CN114890629B - Method for recycling high-salt wastewater - Google Patents

Method for recycling high-salt wastewater Download PDF

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CN114890629B
CN114890629B CN202210612483.5A CN202210612483A CN114890629B CN 114890629 B CN114890629 B CN 114890629B CN 202210612483 A CN202210612483 A CN 202210612483A CN 114890629 B CN114890629 B CN 114890629B
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CN114890629A (en
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黄一东
肖长洪
莫振军
刘雨林
吴双桥
廖圆
周游
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Zijin Mining Group Co Ltd
Heilongjiang Duobaoshan Copper Inc
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Heilongjiang Duobaoshan Copper Inc
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Abstract

The invention relates to the field of wastewater treatment, and particularly discloses a method for recycling high-salt wastewater, which comprises the following steps: the method comprises (1) pretreatment of high-salt wastewater; (2) Removing suspended matters and colloid substances by multi-medium filtration and ultrafiltration; (3) softening water quality; (4) RO membrane reverse osmosis; the effluent of the softening pond is conveyed to a first-stage reverse osmosis for concentration, the first-stage reverse osmosis fresh water enters a second-stage reverse osmosis for further desalination, the second-stage reverse osmosis fresh water is used for production, and the second-stage reverse osmosis concentrated water returns to the first-stage reverse osmosis; (5) fractional evaporation crystallization of sodium sulfate and sodium nitrate. The invention solves the problem of resource waste caused by difficult recovery and utilization of sodium nitrate and sodium sulfate in molybdenum concentrate smelting wastewater in the prior art.

Description

Method for recycling high-salt wastewater
Technical Field
The invention belongs to the field of wastewater treatment, and particularly relates to a method for recycling high-salt wastewater.
Background
The ammonium molybdate production process comprises the steps of roasting, pre-pickling, ammonia leaching, impurity removal and acid precipitation, wherein a large amount of nitric acid is added in the pre-pickling and acid precipitation processes, and ammonia stripping and ammonia distillation of the ammonia-containing wastewater are carried out by adopting liquid alkali to adjust the pH value, and sodium ions are introduced. At the same time, the flue gas washing process and the flue gas desulfurization process also generate a part of waste water containing sulfate radicals. Finally, the main salt of the total wastewater in the molybdenum concentrate smelting is sodium nitrate and sodium sulfate, and the disposal mode is that the treatment reaches the standard and is discharged outwards or recycled for production procedures. The wastewater contains high-concentration sodium nitrate and sodium sulfate salt, and if the wastewater is directly recycled to other production processes, adverse effects on a production system can be generated; if the treatment reaches the standard, the treatment is discharged, and nitrate nitrogen and high salt content still have some influence on the environment.
Disclosure of Invention
The invention provides a method for recycling high-salt wastewater, which aims to solve the problem that sodium nitrate and sodium sulfate in molybdenum concentrate smelting wastewater are difficult to recycle and cause resource waste in the prior art.
The technical scheme of the invention is as follows: a method for recycling high-salt wastewater comprises the following steps:
(1) Pretreatment of high-salt wastewater; the wastewater is collected and enters a water collecting tank, then sequentially passes through a first-stage reaction tank, a second-stage reaction tank, a third-stage reaction tank and a fourth-stage reaction tank, then enters a sedimentation tank for solid-liquid separation, the supernatant enters a clean water tank, the solid is subjected to filter pressing, and filter residues after filter pressing are safely disposed;
(2) Removing suspended matters and colloid substances by multi-medium filtration and ultrafiltration; the clear water in the clear water tank is returned to pH6-9 through sulfuric acid, and then is pumped into a multi-medium filtration to remove suspended matters and colloid substances in the waste water, and the backwash water after the multi-medium filtration and ultrafiltration is returned to the pretreatment system in the step (1);
(3) Softening water quality; in the step (2), filtering the produced water, and sending the filtered produced water into a resin softening and regulating the hardness of the waste water through a produced water tank; returning the resin softening regeneration wastewater to a pretreatment system;
(4) Reverse osmosis of RO membrane; the effluent of the softening pond is conveyed to a first-stage reverse osmosis for concentration, the first-stage reverse osmosis fresh water enters a second-stage reverse osmosis for further desalination, the second-stage reverse osmosis fresh water is used for production, and the second-stage reverse osmosis concentrated water returns to the first-stage reverse osmosis;
(5) Fractional evaporation to crystallize sodium sulfate and nitrate.
In the step (1), the heavy metal ions are removed by the cooperation reaction in a first-stage reaction tank, the pH value of a system is regulated by adding liquid alkali in a second-stage reaction tank, full hydrolysis is carried out, the synergistic decalcification of sodium carbonate is added in a third-stage reaction tank, and the PAM is added in a fourth-stage reaction tank to realize solid-liquid separation after flocculation.
In the step (1), a biological agent is added in the coordination reaction, and the dosage of the biological agent is 150-400g/t of wastewater.
The filler of the multi-medium filter adopted in the step (2) is paved layer by adopting quartz sand with the thickness of 0.5-8mm, and the specification and the thickness of each layer of quartz sand are respectively as follows: quartz sand with the thickness of 0.5-1mm and 500mm, quartz sand with the thickness of 1.0-2.0mm and 400mm, quartz sand with the thickness of 2.0-4.0mm and 300mm, and cushion quartz sand with the thickness of 4-8mm and 200mm; the ultrafiltration membrane adopted by ultrafiltration is made of PVDF.
The resin in the resin softening device adopts divinylbenzene resin or modified macroporous styrene chelating cation exchange resin.
The RO membrane adopted in the step (4) is an 8040 polyamide high-pressure membrane, and the RO membrane adopted in the step (4) is a 4040 polyamide anti-pollution membrane.
The step evaporation crystallization salt separation process in the step (5) comprises the following steps: the first-stage reverse osmosis concentrated water enters a multistage high-efficiency separation MVR system, is preheated and then pressurized, enters a heating chamber, is subjected to high-speed turbulence from bottom to top to a separator flash evaporation in the heating chamber through a full pipe, and is circulated, and sodium sulfate separated out by crystallization is separated out into sodium sulfate through a first-stage high-efficiency separator; after sodium sulfate is separated, mother liquor of the first-stage high-efficiency separator is pumped into the first-efficiency DTB crystallization separator through a pump, flash evaporation is carried out to cool, crystal grains grow, the mother liquor is pumped into the second-efficiency DTB crystallization separator through the pump, the second-stage high-efficiency separator is pumped into the second-stage high-efficiency separator to separate sodium nitrate after flash evaporation is carried out to cool again, and the second-stage mother liquor is returned and combined into evaporation stock solution to be evaporated together.
The crystallization temperature of the sodium sulfate salt is controlled to be 100-120 ℃, and the crystallization temperature of the sodium nitrate salt is controlled to be 20-50 ℃.
The invention has the beneficial effects that:
the method removes suspended matters and colloid substances through pretreatment, multi-medium filtration and ultrafiltration of the high-salt wastewater, softens water, reverse osmosis of RO membrane, and carries out fractional evaporation crystallization to separate salt, and according to the characteristic that the solubility of each salt in the high-salt wastewater is different at different temperatures, each salt is separated through fractional crystallization, and the method has the advantages of short process flow, small occupied area, energy conservation, high production efficiency, high energy direct selling of the produced salt quality, realizes the effect of recycling the wastewater, can recover the salt from the wastewater containing high salt, and has the recycling rate of the salt reaching more than 90 percent; the qualified produced water is more than 93 percent and used for production, so that the clean production requirement is met, the high-salinity wastewater is changed into valuables, the resources are fully utilized, and the method has important environmental benefit and economic benefit.
Drawings
Fig. 1 is a flow chart of the invention.
Detailed Description
The present invention will be described in more detail with reference to the following examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the description is only illustrative and is not intended to limit the scope of the invention. In addition, in the following description, descriptions of well-known structures and techniques are omitted so as not to unnecessarily obscure the present invention.
The invention provides a method for recycling high-salt wastewater,
(1) Pretreatment of high-salt wastewater; the wastewater is collected and enters a water collecting tank, then sequentially passes through a first-stage reaction tank, a second-stage reaction tank, a third-stage reaction tank and a fourth-stage reaction tank, then enters a sedimentation tank for solid-liquid separation, the supernatant enters a clean water tank, the solid is subjected to filter pressing, and filter residues after filter pressing are safely disposed;
(2) Removing suspended matters and colloid substances by multi-medium filtration and ultrafiltration; the clear water in the clear water tank is returned to pH6-9 through sulfuric acid, and then is pumped into a multi-medium filtration to remove suspended matters and colloid substances in the waste water, and the backwash water after the multi-medium filtration and ultrafiltration is returned to the pretreatment system in the step (1);
(3) Softening water quality; the filtered produced water in the step (2) is sent into a resin softening device through a produced water tank to deeply remove the hardness in the wastewater; returning the resin softening regeneration wastewater to a pretreatment system;
(4) Reverse osmosis of RO membrane; the effluent of the softening pond is conveyed to a first-stage reverse osmosis for concentration, the first-stage reverse osmosis fresh water enters a second-stage reverse osmosis for further desalination, the second-stage reverse osmosis fresh water is used for production, and the second-stage reverse osmosis concentrated water returns to the first-stage reverse osmosis;
(5) Fractional evaporation crystallization and salt separation.
In the step (1), the heavy metal ions are removed by the cooperation reaction in a first-stage reaction tank, the pH value of a system is regulated by adding liquid alkali in a second-stage reaction tank, full hydrolysis is carried out, the synergistic decalcification of sodium carbonate is added in a third-stage reaction tank, and the PAM is added in a fourth-stage reaction tank to realize solid-liquid separation after flocculation. The step plays roles of pretreatment of wastewater, removal of heavy metal ions and most of calcium ions, and removal of most of suspended matters by flocculation precipitation to produce clear water.
In the step (1), a biological agent is added in the matching reaction in the step (1), the biological agent adopted in the invention is SES-FS-biological agent-S002, and the dosage of the biological agent is 150-400g/t of wastewater. The biological preparation is a polymer which is formed by compounding a metabolite formed by large-scale culture of a complex specific functional bacterial colony taking thiobacillus as a main component under the condition of unbalanced growth (lack of nitrogen, oxygen, phosphorus and sulfur) with an inorganic compound and has a large number of functional groups such as hydroxyl, sulfhydryl, carboxyl and amino, and the like, and the use process does not need separation and purification and does not need additional nutrition sources. The biological agent exists in the form of colloid particles under low pH, and is rich in multifunctional groups capable of being combined with Cu 2+ ，Pb 2+ ，Zn 2+ ，Hg 2+ ，Cd 2+ The equivalent heavy metal ions form bonds to form a stable biological complex with very small solubility product constant, and the biological agent is used for synergistic decalcification, and because the biological agent has high-efficiency flocculation effect, the biological agent quickly flocculates to form a micelle after the heavy metal complex is hydrolyzed to form particles, so that the biological agent is used for realizing the effect of simultaneously purifying various heavy metal ions (arsenic, cadmium, chromium, lead, mercury, copper, zinc and the like) and calcium ions.
The filler of the multi-medium filter adopted in the step (2) is paved layer by adopting quartz sand with the thickness of 0.5-8mm, and the specification and the thickness of each layer of quartz sand are respectively as follows: quartz sand with the thickness of 0.5-1mm and 500mm, quartz sand with the thickness of 1.0-2.0mm and 400mm, quartz sand with the thickness of 2.0-4.0mm and 300mm, and cushion quartz sand with the thickness of 4-8mm and 200mm; the ultrafiltration membrane adopted by ultrafiltration is made of PVDF. The multi-medium filtration mainly has the function of removing large-particle suspended matters in water, so that the SDI value of the water is reduced, and the water quality requirement of deep purification is met; the ultrafiltration device has the main functions of separating suspended matter macromolecular colloid, slime, microorganisms, organic matters (molecular weight is more than 500) and the like, which can cause fouling and blocking of the reverse osmosis membrane, and creates good preconditions for the subsequent advanced treatment and separation of water.
The resin in the resin softening device adopts macromolecule chelating softening resin. The resin softening device has the main function of deeply removing hardness in the wastewater and preventing scaling and blocking in the membrane concentration and evaporation processes.
The RO membrane adopted in the step (4) is an 8040 polyamide high-pressure membrane, and the RO membrane adopted in the step (4) is a 4040 polyamide anti-pollution membrane. The reverse osmosis RO membrane has the main function of removing organic matters with small ion range and molecular weight in filtrate to produce fresh water and concentrated water, and salt is trapped in the concentrated water. The primary reverse osmosis is used for removing most of salt, so that the operation pressure is higher, the salt removal rate can be up to 99.6% by adopting an 8040 polyamide high-pressure membrane, and the water yield is between 40% and 80%; the second-stage reverse osmosis further purifies the produced fresh water and trapped salt in the concentrated water, the operating pressure is lower than the first-stage operation pressure, a 4040 polyamide anti-pollution membrane is adopted, the desalination rate is more than 90%, and the water production rate is between 70% and 95%.
The step evaporation crystallization salt separation process in the step (5) comprises the following steps: the first-stage reverse osmosis concentrated water enters a multistage high-efficiency separation MVR system, is preheated and then pressurized, enters a heating chamber, is subjected to high-speed turbulence from bottom to top to a separator flash evaporation in the heating chamber through a full pipe, and is circulated, and sodium sulfate separated out by crystallization is separated out into sodium sulfate through a first-stage high-efficiency separator; after sodium sulfate is separated, mother liquor of the first-stage high-efficiency separator is pumped into the first-efficiency DTB crystallization separator through a pump, flash evaporation is carried out to cool, crystal grains grow, the mother liquor is pumped into the second-efficiency DTB crystallization separator through the pump, the second-stage mother liquor is pumped into the second-stage high-efficiency separator to separate sodium nitrate after flash evaporation is carried out to cool again, and the second-stage mother liquor is returned and is combined into evaporation stock solution to be evaporated together. The main function of the step is to separate sodium sulfate and sodium nitrate products by fractional crystallization according to the solubility difference of the sodium sulfate and the sodium nitrate at different temperatures.
The sodium sulfate is sodium sulfate, the solubility of the sodium sulfate in the aqueous solution is gradually increased along with the temperature rise, but the solubility tends to be gentle and the change is not obvious after the temperature is higher than 90 ℃; however, the solubility of sodium nitrate, namely sodium nitrate, is continuously increased along with the temperature rise in the aqueous solution, and no obvious inflection point of change exists. Therefore, according to the different change relation of the solubility of the two salts with the temperature, the sodium sulfate salt is crystallized and precipitated at high temperature, and at the moment, the sodium nitrate salt can not be crystallized and precipitated continuously to be dissolved in the solution due to the high solubility of the sodium nitrate salt at high temperature. Separating sodium sulfate from the solution after crystallizing and separating out sulfate at high temperature; the solution after removing the sodium sulfate contains sodium nitrate, so that the temperature is reduced by flash evaporation, the solubility of the sodium nitrate is reduced, and the sodium nitrate is separated out after reaching the saturated concentration. According to the change relation of the solubility of two salts with different temperatures, the separation temperature of the two salts is designed as follows: the crystallization temperature of the sodium sulfate salt is 100-120 ℃, and the crystallization temperature of the sodium nitrate salt is 20-50 ℃.
Example 1
A method for recycling high-salt wastewater, as shown in the attached drawing, comprises the following steps:
pretreatment of wastewater. 50 tons of wastewater shown in Table 1 enters a water collecting tank and then enters a primary reaction tank through a wastewater lifting pump, and biological agents are added into the primary reaction tank to carry out a matching reaction; adding liquid alkali into a second-stage reaction tank to adjust the pH value of the system, fully hydrolyzing, adding sodium carbonate into a third-stage reaction tank to cooperatively decalcify, adding PAM into a fourth-stage reaction tank to perform flocculation, and then, entering a sedimentation tank to realize solid-liquid separation, wherein the supernatant after separation enters a clean water tank. The underflow of the sedimentation tank is temporarily stored in the mud storage tank, then is conveyed to the filter press by the mud pump for filter pressing, the filter liquor after filter pressing flows back into the water collecting tank, and filter residues after filter pressing are safely disposed. The step plays roles of pretreatment of wastewater, adjustment of pH value of wastewater, efficient removal of heavy metal ions and most of calcium ions by biological agents, and removal of most of suspended matters by flocculation and precipitation to produce clear water.
TABLE 1 high salt wastewater quality
Figure BDA0003672467030000051
Multi-medium filtration and ultrafiltration remove suspended and colloidal substances. After the pH value of the clear water in the water tank is adjusted back to 6 by sulfuric acid, the clear water is pumped into a multi-medium filter and ultrafiltration system to remove suspended matters and colloid substances in the waste water, the filler of the multi-medium filter is paved layer by adopting quartz sand with the thickness of 0.5-8mm, and the specification and the thickness of each layer of quartz sand are respectively as follows: quartz sand with the thickness of 0.5 mm, 1.0mm, 400mm, 2.0mm, 300mm and 4mm and 200mm. The multi-medium filtration removes large particle suspended matters in water, reduces SDI value of the water, and meets ultrafiltration conditions. The ultrafiltration membrane is made of PVDF, and the main function of the ultrafiltration device is to separate suspended matter macromolecular colloid, slime, microorganisms, organic matters (molecular weight is more than 500) and the like, which can cause fouling and blocking of the reverse osmosis membrane, thereby creating good preconditions for the subsequent advanced treatment and separation of water. The multi-medium and ultrafiltration backwash water are returned to the pretreatment system.
Softening water. The ultrafiltration produced water is sent into a resin softening device through a water producing tank to deeply remove the hardness in the wastewater, so that scaling and fouling are prevented from being generated in the membrane concentration and evaporation processes. The resin adopts divinylbenzene resin. And the wastewater after softening and regenerating is returned to the pretreatment system.
Reverse osmosis of RO membrane. And the effluent of the softening water tank is conveyed to the first-stage reverse osmosis by a water conveying pump for concentration, the first-stage reverse osmosis fresh water enters the second-stage reverse osmosis for further desalination, the yield of the second-stage reverse osmosis fresh water is 23.28 tons and the second-stage reverse osmosis concentrated water returns to the first-stage reverse osmosis. The first-stage reverse osmosis RO membrane is an 8040 polyamide high-pressure membrane, and the second-stage reverse osmosis RO membrane is a 4040 polyamide anti-pollution membrane. The reverse osmosis RO membrane has the main function of removing organic matters with small ion range and molecular weight in filtrate to produce fresh water and concentrated water, and salt is trapped in the concentrated water. The primary reverse osmosis is used for removing most of salt, and the operation pressure is higher, so that an 8040 polyamide high-pressure membrane is adopted; the second-stage reverse osmosis further purifies the produced fresh water and trapped salt in the concentrated water, and the operation pressure is lower than the first-stage reverse osmosis, so that a 4040 polyamide anti-pollution membrane is adopted.
Evaporating and crystallizing to separate salt. Evaporating and crystallizing sodium sulfate salt. The primary reverse osmosis concentrated water enters a multistage high-efficiency separation MVR system, is preheated and then pressurized to enter a heating chamber, and is fully circulated in the heating chamber from bottom to top to high-speed turbulence to a separator for flash evaporation. Since there is no solvent vaporization during heating, for solutions with normal solubility substances, no scale will crystallize on the walls of the heating tube. The heated slurry is returned to the crystallization chamber and mixed with the slurry in the chamber, raising the temperature of the slurry near the inlet to 110 ℃. Boiling phenomenon appears on the surface of liquid in the crystallization chamber, solvent evaporates, supersaturation degree crystallization is generated to separate out sodium sulfate crystals, and solute is deposited on the surface of suspended crystals in rotary motion. The material in the crystallizer grows up fast through the growth area and the suspension area in the equipment, the sedimentation speed of the large crystal particles is larger than the suspension speed, the crystal slurry area with stable suspension density is formed by the conical bottom salt of the crystallizer, the crystal slurry containing the crystal is conveyed to the crystal slurry tank by utilizing the conveying of the crystal slurry pump to grow up the crystal particles, 945kg of sodium sulfate is produced by the separation of the first-stage high-efficiency separator, the sodium sulfate is a qualified product, and the sodium sulfate is sold after being dried and packaged. The MVR evaporator solvent is evaporated, and then 23.75 tons of condensed water is recycled to the production system. The specification and model of the high-efficiency separator are as follows: LW300 horizontal screw centrifuge.
Evaporating and crystallizing sodium nitrate salt. After separating sodium sulfate, the mother liquor of the first-stage high-efficiency separator is pumped into a first-efficiency DTB crystallization separator through a pump, flash evaporation is carried out to cool, the process of crystal grain growth is carried out, the mother liquor is pumped into a second-efficiency DTB crystallization separator through a pump, the mother liquor is pumped into a second-stage high-efficiency separator to separate 2545kg of sodium nitrate crystal salt after flash evaporation is carried out to cool to 40 ℃, sodium nitrate is taken as a qualified product, and the sodium nitrate is dried, packed and sold. The secondary mother liquor is combined with the evaporation stock solution step (5) to be evaporated together, and part of the mother liquor is opened according to the impurity concentration in order to ensure the purity and quality of the product. The specification and model of the DTB crystallization separator are as follows: phi 2000 x 6000 x 2mm with stirring and guide cylinder; the specification and model of the second-stage efficient separator are as follows: HR400 centrifuge.
Example 2
A method for recycling high-salt wastewater, as shown in the attached drawing, comprises the following steps:
pretreatment of wastewater. 50 tons of wastewater shown in Table 1 enters a water collecting tank and then enters a primary reaction tank through a wastewater lifting pump, and biological agents are added into the primary reaction tank to carry out a matching reaction; adding liquid alkali into a second-stage reaction tank to adjust the pH value of the system, fully hydrolyzing, adding sodium carbonate into a third-stage reaction tank to cooperatively decalcify, adding PAM into a fourth-stage reaction tank to perform flocculation, and then, entering a sedimentation tank to realize solid-liquid separation, wherein the supernatant after separation enters a clean water tank. The underflow of the sedimentation tank is temporarily stored in the mud storage tank, then is conveyed to the filter press by the mud pump for filter pressing, the filter liquor after filter pressing flows back into the water collecting tank, and filter residues after filter pressing are safely disposed. The step plays roles of pretreatment of wastewater, adjustment of pH value of wastewater, efficient removal of heavy metal ions and most of calcium ions by biological agents, and removal of most of suspended matters by flocculation and precipitation to produce clear water.
Multi-medium filtration and ultrafiltration remove suspended and colloidal substances. After the pH value of the clear water in the water tank is adjusted back to 9 by sulfuric acid, the clear water is pumped into a multi-medium filter and ultrafiltration system to remove suspended matters and colloid substances in the waste water, the filler of the multi-medium filter is paved layer by adopting quartz sand with the thickness of 0.5-8mm, and the specification and the thickness of each layer of quartz sand are respectively as follows: 1mm thick quartz sand 500mm, 2.0mm thick quartz sand 400mm thick, 4.0mm thick cushion layer 300mm thick, 8mm thick cushion layer quartz sand 200mm thick. The multi-medium filtration removes large particle suspended matters in water, reduces SDI value of the water, and meets ultrafiltration conditions. The ultrafiltration membrane is made of PVDF, and the main function of the ultrafiltration device is to separate suspended matter macromolecular colloid, slime, microorganisms, organic matters (molecular weight is more than 500) and the like, which can cause fouling and blocking of the reverse osmosis membrane, thereby creating good preconditions for the subsequent advanced treatment and separation of water. The multi-medium and ultrafiltration backwash water are returned to the pretreatment system.
Softening water. The ultrafiltration produced water is sent into a resin softening device through a water producing tank to deeply remove the hardness in the wastewater, so that scaling and fouling are prevented from being generated in the membrane concentration and evaporation processes. The resin adopts modified macroporous styrene chelating cation exchange resin. The main components of the modified resin are a styrene skeleton and a carboxylic acid group functional group, and the preparation method comprises the following steps: mixing 20% toluene and 80% hexane, then mixing with styrene and p-divinylbenzene, adding into dibenzoyl peroxide in a cooling state, uniformly mixing and dissolving, adding into deionized water containing 0.1-2.0% of calcium carbonate under stirring, and heating at 80 ℃ under stirring for 5-10 hours to obtain a spherical polymer. The spherical polymer is filtered, washed with water and dried at 100-125 ℃. The dried spherical polymer is added into tetrachloroethane solvent to be swelled, and after chloromethylation, the iminodiacetic acid group is introduced. Then the mixture is treated with sodium hydroxide to transform into Na-type chelating cation exchange resin. The modified macroporous chelating cation exchange resin has the characteristics that the specific surface area is up to 180m < 2 >/g, the aperture is 12.5nm, the chelating capacity is strong, almost all heavy metal ions can be chelated, the exchange capacity is large, calcium and magnesium ions and heavy metal ions in the wastewater can be rapidly and strongly removed, and organic macromolecular substances, COD (chemical oxygen demand) and other substances can be removed, so that the modified macroporous chelating cation exchange resin has the function of deep purification treatment on the wastewater; however, the sodium nitrate and the sodium sulfate are not chelated or adsorbed, so that the quantity of the two salts is not reduced, and the regenerated wastewater is returned to the pretreatment system.
Reverse osmosis of RO membrane. And the effluent of the chemical pond is conveyed to the first-stage reverse osmosis by a water conveying pump for concentration, the first-stage reverse osmosis fresh water enters the second-stage reverse osmosis for further desalination, the yield of the second-stage reverse osmosis fresh water is 24.32 tons and the second-stage reverse osmosis concentrated water returns to the first-stage reverse osmosis. The first-stage reverse osmosis RO membrane is an 8040 polyamide high-pressure membrane, and the second-stage reverse osmosis RO membrane is a 4040 polyamide anti-pollution membrane. The reverse osmosis RO membrane has the main function of removing organic matters with small ion range and molecular weight in filtrate to produce fresh water and concentrated water, and salt is trapped in the concentrated water. The primary reverse osmosis removes most of salt, so that the operation pressure is higher, the retention salt rate can be up to 99.6% by adopting an 8040 polyamide high-pressure membrane, and the water yield is between 40% and 80%; the second-stage reverse osmosis further purifies the produced fresh water and trapped salt in the concentrated water, the operating pressure is lower than the first-stage operation pressure, a 4040 polyamide anti-pollution membrane is adopted, the trapped salt rate is more than 90%, and the water production rate is between 70% and 95%.
Evaporating and crystallizing to separate salt. Evaporating and crystallizing sodium sulfate salt. The primary reverse osmosis concentrated water enters a multistage high-efficiency separation MVR system, is preheated and then pressurized to enter a heating chamber, and is fully circulated in the heating chamber from bottom to top to high-speed turbulence to a separator for flash evaporation. Since there is no solvent vaporization during heating, for solutions with normal solubility substances, no scale will crystallize on the walls of the heating tube. The heated slurry is returned to the crystallization chamber and mixed with the slurry in the chamber, raising the temperature of the slurry near the inlet to 110 ℃. Boiling phenomenon appears on the surface of liquid in the crystallization chamber, solvent evaporates, supersaturation degree crystallization is generated to separate out sodium sulfate crystals, and solute is deposited on the surface of suspended crystals in rotary motion. The material in the crystallizer is grown up fast after passing through the growth area and the suspension area in the equipment, the sedimentation speed of the large crystal particles is larger than the suspension speed, the crystal slurry area with stable suspension density is formed by the salt at the conical bottom of the crystallizer, the crystal slurry containing the crystal is conveyed to the crystal slurry tank by utilizing the conveying of the crystal slurry pump to grow up the crystal particles, 1013kg of sodium sulfate is produced by the separation of the first-stage high-efficiency separator, the sodium sulfate is a qualified product, and the sodium sulfate is sold after being dried and packaged. The MVR evaporator solvent is evaporated, and then the condensed water produced by 24.87 tons is recycled to the production system. The specification and model of the high-efficiency separator are as follows: LW300 horizontal screw centrifuge.
Evaporating and crystallizing sodium nitrate salt. After separating sodium sulfate, the mother liquor of the first-stage high-efficiency separator is pumped into a first-effect DTB crystallization separator through a pump, flash evaporation is carried out to cool, the process of crystal grain growth is carried out, the mother liquor is pumped into a second-effect DTB crystallization separator through a pump, the mother liquor is pumped into a second-stage high-efficiency separator to separate 2736kg of sodium nitrate crystal salt after flash evaporation is carried out to cool to 40 ℃, sodium nitrate is taken as a qualified product, and the product is dried, packed and sold. The secondary mother liquor is combined with the evaporation stock solution step (5) to be evaporated together, and part of the mother liquor is opened according to the impurity concentration in order to ensure the purity and quality of the product. The specification and model of the DTB crystallization separator are as follows: phi 2000 x 6000 x 2mm with stirring and guide cylinder; the specification and model of the second-stage efficient separator are as follows: HR400 centrifuge. In example 2, the yields of sodium sulfate and sodium nitrate are about 7% higher than those of example 1, mainly because the modified macroporous chelate cation exchange resin not only softens the water quality, but also can effectively remove heavy metal ions, COD and other substances, further purifies the water quality, reduces the impurity salt content, and thus improves the yields of sodium sulfate and sodium nitrate. Therefore, the modified chelate cation exchange resin has remarkable effect and advantage.
Example 3
A method for recycling high-salt wastewater, as shown in the attached drawing, comprises the following steps:
pretreatment of wastewater. 50 tons of wastewater shown in Table 1 enters a water collecting tank and then enters a primary reaction tank through a wastewater lifting pump, and biological agents are added into the primary reaction tank to carry out a matching reaction; adding liquid alkali into a second-stage reaction tank to adjust the pH value of the system, fully hydrolyzing, adding sodium carbonate into a third-stage reaction tank to cooperatively decalcify, adding PAM into a fourth-stage reaction tank to perform flocculation, and then, entering a sedimentation tank to realize solid-liquid separation, wherein the supernatant after separation enters a clean water tank. The underflow of the sedimentation tank is temporarily stored in the mud storage tank, then is conveyed to the filter press by the mud pump for filter pressing, the filter liquor after filter pressing flows back into the water collecting tank, and filter residues after filter pressing are safely disposed. The step plays roles of pretreatment of wastewater, adjustment of pH value of wastewater, efficient removal of heavy metal ions and most of calcium ions by biological agents, and removal of most of suspended matters by flocculation and precipitation to produce clear water.
Multi-medium filtration and ultrafiltration remove suspended and colloidal substances. After the pH value of the clear water in the water tank is adjusted back to 9 by sulfuric acid, the clear water is pumped into a multi-medium filter and ultrafiltration system to remove suspended matters and colloid substances in the waste water, the filler of the multi-medium filter is paved layer by adopting quartz sand with the thickness of 0.5-8mm, and the specification and the thickness of each layer of quartz sand are respectively as follows: quartz sand with the thickness of 0.8mm and 500mm, quartz sand with the thickness of 1.5mm and 400mm, quartz sand with the thickness of 3.0mm and 300mm and cushion quartz sand with the thickness of 6mm and 200mm. The multi-medium filtration removes large particle suspended matters in water, reduces SDI value of the water, and meets ultrafiltration conditions. The ultrafiltration membrane is made of PVDF, and the main function of the ultrafiltration device is to separate suspended matter macromolecular colloid, slime, microorganisms, organic matters (molecular weight is more than 500) and the like, which can cause fouling and blocking of the reverse osmosis membrane, thereby creating good preconditions for the subsequent advanced treatment and separation of water. The multi-medium and ultrafiltration backwash water are returned to the pretreatment system.
Softening water. The ultrafiltration produced water is sent into a resin softening device through a water producing tank to deeply remove the hardness in the wastewater, so that scaling and fouling are prevented from being generated in the membrane concentration and evaporation processes. Resin TP260 was used as the resin.
Reverse osmosis of RO membrane. And the effluent of the chemical pond is conveyed to the first-stage reverse osmosis by a water conveying pump for concentration, the first-stage reverse osmosis fresh water enters the second-stage reverse osmosis for further desalination, the yield of the second-stage reverse osmosis fresh water is 23.16 tons and the second-stage reverse osmosis concentrated water returns to the first-stage reverse osmosis for production. The first-stage reverse osmosis RO membrane is an 8040 polyamide high-pressure membrane, and the second-stage reverse osmosis RO membrane is a 4040 polyamide anti-pollution membrane. The reverse osmosis RO membrane has the main function of removing organic matters with small ion range and molecular weight in filtrate to produce fresh water and concentrated water, and salt is trapped in the concentrated water. The primary reverse osmosis removes most of salt, so that the operation pressure is higher, the retention salt rate can be up to 99.6% by adopting an 8040 polyamide high-pressure membrane, and the water yield is between 40% and 80%; the second-stage reverse osmosis further purifies the produced fresh water and trapped salt in the concentrated water, the operating pressure is lower than the first-stage operation pressure, a 4040 polyamide anti-pollution membrane is adopted, the trapped salt rate is more than 90%, and the water production rate is between 70% and 95%.
Evaporating and crystallizing to separate salt. Evaporating and crystallizing sodium sulfate salt. The primary reverse osmosis concentrated water enters a multistage high-efficiency separation MVR system, is preheated and then pressurized to enter a heating chamber, and is fully circulated in the heating chamber from bottom to top to high-speed turbulence to a separator for flash evaporation. Since there is no solvent vaporization during heating, for solutions with normal solubility substances, no scale will crystallize on the walls of the heating tube. The heated slurry is returned to the crystallization chamber and mixed with the slurry in the chamber, raising the temperature of the slurry near the inlet to 110 ℃. Boiling phenomenon appears on the surface of liquid in the crystallization chamber, solvent evaporates, supersaturation degree crystallization is generated to separate out sodium sulfate crystals, and solute is deposited on the surface of suspended crystals in rotary motion. The material in the crystallizer is grown up fast after passing through the growth area and the suspension area in the equipment, the sedimentation speed of the large crystal particles is larger than the suspension speed, the crystal slurry area with stable suspension density is formed by the salt at the conical bottom of the crystallizer, the crystal slurry containing the crystal is conveyed to the crystal slurry tank by utilizing the conveying of the crystal slurry pump to grow up the crystal particles, 928kg of sodium sulfate salt is produced by the separation of the first-stage high-efficiency separator, the sodium sulfate salt is a qualified product, and the sodium sulfate salt is sold after being dried and packaged. The MVR evaporator solvent is evaporated, and then 23.52 tons of condensed water is recycled to the production system. The specification and model of the high-efficiency separator are as follows: LW300 horizontal screw centrifuge.
Evaporating and crystallizing sodium nitrate salt. After separating sodium sulfate, the mother liquor of the first-stage high-efficiency separator is pumped into a first-efficiency DTB crystallization separator through a pump, flash evaporation is carried out to cool, the process of crystal grain growth is carried out, the mother liquor is pumped into a second-efficiency DTB crystallization separator through a pump, the mother liquor is pumped into a second-stage high-efficiency separator to separate 2496kg of sodium nitrate crystal salt after flash evaporation is carried out to cool to 40 ℃, sodium nitrate is taken as a qualified product, and the sodium nitrate is dried, packed and sold. The secondary mother liquor is combined with the evaporation stock solution step (5) to be evaporated together, and part of the mother liquor is opened according to the impurity concentration in order to ensure the purity and quality of the product. The specification and model of the DTB crystallization separator are as follows: phi 2000 x 6000 x 2mm with stirring and guide cylinder; the specification and model of the second-stage efficient separator are as follows: HR400 centrifuge.
The invention solves the problem that the recycling recovery of the molybdenum concentrate smelting wastewater is difficult to effectively use by pretreatment of high-salt wastewater, multi-medium filtration and ultrafiltration to remove suspended matters and colloid substances, softening of water quality, reverse osmosis of RO membrane, fractional evaporation crystallization and salt separation. The treatment process of the high-salt wastewater changes waste into valuable, sodium nitrate and sodium sulfate are recovered, and the treated water is reused in the production process, so that the treatment process has important environmental benefit and economic value.
The specific protection scope of the present invention is not limited to the above explanation, and any simple replacement or modification within the scope of the technical idea disclosed in the present invention and according to the technical scheme of the present invention should be within the protection scope of the present invention.

Claims (4)

1. The method for recycling the high-salt wastewater is characterized by comprising the following steps of:
(1) Pretreatment of high-salt wastewater; the wastewater is collected and enters a water collecting tank, then sequentially passes through a first-stage reaction tank, a second-stage reaction tank, a third-stage reaction tank and a fourth-stage reaction tank, then enters a sedimentation tank for solid-liquid separation, the supernatant enters a clean water tank, the solid is subjected to filter pressing, and filter residues after filter pressing are safely disposed;
(2) Removing suspended matters and colloid substances by multi-medium filtration and ultrafiltration; the clear water in the clear water tank is returned to pH6-9 through sulfuric acid, and then is pumped into a multi-medium filtration to remove suspended matters and colloid substances in the waste water, and the backwash water after the multi-medium filtration and ultrafiltration is returned to the pretreatment system in the step (1);
(3) Softening water quality; in the step (2), filtering the produced water, and sending the filtered produced water into a resin softening and regulating the hardness of the waste water through a produced water tank; returning the resin softening regeneration wastewater to a pretreatment system;
(4) Reverse osmosis of RO membrane; the effluent of the softening pond is conveyed to a first-stage reverse osmosis for concentration, the first-stage reverse osmosis fresh water enters a second-stage reverse osmosis for further desalination, the second-stage reverse osmosis fresh water is used for production, and the second-stage reverse osmosis concentrated water returns to the first-stage reverse osmosis;
(5) Fractional evaporation crystallization of sodium sulfate and nitrate;
the resin in the resin softening device adopts modified macroporous styrene chelating cation exchange resin;
the main components of the modified resin are a styrene skeleton and a carboxylic acid group functional group, and the preparation method comprises the following steps: mixing 20% of toluene and 80% of hexane, then mixing with styrene and paradivinylbenzene, adding into dibenzoyl peroxide in a cooling state, adding into deionized water containing 0.1-2.0% of calcium carbonate under stirring after uniformly mixing and dissolving, and heating for 5-10 hours under stirring at 80 ℃ to obtain a spherical polymer; filtering and washing the spherical polymer, and drying at 100-125 ℃; adding the dried spherical polymer into tetrachloroethane solvent to swell, and introducing iminodiacetic acid group after chloromethylation; then sodium hydroxide is used for treatment and transformation to form Na-type chelating cation exchange resin;
in the step (1), carrying out a matching reaction in a first-stage reaction tank to remove heavy metal ions, adding liquid alkali in a second-stage reaction tank to adjust the pH value of a system, carrying out full hydrolysis, adding sodium carbonate in a third-stage reaction tank to carry out synergistic decalcification, adding PAM in a fourth-stage reaction tank to carry out flocculation, and then entering a sedimentation tank to realize solid-liquid separation; in the step (1), a biological agent is added in the coordination reaction, the dosage of the biological agent is 150-400g/t of wastewater, and the biological agent is SES-FS-biological agent-S002;
the step-by-step evaporation crystallization salt separation process in the step (5) is to crystallize and evaporate sodium sulfate firstly, the first-stage reverse osmosis concentrated water enters a multi-stage efficient separation MVR system, the first-stage reverse osmosis concentrated water is preheated and then pressurized to enter a heating chamber, the heating chamber is filled with a pipe to be subjected to high-speed turbulence from bottom to top to a separator for flash evaporation, the above process is circulated, and sodium sulfate separated out by crystallization is separated out into sodium sulfate through the first-stage efficient separator; and evaporating and crystallizing sodium nitrate, separating sodium sulfate, pumping mother liquor of the first-stage high-efficiency separator into a first-effect DTB (draw-in and draw-out) crystallization separator by a pump, carrying out flash evaporation and cooling, pumping into a second-effect DTB crystallization separator by a pump in the process of crystal grain growth, crystallizing sodium nitrate by flash evaporation and cooling again, pumping into the second-stage high-efficiency separator to separate sodium nitrate, and returning the second-stage mother liquor to be combined with first-stage reverse osmosis concentrated water for evaporation.
2. The method for recycling high-salt wastewater according to claim 1, wherein the filler of the multi-medium filter adopted in the step (2) is paved layer by adopting 0.5-8mm quartz sand, and the specification and the thickness of each layer of quartz sand are as follows: quartz sand with the thickness of 0.5-1mm and 500mm, quartz sand with the thickness of 1.0-2.0mm and 400mm, quartz sand with the thickness of 2.0-4.0mm and 300mm, and cushion quartz sand with the thickness of 4-8mm and 200mm; the ultrafiltration membrane adopted by ultrafiltration is made of PVDF.
3. The method for recycling high-salt wastewater according to claim 1, wherein the RO membrane adopted in the step (4) is an 8040 polyamide high-pressure membrane, and the RO membrane adopted in the step (4) is a 4040 polyamide anti-pollution membrane.
4. The method for recycling high-salt wastewater according to claim 1, wherein the crystallization temperature of sodium sulfate is controlled to be 100-120 ℃, and the crystallization temperature of sodium nitrate is controlled to be 20-50 ℃.
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2009147974A (en) * 2009-12-23 2011-06-27 Государственное образовательное учреждение высшего профессионального образования "Санкт-Петербургский государственный горный инсти METHOD FOR CLEANING WATER-TURNING WATERS OF METALLURGICAL PRODUCTION
CN105294907A (en) * 2015-11-16 2016-02-03 徐富春 Preparation method of highly acid styrene series macroporous cation exchange resin
CN110606612A (en) * 2019-11-04 2019-12-24 江苏中电创新环境科技有限公司 Coal coking high-salinity wastewater recycling treatment process
CN112707563A (en) * 2020-12-14 2021-04-27 江苏卓博环保科技有限公司 Membrane method recycling treatment device and treatment method for copper smelting high-salinity wastewater
CN113716772A (en) * 2021-05-28 2021-11-30 清创人和生态工程技术有限公司 Recycling and zero-discharge process for divalent salt in organic wastewater of synthetic ammonia
CN216236501U (en) * 2021-09-01 2022-04-08 蓝星工程有限公司 Integrated device for zero discharge and resource recycling of refining wastewater

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104692574B (en) * 2014-12-22 2017-05-03 内蒙古久科康瑞环保科技有限公司 Treatment method of high saline wastewater
CN108128961A (en) * 2018-01-25 2018-06-08 东莞市圆明生物科技有限公司 Brine waste zero emission method and system
WO2021093773A1 (en) * 2019-11-15 2021-05-20 清大国华环境集团股份有限公司 Method and device for resourceful treatment of industrial waste salt
CN113955888A (en) * 2020-07-21 2022-01-21 蓝星工程有限公司 Integrated treatment system and process for recycling concentrated brine in coking wastewater
CN112919734A (en) * 2021-01-26 2021-06-08 北京今大禹环境技术股份有限公司 Coking wastewater deep treatment and evaporative crystallization zero-discharge process
CN112811701A (en) * 2021-02-07 2021-05-18 北京鑫佰利科技发展有限公司 Method for treating carbonate-containing wastewater

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2009147974A (en) * 2009-12-23 2011-06-27 Государственное образовательное учреждение высшего профессионального образования "Санкт-Петербургский государственный горный инсти METHOD FOR CLEANING WATER-TURNING WATERS OF METALLURGICAL PRODUCTION
CN105294907A (en) * 2015-11-16 2016-02-03 徐富春 Preparation method of highly acid styrene series macroporous cation exchange resin
CN110606612A (en) * 2019-11-04 2019-12-24 江苏中电创新环境科技有限公司 Coal coking high-salinity wastewater recycling treatment process
CN112707563A (en) * 2020-12-14 2021-04-27 江苏卓博环保科技有限公司 Membrane method recycling treatment device and treatment method for copper smelting high-salinity wastewater
CN113716772A (en) * 2021-05-28 2021-11-30 清创人和生态工程技术有限公司 Recycling and zero-discharge process for divalent salt in organic wastewater of synthetic ammonia
CN216236501U (en) * 2021-09-01 2022-04-08 蓝星工程有限公司 Integrated device for zero discharge and resource recycling of refining wastewater

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