnesium ions in the coal mine wastewater and soften the wastewater to obtain ion exchange product water and resin regeneration waste liquid, the secondary self-cleaning filter and the secondary ultrafiltration device are used for further filtering fine suspended matters in the ion exchange product water, and the secondary reverse osmosis device is used for concentrating the ion exchange product water to obtain softened coal mine wastewater concentrated liquid; the regeneration waste liquid treatment system is used for precipitating calcium and magnesium ions in the resin regeneration waste liquid by using bicarbonate and sulfate radicals of the softened coal mine waste water concentrated liquid to obtain supernatant of the regeneration waste liquid system and chemical sludge; the inclined plate sedimentation tank is used for mixing part of softened coal mine wastewater concentrated solution with desulfurization wastewater, then precipitating magnesium ions, calcium ions, silicon dioxide and sulfate radicals under the action of sulfate radicals and a first agent in the softened coal mine wastewater concentrated solution, removing colloid particles, suspended matters and part of organic matters to obtain primary softened and clarified produced water and chemical sludge, the triple box is used for uniformly mixing the produced water of the inclined plate sedimentation tank with the rest softened coal mine wastewater concentrated solution, and further precipitating the calcium ions, the magnesium ions and the silicon dioxide under the action of bicarbonate, a second agent and/or a third agent in the softened coal mine wastewater concentrated solution to obtain secondary softened produced water and chemical sludge, and the tubular ultrafiltration device is used for filtering the secondary softened produced water to obtain co-treated produced water.
The low-cost recycling cooperative treatment system for negative-hardness wastewater disclosed by the invention further comprises a subsequent treatment unit connected with an outlet of the tubular ultrafiltration membrane, wherein the subsequent treatment unit is used for carrying out zero-emission treatment on the cooperative treatment produced water and comprises a nanofiltration device and/or a high-pressure reverse osmosis device and/or an evaporative crystallization device;
the water outlet of the first-stage ultrafiltration device is connected with the water inlet of the first-stage reverse osmosis device;
the second-stage reverse osmosis device also comprises a second-stage reverse osmosis water inlet arranged on the second-stage reverse osmosis device body, and the second-stage reverse osmosis water inlet is connected with a water production outlet of the second-stage ultrafiltration device;
the water outlet of the circulating pipeline of the tubular ultrafiltration device is connected with the water inlet of the triple box concentration tank.
The coal mine wastewater with negative hardness is lifted to the V-shaped filter tank through a water pump, and the effect of removing colloid particles, suspended matters and partial organic matters in the wastewater is achieved. The water produced by the V-shaped filter chamber is lifted to a first-level self-cleaning filter by a water pump, the effect of removing fine suspended matters in the wastewater is achieved, the filtering precision of the first-level self-cleaning filter is less than or equal to 100 mu m, and a motor-driven suction type self-cleaning filter is preferred. The water produced by the first-stage self-cleaning filter is conveyed to the first-stage ultrafiltration to remove fine suspended matters in the wastewater and delay the pollution of the reverse osmosis membrane, an external pressure type ultrafiltration membrane or an immersed type ultrafiltration membrane can be adopted, the external pressure type ultrafiltration membrane is preferably selected, and PVDF is preferably selected as the material of the ultrafiltration membrane. After the primary ultrafiltration produced water is collected, the PH value is adjusted to 7.5-8.0, the water is conveyed to primary reverse osmosis through a water pump to play a role in concentration and reduction, a low-pressure pollution-resistant rolled reverse osmosis membrane is adopted, the recovery rate can be designed to be 70% -75%, and a scale inhibitor is considered to be added according to the scaling tendency of calcium carbonate, magnesium carbonate, calcium sulfate, magnesium sulfate, calcium fluoride, barium sulfate and the like. And collecting the first-stage reverse osmosis produced water for reuse, and conveying the first-stage reverse osmosis concentrated water to the ion exchanger through a water pump.
The filling resin of the ion exchanger is chelating resin, the type of the filling resin is weak acid type cation exchange resin, the running flow rate is 25m/h, the downstream acid-base regeneration mode and the regeneration period are 24h, and the active groups in the resin are utilized to exchange with calcium and magnesium ions in the wastewater, so that the effects of removing the calcium and magnesium ions in the wastewater, softening the wastewater and retaining bicarbonate are achieved. The regeneration waste liquid treatment system is used for precipitating calcium ions and magnesium ions absorbed by the resin from the waste water in the regeneration waste liquid, and after the chemical sludge is precipitated and filtered, the supernatant is conveyed to the inclined plate sedimentation tank.
The water produced by the ion exchanger is lifted by a water pump to play a role in removing fine suspended matters in the wastewater, the filtering precision of the secondary self-cleaning filter is less than or equal to 100 mu m, and a motor-driven suction type self-cleaning filter is preferred. And the produced water of the secondary self-cleaning filter is conveyed to secondary ultrafiltration to remove fine suspended matters in the wastewater and delay the pollution of the reverse osmosis membrane, an external pressure type ultrafiltration membrane or an immersed type ultrafiltration membrane can be adopted, the external pressure type ultrafiltration membrane is preferably selected, and PVDF is preferably selected as the material of the ultrafiltration membrane. After the second-stage ultrafiltration produced water is collected, the PH value is adjusted to 7.5-8.0, the water is conveyed to the second-stage reverse osmosis by a water pump to play a role in concentration and reduction, an anti-pollution roll type reverse osmosis membrane is adopted, the recovery rate can be designed to be 70% -80%, and when the high recovery rate is selected, the scale inhibitor is considered to be added. Collecting and recycling secondary reverse osmosis produced water, conveying the secondary reverse osmosis concentrated water to a regeneration waste liquid treatment system, an inclined plate sedimentation tank and a triple box in proportion, determining the distribution proportion according to the precipitation reaction of calcium ions, magnesium ions, sulfate radicals, bicarbonate radicals and hydroxyl radicals in a waste water system, preferentially selecting bicarbonate radicals and sulfate radicals in the secondary reverse osmosis concentrated water to be supplemented in the regeneration waste liquid treatment system, and meeting the requirement of carbonate radicals and sulfate radicals required by the precipitation of calcium ions and magnesium ions in the resin regeneration waste liquid; secondly, sulfate radicals in the second-stage reverse osmosis concentrated water are supplemented in the inclined plate sedimentation tank, so that after calcium hydroxide is added into the inclined plate sedimentation tank, the ratio of the sum of the mole numbers of the sulfate radicals and carbonate radicals in the wastewater to the mole number of calcium ions is 1: 1, ensuring the maximum precipitation of calcium ions; and (3) conveying the residual second-stage reverse osmosis concentrated water to a triple box, mainly supplementing bicarbonate in the second-stage reverse osmosis concentrated water for precipitating residual calcium ions in the produced water of the inclined plate sedimentation tank, and if the bicarbonate in the residual second-stage reverse osmosis concentrated water is not more than the residual calcium ions in the produced water of the complete precipitation inclined plate sedimentation tank, precipitating the residual calcium ions by supplementing extra sodium carbonate.
The desulfurization wastewater is lifted to an inclined plate sedimentation tank through a water pump, concentrated water of a second-stage reverse osmosis part and the desulfurization wastewater are fully mixed in the inclined plate sedimentation tank, calcium hydroxide is added into the inclined plate sedimentation tank, the purity of the calcium hydroxide is preferably higher than 85%, the molar ratio of the added calcium hydroxide to magnesium ions in the wastewater is 1-1.5, the pH is controlled to be 10.5-12, the calcium ions, the magnesium ions, silicon dioxide and sulfate radicals are precipitated, and colloidal particles, suspended matters and part of organic matters in the wastewater are removed. Lifting the water produced by the inclined plate sedimentation tank to a triple box through a water pump, fully mixing the water produced by the inclined plate sedimentation tank and the secondary reverse osmosis residual concentrated water in the triple box, adding sodium hydroxide and sodium carbonate into the triple box, controlling the pH value to be 11-12 by adding the sodium hydroxide, and precipitating calcium ions, magnesium ions and a small amount of silicon dioxide. If the bicarbonate in the residual second-stage reverse osmosis concentrated water is sufficient, sodium carbonate does not need to be added; if the residual calcium ions in the water produced by the complete precipitation inclined plate sedimentation tank are not enough, the residual calcium ions are precipitated by supplementing additional sodium carbonate. The effluent of the triple box is conveyed to a tubular ultrafiltration membrane through a high-flow circulating pump, chemical precipitation sludge, colloidal particles and suspended matters intercepted by the tubular ultrafiltration membrane are conveyed to the triple box through a return pipeline to form a circulating cross-flow filtration system, and the material of the tubular ultrafiltration membrane is preferably PVDF; and conveying the produced water filtered by the tubular ultrafiltration membrane to a subsequent treatment unit, wherein the subsequent treatment unit can comprise a nanofiltration device, a high-pressure reverse osmosis device, an evaporative crystallization device and the like, and finally realizing zero-emission treatment.
The invention has the following advantages:
(1) the wastewater is softened by adopting an ion exchange method, so that a large amount of chloride ions or sulfate ions are prevented from being introduced, and the corrosion resistance grade of equipment of a zero-emission system can be reduced; the energy consumption for overcoming osmotic pressure is reduced; the adding cost of the medicament is reduced.
(2) And the wastewater is softened by adopting an ion exchange method, so that the influence caused by a buffer system consisting of carbonate and bicarbonate caused by dosing treatment is avoided, and the running stability of the system is ensured.
(3) And the desulfurization wastewater and the coal mine wastewater are subjected to cooperative treatment, so that the resource recycling of bicarbonate is realized, the adding cost of the medicament is reduced, and the economic benefit is increased.
Drawings
FIG. 1 is a flow chart of a low-cost recycling cooperative treatment method for negative hardness wastewater;
FIG. 2 is a flow chart of a low-cost recycling cooperative processing method for negative hardness wastewater, step S1;
FIG. 3 is a flow chart of a low-cost recycling cooperative processing method for negative hardness wastewater, step S2;
FIG. 4 is a schematic structural diagram of an embodiment 3 of a low-cost recycling cooperative treatment system for negative-hardness wastewater;
FIG. 5 is a schematic structural diagram of the negative hardness wastewater low-cost recycling cooperative treatment system of the embodiments 4 and 5.
Reference numerals:
1. a V-shaped filter chamber; 2. a primary self-cleaning filter; 3. a primary ultrafiltration device; 4. a first-stage reverse osmosis device; 5. an ion exchanger; 51. an ion exchanger body; 52. a water inlet of the ion exchanger; 53. a water outlet of the ion exchanger; 54. a resin regeneration waste liquid outlet; 6. a secondary self-cleaning filter; 7. a secondary ultrafiltration device; 8. a secondary reverse osmosis device; 81. a secondary reverse osmosis device body; 82. a secondary reverse osmosis water inlet; 83. a second-stage reverse osmosis first concentrated water outlet; 84. a second-stage reverse osmosis second concentrated water outlet; 85. a second-stage reverse osmosis third concentrated water outlet; 86. a secondary reverse osmosis water outlet; 9. a regeneration waste liquid treatment system; 10. a sloping plate sedimentation tank; 101. a sloping plate sedimentation tank body; 102. a first water inlet of the inclined plate sedimentation tank; 103. a second water inlet of the inclined plate sedimentation tank; 104. a third water inlet of the inclined plate sedimentation tank; 105. a water outlet of the inclined plate sedimentation tank; 106. a sludge outlet of the inclined plate sedimentation tank; 11. a triple header; 12. a tubular ultrafiltration membrane; 13. and a subsequent processing unit.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments.
Example 1
As shown in figure 1, the low-cost recycling cooperative treatment method for negative-hardness wastewater comprises the following steps:
s1, purifying, concentrating and reducing the coal mine wastewater, softening the coal mine wastewater by using ion exchange groups in resin, and retaining bicarbonate to obtain a softened coal mine wastewater concentrated solution;
s2, mixing the softened coal mine wastewater concentrated solution with desulfurization wastewater for cooperative softening treatment and purification treatment, so that sulfate radicals and bicarbonate radicals in the coal mine wastewater fully participate in the precipitation reaction of calcium ions in the desulfurization wastewater softening treatment, and obtaining cooperative treatment water.
Example 2
As shown in figure 1, the low-cost recycling cooperative treatment method for negative-hardness wastewater comprises the following steps:
s1, purifying, concentrating and reducing the coal mine wastewater, softening the coal mine wastewater by using ion exchange groups in resin, and retaining bicarbonate to obtain a softened coal mine wastewater concentrated solution;
as shown in fig. 2, S11, first stage filtering: lifting the coal mine wastewater to a V-shaped filter 1 through a lifting pump to filter colloid particles, suspended matters and part of organic matters to obtain filtered coal mine wastewater;
s12, primary concentration and decrement: the filtered coal mine wastewater sequentially passes through a primary self-cleaning filter 2 and a primary ultrafiltration device 3 to filter suspended matters and then enters a primary reverse osmosis device 4, the primary reverse osmosis device 4 is concentrated to obtain primary concentrated and reduced coal mine wastewater, the produced water of the primary reverse osmosis device 4 is recycled, the produced water of the primary ultrafiltration device 3 is collected, the pH is adjusted to 7.5-8.0, and then the water is conveyed to the primary reverse osmosis device 4 through a water pump for concentration and reduction;
the first-stage ultrafiltration device 3 uses an external pressure type ultrafiltration membrane or an immersion type ultrafiltration membrane; the first-stage reverse osmosis device 4 uses an antipollution roll type reverse osmosis membrane, the recovery rate is 70-75%, and a scale inhibitor can be added according to the scaling tendency of calcium carbonate, magnesium carbonate, calcium sulfate, magnesium sulfate, calcium fluoride, barium sulfate and the like;
s13, ion exchange: the coal mine wastewater after the first-stage concentration and decrement enters an ion exchanger 5, resin is filled in the ion exchanger 5, ion exchange groups of the resin exchange calcium and magnesium ions in the coal mine wastewater after the first-stage concentration and decrement, so that the calcium and magnesium ions in the coal mine wastewater are removed, the wastewater is softened, ion exchange product water and resin regeneration waste liquid are obtained, the ion exchange product water enters step S14 for treatment, and the resin regeneration waste liquid enters step S15 for treatment;
s14, secondary concentration and decrement: the ion exchange produced water is filtered by a secondary self-cleaning filter 6 and a secondary ultrafiltration device 7 in sequence, and then enters a secondary reverse osmosis device 8 for concentration to obtain softened coal mine wastewater concentrated solution, the produced water of the secondary reverse osmosis device 8 is recycled, the produced water of the secondary ultrafiltration device 7 is collected, the pH is adjusted to 7.5-8.0, and then the water is conveyed to the secondary reverse osmosis device 8 through a water pump for concentration and decrement;
the second-stage ultrafiltration device 7 uses an external pressure type ultrafiltration membrane or an immersion type ultrafiltration membrane; the secondary reverse osmosis device 8 uses an antipollution roll type reverse osmosis membrane, the recovery rate is 70-80%, and a scale inhibitor can be added according to the scaling tendency of calcium carbonate, magnesium carbonate, calcium sulfate, magnesium sulfate, calcium fluoride, barium sulfate and the like;
s15, treatment of the regenerated waste liquid: the resin regeneration waste liquid and part of softened coal mine waste water concentrated liquid enter a regeneration waste liquid treatment system 9, and calcium and magnesium ions in the resin regeneration waste liquid are precipitated by using bicarbonate and sulfate radicals of the softened coal mine waste water concentrated liquid to obtain supernatant of a regeneration waste liquid system and chemical sludge;
supernatant of the regeneration waste liquid system enters a water inlet of the inclined plate sedimentation tank 10;
s2, mixing the softened coal mine wastewater concentrated solution with desulfurization wastewater for cooperative softening treatment and purification treatment, so that sulfate radicals and bicarbonate radicals in the coal mine wastewater fully participate in the precipitation reaction of calcium ions in the desulfurization wastewater softening treatment, and obtaining cooperative treatment water;
as shown in fig. 3, S21, primary softening: the desulfurization wastewater and part of softened coal mine wastewater concentrated solution enter an inclined plate sedimentation tank 10 to be mixed, then magnesium ions, calcium ions, silicon dioxide and sulfate radicals are precipitated under the action of sulfate radicals, carbonate radicals and a first reagent in the softened coal mine wastewater concentrated solution, and colloid particles, suspended matters and part of organic matters are removed to obtain primary softened and clarified produced water and chemical sludge;
the first agent is calcium hydroxide, the molar ratio of the added calcium hydroxide to magnesium ions in the inclined plate sedimentation tank 10 is 1-1.5, and the pH value is 10.5-12;
the ratio of the sum of the mole numbers of sulfate radicals and carbonate radicals to the mole number of calcium ions in the inclined plate sedimentation tank 10 is 1: 1;
s22, secondary softening: uniformly mixing the primary softened and clarified produced water and the rest softened coal mine wastewater concentrated solution in a triple box 11, and further precipitating calcium ions, magnesium ions and silicon dioxide by using bicarbonate, a second medicament and/or a third medicament in the softened coal mine wastewater concentrated solution to obtain secondary softened produced water and chemical sludge;
the second agent is sodium hydroxide, and the pH value in the triple box 11 is 11-12 after the sodium hydroxide is added; the third agent is sodium carbonate;
if the produced water after the primary softening and clarification is mixed with the rest softened coal mine wastewater concentrated solution to supplement the bicarbonate is insufficient, adding sodium carbonate into the triple box 11 to supplement the carbonate to precipitate calcium ions;
s23, filtering: the product water after the secondary softening is filtered by a tubular ultrafiltration device 12 to obtain co-processed product water;
the effluent of the triple box 11 is conveyed to a tubular ultrafiltration device 12 through a circulating pump, and chemical precipitated sludge, colloidal particles and suspended matters intercepted by the tubular ultrafiltration device 12 are conveyed to the triple box 11 through a return pipeline to form a circulating cross-flow filtration system;
the filter membrane materials of the primary ultrafiltration device 3, the secondary ultrafiltration device 7 and the tubular ultrafiltration device 12 are all PVDF;
s24, subsequent processing: the co-processing produced water enters a nano-filtration device and/or a high-pressure reverse osmosis filtration device and/or an evaporative crystallization device for zero discharge processing, and the low-cost recycling co-processing of the negative-hardness wastewater is completed.
Example 3
As shown in fig. 4, a low-cost recycling cooperative treatment system for negative-hardness wastewater comprises a V-shaped filter 1, a primary self-cleaning filter 2, a primary ultrafiltration device 3, a primary reverse osmosis device 4, an ion exchanger 5, a secondary self-cleaning filter 6, a secondary ultrafiltration device 7, a secondary reverse osmosis device 8, a regenerative waste liquid treatment system 9, an inclined plate sedimentation tank 10, a triple box 11 and a tubular ultrafiltration device 12 connected with a water outlet of the triple box 11, which are connected in sequence;
the ion exchanger 5 comprises an ion exchanger body 51, and an ion exchanger water inlet 52, an ion exchanger water outlet 53 and a resin regeneration waste liquid water outlet 54 which are arranged on the ion exchanger body 51, wherein the ion exchanger water inlet 52 is connected with a concentrated water outlet of the primary reverse osmosis device 4, the ion exchanger water outlet 53 is connected with a water inlet of the secondary self-cleaning filter 6, and the resin regeneration waste liquid water outlet 54 is connected with a water inlet of the regeneration waste liquid treatment system 9;
the second-stage reverse osmosis device 8 comprises a second-stage reverse osmosis device body 81, and a second-stage reverse osmosis water inlet 82, a second-stage reverse osmosis first concentrated water outlet 83, a second-stage reverse osmosis second concentrated water outlet 84, a second-stage reverse osmosis third concentrated water outlet 85 and a second-stage reverse osmosis produced water outlet 86 which are arranged on the second-stage reverse osmosis device body 81, wherein the second-stage reverse osmosis water inlet 82 is connected with a water outlet of the second-stage ultrafiltration device 7, the second-stage reverse osmosis first concentrated water outlet 83 is connected with a water inlet of the regeneration waste liquid treatment system 9, and the second-stage reverse osmosis third concentrated water outlet 85 is connected with a water inlet of the triple box 11;
the inclined plate sedimentation tank 10 comprises an inclined plate sedimentation tank body 101 and an inclined plate sedimentation tank first water inlet 102, an inclined plate sedimentation tank second water inlet 103, an inclined plate sedimentation tank third water inlet 104, an inclined plate sedimentation tank water outlet 105 and an inclined plate sedimentation tank sludge outlet 106 which are arranged on the inclined plate sedimentation tank body 101, wherein the inclined plate sedimentation tank first water inlet 102 is connected with a second-stage reverse osmosis second concentrated water outlet 84, the inclined plate sedimentation tank second water inlet 103 is connected with a water outlet of a desulfurization wastewater system, the inclined plate sedimentation tank third water inlet 104 is connected with a supernatant outlet of a regeneration wastewater treatment system 9, and the inclined plate sedimentation tank water outlet 105 is connected with a water inlet of a triple box 11;
the V-shaped filter 1 is used for filtering colloidal particles, suspended matters and partial organic matters of the coal mine wastewater to obtain filtered coal mine wastewater, the primary self-cleaning filter 2 and the primary ultrafiltration device 3 are used for filtering fine suspended matters of the filtered coal mine wastewater, the primary reverse osmosis device 4 is used for concentrating the filtered coal mine wastewater to obtain primary concentrated and reduced coal mine wastewater, the ion exchanger 5 is used for utilizing ion exchange groups in filled resin to exchange calcium and magnesium ions of the coal mine wastewater mutually to remove the calcium and magnesium ions in the coal mine wastewater and soften the wastewater to obtain ion exchange product water and resin regeneration waste liquid, the secondary self-cleaning filter 6 and the secondary ultrafiltration device 7 are used for further filtering fine suspended matters in the ion exchange product water, and the secondary reverse osmosis device 8 is used for concentrating the ion exchange product water to obtain softened coal mine wastewater concentrated liquid; the regeneration waste liquid treatment system 9 is used for precipitating calcium and magnesium ions in the resin regeneration waste liquid by using bicarbonate and sulfate radicals of the softened coal mine waste water concentrated liquid to obtain supernatant of the regeneration waste liquid system and chemical sludge; the inclined plate sedimentation tank 10 is used for mixing part of softened coal mine wastewater concentrated solution with desulfurization wastewater, then precipitating magnesium ions, calcium ions, silicon dioxide and sulfate radicals under the action of sulfate radicals and a first agent in the softened coal mine wastewater concentrated solution, removing colloid particles, suspended matters and part of organic matters to obtain once softened and clarified produced water and chemical sludge, the triple box 11 is used for uniformly mixing the once softened and clarified produced water with the rest softened coal mine wastewater concentrated solution, further precipitating the calcium ions, the magnesium ions and the silicon dioxide under the action of bicarbonate, a second agent and/or a third agent in the softened coal mine wastewater concentrated solution to obtain twice softened produced water and chemical sludge, and the tubular ultrafiltration device 12 is used for filtering the twice softened produced water to obtain co-processed produced water.
Example 4
As shown in fig. 5, a low-cost recycling cooperative treatment system for negative-hardness wastewater comprises a V-shaped filter 1, a primary self-cleaning filter 2, a primary ultrafiltration device 3, a primary reverse osmosis device 4, an ion exchanger 5, a secondary self-cleaning filter 6, a secondary ultrafiltration device 7, a secondary reverse osmosis device 8, a regenerated waste liquid treatment system 9, an inclined plate sedimentation tank 10, a triple box 11, a tubular ultrafiltration device 12 connected with a water outlet of the triple box 11 and a subsequent treatment unit 13 connected with an outlet of the tubular ultrafiltration membrane 12, which are connected in sequence, wherein the subsequent treatment unit 13 is used for performing zero-emission treatment on the cooperative treatment produced water, and the subsequent treatment unit 13 comprises a nanofiltration device and/or a high-pressure reverse osmosis device and/or an evaporative crystallization device;
the water outlet of the primary ultrafiltration device 3 is connected with the water inlet of the primary reverse osmosis device 4;
the ion exchanger 5 comprises an ion exchanger body 51, and an ion exchanger water inlet 52, an ion exchanger water outlet 53 and a resin regeneration waste liquid water outlet 54 which are arranged on the ion exchanger body 51, wherein the ion exchanger water inlet 52 is connected with a concentrated water outlet of the primary reverse osmosis device 4, the ion exchanger water outlet 53 is connected with a water inlet of the secondary self-cleaning filter 6, and the resin regeneration waste liquid water outlet 54 is connected with a water inlet of the regeneration waste liquid treatment system 9;
the second-stage reverse osmosis device 8 comprises a second-stage reverse osmosis device body 81, and a second-stage reverse osmosis water inlet 82, a second-stage reverse osmosis first concentrated water outlet 83, a second-stage reverse osmosis second concentrated water outlet 84, a second-stage reverse osmosis third concentrated water outlet 85 and a second-stage reverse osmosis water production water outlet 86 which are arranged on the second-stage reverse osmosis device body 81, wherein the second-stage reverse osmosis water inlet 82 is connected with a water outlet of the second-stage ultrafiltration device 7, the second-stage reverse osmosis first concentrated water outlet 83 is connected with a water inlet of the regeneration waste liquid treatment system 9, and the second-stage reverse osmosis third concentrated water outlet 85 is connected with a water inlet of the triple box 11;
the inclined plate sedimentation tank 10 comprises an inclined plate sedimentation tank body 101 and an inclined plate sedimentation tank first water inlet 102, an inclined plate sedimentation tank second water inlet 103, an inclined plate sedimentation tank third water inlet 104, an inclined plate sedimentation tank water outlet 105 and an inclined plate sedimentation tank mud outlet 106 which are arranged on the inclined plate sedimentation tank body 101, wherein the inclined plate sedimentation tank first water inlet 102 is connected with a second-stage reverse osmosis second concentrated water outlet 84, the inclined plate sedimentation tank second water inlet 103 is connected with a water outlet of a desulfurization wastewater system, the inclined plate sedimentation tank third water inlet 104 is connected with a supernatant outlet of a regeneration wastewater treatment system 9, and the inclined plate sedimentation tank water outlet 105 is connected with a water inlet of a triple box 11;
a water outlet of a circulating pipeline of the tubular ultrafiltration device 12 is connected with a water inlet of a concentration tank of the triple box 11;
the V-shaped filter 1 is used for filtering colloidal particles, suspended matters and partial organic matters of the coal mine wastewater to obtain filtered coal mine wastewater, the primary self-cleaning filter 2 and the primary ultrafiltration device 3 are used for filtering fine suspended matters of the filtered coal mine wastewater, the primary reverse osmosis device 4 is used for concentrating the filtered coal mine wastewater to obtain primary concentrated and reduced coal mine wastewater, the ion exchanger 5 is used for utilizing ion exchange groups in filled resin to exchange calcium and magnesium ions of the coal mine wastewater mutually to remove the calcium and magnesium ions in the coal mine wastewater and soften the wastewater to obtain ion exchange product water and resin regeneration waste liquid, the secondary self-cleaning filter 6 and the secondary ultrafiltration device 7 are used for further filtering fine suspended matters in the ion exchange product water, and the secondary reverse osmosis device 8 is used for concentrating the ion exchange product water to obtain softened coal mine wastewater concentrated liquid; the regeneration waste liquid treatment system 9 is used for precipitating calcium and magnesium ions in the resin regeneration waste liquid by using bicarbonate and sulfate radicals of the softened coal mine waste water concentrated liquid to obtain supernatant of the regeneration waste liquid system and chemical sludge; the inclined plate sedimentation tank 10 is used for mixing part of softened coal mine wastewater concentrated solution with desulfurization wastewater, then precipitating magnesium ions, calcium ions, silicon dioxide and sulfate radicals under the action of sulfate radicals and a first agent in the softened coal mine wastewater concentrated solution, removing colloid particles, suspended matters and part of organic matters to obtain once softened and clarified produced water and chemical sludge, the triple box 11 is used for uniformly mixing the once softened and clarified produced water with the rest softened coal mine wastewater concentrated solution, further precipitating the calcium ions, the magnesium ions and the silicon dioxide under the action of bicarbonate, a second agent and/or a third agent in the softened coal mine wastewater concentrated solution to obtain twice softened produced water and chemical sludge, and the tubular ultrafiltration device 12 is used for filtering the twice softened produced water to obtain co-processed produced water.
Example 5
As shown in fig. 1, 2, 3 and 5, the coal mine wastewater to be treated has the following water quality:
Ca2+＝59.2mg/L；Mg2+＝8.3mg/L，SO4 2-＝1270mg/L；HCO3 -＝238mg/L；pH＝8.15，SiO2＝4.5mg/L，TDS＝3208mg/L，SS＝8mg/L，Cl-＝643.5mg/L
the quality of the desulfurization wastewater to be treated is as follows:
Ca2+＝709.5mg/L，Mg2+＝5267.5mg/L，SO4 2-＝16030mg/L，HCO3 -＝93.8mg/L，pH＝6.5，SiO2＝122.7mg/L，TDS＝44205mg/L，SS＝62mg/L，Cl-＝15256mg/L
coal mine wastewater inflow rate is 500m3And h, after buffering and adjusting by a coal mine wastewater adjusting tank, lifting to a V-shaped filter tank 1 by a water inlet pump, designing the normal filtering speed of the V-shaped filter tank 1 to be 8m/h, producing water turbidity to be less than or equal to 2NTU, collecting backwashing water, and returning to the coal mine wastewater adjusting tank at the front end of the system for circulating treatment.
The water produced by the V-shaped filter 1 is pumped to the first-level self-cleaning filter 2 by a water pump, the filtering precision of the first-level self-cleaning filter 2 is less than or equal to 100 mu m, a motor-driven suction type self-cleaning filter is selected, and a filter screen is made of SS316L material.
The produced water of the first-level self-cleaning filter 2 is conveyed to the first-level ultrafiltration device 3, the recovery rate of the first-level ultrafiltration device 3 is 92%, an external pressure type hollow fiber membrane is adopted, the ultrafiltration membrane is made of PVDF (polyvinylidene fluoride), the SDI (standard deviation index) index of the produced water is less than or equal to 3.0, the turbidity is less than or equal to 0.2NTU, and backwashing water is returned to a coal mine wastewater adjusting tank at the front end of the system for circular treatment after being collected and treated.
The pH value of the produced water of the primary ultrafiltration device 3 is adjusted to 7.5-8.0, the water is lifted to a primary reverse osmosis device 4 by a booster pump and a high-pressure pump, the primary reverse osmosis device 4 adopts a low-pressure anti-pollution roll type brackish water film, the recovery rate is 75 percent, the product water is collected and recycled, and the product water flow is 375m3The TDS of the product water is 41.86 mg/L; concentrated water flow 125m3H, concentrated water SO4 2-5048mg/L, Ca2+234.65Mg/L, Mg2+32.89mg/L, Cl-2545mg/L of HCO3 -920.2mg/L, TDS 13656mg/L, SiO218mg/L, pH 7.5.
The concentrated water of the first-stage reverse osmosis device 4 is conveyed to the ion exchanger 5 through a water pump. The filling resin of the ion exchanger 5 is chelate resin, the type is weak acid type cation exchange resin, the running flow rate is 25m/h, the downstream acid-base regeneration mode and the regeneration period are 24h, and the quality SO of the produced water of the ion exchanger 54 2-5048mg/L, Ca2+Is less than or equal to 1Mg/L, Mg2+Is less than or equal to 1mg/L, Cl-2545mg/L of HCO3 -886mg/L, TDS 13348mg/L, SiO2＝18mg/L。
The water produced by the ion exchanger 5 is pumped to the second-stage self-cleaning filter 6 by a water pump, the filtering precision of the second-stage self-cleaning filter 6 is less than or equal to 100 mu m, a motor is used for driving the suction type self-cleaning filter, and the filter screen is made of 2205 dual-phase steel.
The produced water of the second-stage self-cleaning filter 6 is conveyed to a second-stage ultrafiltration device 7, the recovery rate of the second-stage ultrafiltration device 7 is 92%, an external pressure type hollow fiber membrane is adopted, the ultrafiltration membrane is made of PVDF (polyvinylidene fluoride), the SDI (standard deviation index) index of the produced water is less than or equal to 3.0, the turbidity is less than or equal to 0.2NTU, and backwashing water is returned to a coal mine wastewater adjusting tank at the front end of the system for circular treatment after being collected and treated.
The produced water of the second-stage ultrafiltration device 7 is lifted to a second-stage reverse osmosis device 8 by a booster pump and a high-pressure pump, the second-stage reverse osmosis device 8 adopts an anti-pollution roll type seawater reverse osmosis membrane, the recovery rate is 75 percent, and the product water flow is 93.75m3Collecting and recycling product water, wherein the TDS of the product water is 256 mg/L; concentrated water flow rate of 31.25m3Per, concentrated water quality SO4 2-19985mg/L, Ca2+4.3Mg/L, Mg2+Is 4.3mg/L, Cl-10000mg/L of HCO3 -3277mg/L and TDS 53845 mg/L.
The regeneration waste liquid treatment system 9 of the ion exchanger introduces secondary reverse osmosis concentrated water, the input quantity of the secondary reverse osmosis concentrated water meets the requirement that the ratio of the sum of the mole numbers of calcium ions and magnesium ions and the sum of the mole numbers of bicarbonate radical and sulfate radical in the regeneration waste liquid treatment system 9 of the ion exchanger is 1: 1.2, the introduction amount of the second-stage reverse osmosis concentrated water is calculated to be 4.5m3H is used as the reference value. Regeneration waste liquid treatment system 9 of ion exchanger for calcium carbonate, magnesium sulfate and sulfurAfter the chemical sludge such as calcium carbonate is precipitated and filtered, the supernatant is conveyed to the inclined plate sedimentation tank 10.
The inlet flow of the desulfurization wastewater of the power plant is 20m3And h, after being treated by the original desulfurization wastewater treatment system of the power plant, lifting the wastewater to a desulfurization wastewater buffer tank through a water pump and flowing into an inclined plate sedimentation tank 10, introducing secondary reverse osmosis concentrated water into the inclined plate sedimentation tank 10, wherein the input quantity of the secondary reverse osmosis concentrated water meets the requirement that the ratio of the sum of the mole numbers of sulfate radicals and carbonate radicals in the wastewater to the mole number of calcium ions is 1: 1, the introduction amount of the second-stage reverse osmosis concentrated water is 5.5m by calculation3The dosage of calcium hydroxide is 18.5kg/m3The calcium hydroxide had a purity of 88% and a pH of 11.5. At this time, the water production flow rate is 30m3H, water quality SO of produced water4 2-13680mg/L, Ca2+1616.75Mg/L, Mg2+Not detected, HCO3 -21.6mg/L and TDS 38702 mg/L.
The produced water of the inclined plate sedimentation tank 10 is lifted to a triple box 11 by a water pump, and the triple box 11 introduces the residual second-stage reverse osmosis concentrated water of 21.25m3And h, after the second-stage reverse osmosis concentrated water is uniformly mixed with the produced water of the inclined plate sedimentation tank 10, adding sodium hydroxide until the pH value of the wastewater is 11.5. Because the hydrogen heavy acid radical in the residual secondary reverse osmosis concentrated water is not enough to the residual calcium ion in the produced water of the complete precipitation inclined plate sedimentation tank, additional sodium carbonate is supplemented to 176g/m3And precipitating the remaining calcium ions.
The chemical precipitated sludge in the triple box 11 is conveyed to a tubular ultrafiltration membrane 12 through a high-flow circulating pump for circulating cross-flow filtration, the material of the tubular ultrafiltration membrane is PVDF, the pH value of the produced water of the tubular ultrafiltration membrane 12 is adjusted to 7.0 by adding sulfuric acid, and the quality of the produced water SO is4 2-16787mg/L, Ca2+≤20mg/L，Mg2+≤20mg/L，HCO3 -Not detected, TDS was 44230 mg/L.
The produced water of the tubular ultrafiltration membrane 12 is conveyed to a subsequent treatment unit 13, which comprises a nanofiltration device, a high-pressure reverse osmosis device, an evaporative crystallization device and the like, through a water pump, and finally zero emission treatment is realized.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (10)
1. A low-cost resource cooperative treatment method for negative-hardness wastewater is characterized by comprising the following steps: the method comprises the following steps:
s1, purifying, concentrating and reducing the coal mine wastewater, softening the coal mine wastewater by using ion exchange groups in resin, and retaining bicarbonate to obtain a softened coal mine wastewater concentrated solution;
s2, mixing the softened coal mine wastewater concentrated solution with desulfurization wastewater for cooperative softening treatment and purification treatment, so that sulfate radicals and bicarbonate radicals in the coal mine wastewater fully participate in the precipitation reaction of calcium ions in the desulfurization wastewater softening treatment, and obtaining cooperative treatment water.
2. The low-cost resource cooperative treatment method for negative-hardness wastewater according to claim 1, characterized in that: step S1 includes:
s11, primary filtration: the coal mine wastewater is lifted to a V-shaped filter tank (1) through a lift pump to filter colloid particles, suspended matters and part of organic matters to obtain filtered coal mine wastewater;
s12, primary concentration and decrement: the filtered coal mine wastewater sequentially passes through a primary self-cleaning filter (2) and a primary ultrafiltration device (3) to filter suspended matters and then enters a primary reverse osmosis device (4) to be concentrated to obtain coal mine wastewater after primary concentration and decrement, and produced water is recycled;
s13, ion exchange: the coal mine wastewater subjected to the primary concentration and decrement enters an ion exchanger (5), the ion exchanger (5) is filled with resin, ion exchange groups of the resin exchange with calcium and magnesium ions in the coal mine wastewater subjected to the primary concentration and decrement, so that the effects of removing the calcium and magnesium ions in the coal mine wastewater and softening the wastewater are realized, ion exchange product water and resin regeneration waste liquid are obtained, the ion exchange product water enters step S14 for treatment, and the resin regeneration waste liquid enters step S15 for treatment;
s14, secondary concentration and decrement: the ion exchange produced water is filtered by a secondary self-cleaning filter (6) and a secondary ultrafiltration device (7) in sequence, and then enters a secondary reverse osmosis device (8) for concentration to obtain a softened coal mine wastewater concentrated solution, and the produced water is recycled;
s15, treatment of the regenerated waste liquid: and the resin regeneration waste liquid and part of the softened coal mine waste water concentrated liquid enter the regeneration waste liquid treatment system (9), and calcium and magnesium ions in the resin regeneration waste liquid are precipitated by using bicarbonate and sulfate radicals of the softened coal mine waste water concentrated liquid to obtain supernatant of the regeneration waste liquid system and chemical sludge.
3. The low-cost resource cooperative treatment method for negative-hardness wastewater according to claim 2, characterized in that: step S2 includes:
s21, primary softening: the desulfurization wastewater and part of the softened coal mine wastewater concentrated solution enter an inclined plate sedimentation tank (10) to be mixed, then magnesium ions, calcium ions, silicon dioxide and sulfate radicals are precipitated under the action of sulfate radicals, carbonate radicals and a first reagent in the softened coal mine wastewater concentrated solution, and colloid particles, suspended matters and part of organic matters are removed to obtain primary softened and clarified produced water and chemical sludge;
s22, secondary softening: uniformly mixing the primary softened and clarified produced water with the rest softened coal mine wastewater concentrated solution in a triple box (11), and further precipitating calcium ions, magnesium ions and silicon dioxide by using bicarbonate, a second medicament and/or a third medicament in the softened coal mine wastewater concentrated solution to obtain secondary softened produced water and chemical sludge;
s23, filtering: and filtering the secondary softened produced water by a tubular ultrafiltration device (12) to obtain the co-processed produced water.
4. The low-cost resource cooperative treatment method for negative-hardness wastewater according to claim 3, characterized in that: step S2 further includes step S24:
s24, subsequent processing: the co-processed produced water enters a nano-filtration device and/or a high-pressure reverse osmosis filtration device and/or an evaporative crystallization device for zero discharge treatment, and the low-cost recycling co-processing of the negative-hardness wastewater is completed.
5. The low-cost resource cooperative treatment method for negative-hardness wastewater according to claim 2, characterized in that:
s12, primary concentration and decrement: the filtered coal mine wastewater sequentially passes through the primary self-cleaning filter (2) and the primary ultrafiltration device (3) to filter suspended matters and then enters the primary reverse osmosis device (4), the primary reverse osmosis device (4) is concentrated to obtain the coal mine wastewater after primary concentration and decrement, the produced water of the primary reverse osmosis device (4) is recycled, the produced water of the primary ultrafiltration device (3) is collected, the pH value is adjusted to 7.5-8.0, and then the water is conveyed to the primary reverse osmosis device (4) through a water pump for concentration and decrement;
s14, secondary concentration and decrement: the ion exchange produced water sequentially passes through the secondary self-cleaning filter (6) and the secondary ultrafiltration device (7) to filter suspended matters and then enters the secondary reverse osmosis device (8) to be concentrated to obtain the softened coal mine wastewater concentrated solution, the produced water of the secondary reverse osmosis device (8) is recycled, the produced water of the secondary ultrafiltration device (7) is collected, the pH is adjusted to 7.5-8.0, and then the water is conveyed to the secondary reverse osmosis device (8) through a water pump to be used for concentration and decrement;
in step S12, the primary ultrafiltration device (3) uses an external pressure type ultrafiltration membrane or an immersion type ultrafiltration membrane; the first-stage reverse osmosis device (4) uses an antipollution roll type reverse osmosis membrane, the recovery rate is 70-75%, and a scale inhibitor can be added according to the scaling tendency of calcium carbonate, magnesium carbonate, calcium sulfate, magnesium sulfate, calcium fluoride, barium sulfate and the like;
in step S13, the resin is a chelating resin, the chelating resin is a weak acid type cation exchange resin, and the ion exchanger (5) is a concurrent acid-base regeneration mode;
in step S14, the secondary ultrafiltration device (7) uses an external pressure type ultrafiltration membrane or an immersion type ultrafiltration membrane; the secondary reverse osmosis device (8) uses an antipollution roll type reverse osmosis membrane, the recovery rate is 70-80%, and a scale inhibitor can be added according to the scaling tendency of calcium carbonate, magnesium carbonate, calcium sulfate, magnesium sulfate, calcium fluoride, barium sulfate and the like;
in step S15, the supernatant of the regenerated waste liquid system enters the water inlet of the inclined plate sedimentation tank (10).
6. The low-cost resource cooperative treatment method for negative-hardness wastewater according to claim 3, characterized in that: in the step S21, the first agent is calcium hydroxide, the molar ratio of the added calcium hydroxide to magnesium ions in the inclined plate sedimentation tank (10) is 1-1.5, and the pH value is 10.5-12;
the ratio of the sum of the mole numbers of sulfate radicals and carbonate radicals in the inclined plate sedimentation tank (10) to the mole number of calcium ions is 1: 1.
7. the low-cost resource cooperative treatment method for negative-hardness wastewater according to claim 3, characterized in that: in the step S22, the second agent is sodium hydroxide, and the pH value in the triple box (11) is 11-12 after the sodium hydroxide is added; the third agent is sodium carbonate;
and if the produced water after the primary softening and clarification is mixed with the rest concentrated solution of the softened coal mine wastewater to supplement the bicarbonate, adding sodium carbonate into the triple box (11) to supplement the carbonate so as to precipitate calcium ions.
8. The low-cost resource cooperative treatment method for negative-hardness wastewater according to claim 3, characterized in that: in the step S23, the effluent of the triple box (11) is conveyed to the tubular ultrafiltration device (12) through a circulating pump, and the chemical precipitation sludge, colloidal particles and suspended matters intercepted by the tubular ultrafiltration device (12) are conveyed to the triple box (11) through a return pipeline to form a circulating cross-flow filtration system;
the filter membranes of the primary ultrafiltration device (3), the secondary ultrafiltration device (7) and the tubular ultrafiltration device (12) are made of PVDF.
9. The utility model provides a low-cost resourceful cooperative processing system of negative hardness waste water which characterized in that: the device comprises a V-shaped filter tank (1), a primary self-cleaning filter (2), a primary ultrafiltration device (3), a primary reverse osmosis device (4), an ion exchanger (5), a secondary self-cleaning filter (6), a secondary ultrafiltration device (7), a secondary reverse osmosis device (8), a regenerated waste liquid treatment system (9) respectively connected with a concentrated water outlet of the secondary reverse osmosis device (8), an inclined plate sedimentation tank (10), a triple box (11) and a tubular ultrafiltration device (12) connected with a water outlet of the triple box (11), which are sequentially connected;
the ion exchanger (5) comprises an ion exchanger body (51), and an ion exchanger water inlet (52), an ion exchanger water outlet (53) and a resin regeneration waste liquid water outlet (54) which are arranged on the ion exchanger body (51), wherein the ion exchanger water inlet (52) is connected with a concentrated water outlet of the primary reverse osmosis device (4), the ion exchanger water outlet (53) is connected with a water inlet of the secondary self-cleaning filter (6), and the resin regeneration waste liquid water outlet (54) is connected with a water inlet of the regeneration waste liquid treatment system (9);
the secondary reverse osmosis device (8) comprises a secondary reverse osmosis device body (81) and a secondary reverse osmosis water inlet (82), a secondary reverse osmosis first concentrated water outlet (83), a secondary reverse osmosis second concentrated water outlet (84), a secondary reverse osmosis third concentrated water outlet (85) and a secondary reverse osmosis water outlet (86) which are arranged on the secondary reverse osmosis device body (81), wherein the secondary reverse osmosis water inlet (82) is connected with a water outlet of the secondary ultrafiltration device (7), the secondary reverse osmosis first concentrated water outlet (83) is connected with a water inlet of the regenerated waste liquid treatment system (9), and the secondary reverse osmosis third concentrated water outlet (85) is connected with a water inlet of the triple box (11);
the inclined plate sedimentation tank (10) comprises an inclined plate sedimentation tank body (101) and an inclined plate sedimentation tank first water inlet (102), an inclined plate sedimentation tank second water inlet (103), an inclined plate sedimentation tank third water inlet (104), an inclined plate sedimentation tank water outlet (105) and an inclined plate sedimentation tank sludge outlet (106) which are arranged on the inclined plate sedimentation tank body (101), wherein the inclined plate sedimentation tank first water inlet (102) is connected with the secondary reverse osmosis second concentrated water outlet (84), the inclined plate sedimentation tank second water inlet (103) is connected with a water outlet of a desulfurization wastewater system, the inclined plate sedimentation tank third water inlet (104) is connected with a supernatant outlet of the regeneration waste liquid treatment system (9), and the inclined plate sedimentation tank water outlet (105) is connected with a water inlet of the triple box (11);
the V-shaped filter tank (1) is used for filtering colloidal particles, suspended matters and partial organic matters of the coal mine wastewater to obtain filtered coal mine wastewater, the primary self-cleaning filter (2) and the primary ultrafiltration device (3) are used for filtering fine suspended matters of the filtered coal mine wastewater, the primary reverse osmosis device (4) is used for concentrating the filtered coal mine wastewater to obtain primary concentrated and reduced coal mine wastewater, the ion exchanger (5) is used for utilizing ion exchange groups in filled resin to exchange with calcium and magnesium ions of the coal mine wastewater mutually to remove the calcium and magnesium ions in the coal mine wastewater and soften the wastewater to obtain ion exchange production water and resin regeneration waste liquid, the secondary self-cleaning filter (6) and the secondary ultrafiltration device (7) are used for further filtering fine suspended matters in the ion exchange production water, the secondary reverse osmosis device (8) is used for concentrating the ion exchange produced water to obtain softened coal mine wastewater concentrated solution; the regeneration waste liquid treatment system (9) is used for precipitating calcium and magnesium ions in the resin regeneration waste liquid by using bicarbonate and sulfate radicals of the softened coal mine waste water concentrated liquid to obtain supernatant of the regeneration waste liquid system and chemical sludge; the inclined plate sedimentation tank (10) is used for mixing part of the softened coal mine wastewater concentrated solution with desulfurization wastewater and then precipitating magnesium ions, calcium ions, silicon dioxide and sulfate radicals under the action of sulfate radicals in the softened coal mine wastewater concentrated solution and a first reagent, removing colloid particles, suspended matters and partial organic matters to obtain primary softened and clarified product water and chemical sludge, the triple box (11) is used for uniformly mixing the water produced after the primary softening and clarification and the residual softened coal mine wastewater concentrated solution, and further precipitating calcium ions, magnesium ions and silicon dioxide under the action of bicarbonate, a second medicament and/or a third medicament in the softened coal mine wastewater concentrated solution to obtain secondarily softened water and chemical sludge, and the tubular ultrafiltration device (12) is used for filtering the secondarily softened produced water to obtain the co-processed produced water.
10. The low-cost recycling cooperative treatment system for negative-hardness wastewater according to claim 9, wherein: the device also comprises a subsequent treatment unit (13) connected with an outlet of the tubular ultrafiltration membrane (12), wherein the subsequent treatment unit (13) is used for carrying out zero emission treatment on the co-treatment produced water, and the subsequent treatment unit (13) comprises a nanofiltration device and/or a high-pressure reverse osmosis device and/or an evaporative crystallization device;
the water production outlet of the primary ultrafiltration device (3) is connected with the water inlet of the primary reverse osmosis device (4);
and a water outlet of a circulating pipeline of the tubular ultrafiltration device (12) is connected with a water inlet of the concentration tank of the triple box (11).
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