CN112093965A - Moderate stepwise cooperative pretreatment process for mine water treatment - Google Patents
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Abstract
The invention relates to a mine water treatment process, in particular to a moderate stepwise cooperative pretreatment process for mine water treatment, which comprises membrane concentration treatment and evaporative crystallization treatment, and comprises the following steps: the moderate stepwise cooperative pretreatment process for mine water treatment specifically comprises primary pretreatment, primary concentration, secondary pretreatment, secondary concentration, tertiary pretreatment, tertiary concentration and evaporative crystallization in sequence to finally obtain product water and crystal salt, wherein the primary pretreatment, the secondary pretreatment and the tertiary pretreatment are respectively used for obtaining primary sludge, secondary sludge and tertiary sludge, and the product water obtained by the primary concentration, the secondary concentration, the tertiary concentration and the evaporative crystallization is combined; in the pretreatment, when the concentrated water obtained by the previous stage of membrane concentration is subjected to the current stage of membrane concentration treatment, the concentration recovery rate of the current stage of membrane is fed back, regulated and controlled within a target value range by controlling main factors influencing the recovery rate of the current stage of membrane, so that economical and efficient mine water zero-discharge treatment is realized.
Description
Technical Field
The invention relates to a treatment process of mine water, in particular to a moderate stepwise cooperative pretreatment process for mine water treatment, and belongs to the technical field of water treatment.
Background
With the optimization of the layout of coal production and development, the coal development is further centralized to large coal bases, and the yield of 14 large coal bases accounts for more than 95% of the whole country, wherein the yield of 23.1 hundred million tons of coal in western regions represented by Mongolia, Shaanxi and Xinjiang accounts for 59.2% of the whole country. The water resource and the coal resource are distributed reversely, the areas are in arid and semi-arid areas, the water resource is lack, the vegetation is rare, the ecological environment is fragile, and the water consumption of coal mines and related industries is short; the mine water is mostly high-salinity mine water, TDS is more than or equal to 1000mg/L, and the mine water cannot be utilized after being simply treated; meanwhile, because of lack of a receiving water body, surface water and soil loss, salinization, vegetation withering and the like caused by discharge can be caused, so that the TDS of mine water discharge is limited by multi-site environmental protection departments, the TDS is required to be less than or equal to 1600mg/L in Shandong, Lu, West areas, the mine water zero discharge or the TDS is required to reach the three types of sanitary standards for drinking water and quality standards for surface water in inner Mongolia and Erdos and the like, and the TDS is less than or equal to 1000 mg/L. Aiming at the water demand and discharge limitation of large coal bases, the mine water is subjected to advanced treatment, concentration, crystallization and salt separation, so that the zero emission of the mine water is realized, a large amount of high-quality domestic and production water is obtained, and the method is a necessary choice for solving the problem of water shortage of the large coal bases and environmental protection.
Membrane concentration is required in the mine water zero-discharge treatment process, the inlet water quality is required to be stable in the membrane concentration process, SS is extremely low, turbidity is less than or equal to 5NTU, scaling tendency of various insoluble salts is less than or equal to 80%, and the like, which are extremely strict requirements on mine water. Because the mine water is a natural water body existing underground, the soluble salts causing scaling are different along with the occurrence environment and the rock stratum types, some have extremely high sulfate radicals, some have extremely high chloride ions, some have extremely high bicarbonate radicals, some have extremely high calcium and magnesium, some have extremely high ferro-manganese, and no rule can be followed; meanwhile, coal dust, rock dust and other suspended matters entering mine water in the coal mining process are also main factors influencing mine water film concentration treatment. How to carry out pretreatment economically and efficiently is the key to the success of zero discharge of mine water.
At present, the conventional method is to adopt a high-efficiency reverse osmosis (HERO) process or a similar HERO process before membrane concentration treatment, and reduce suspended matters and easily-scaling substances such as calcium, magnesium, silicon, boron and the like in mine water at one time through unit processes such as coagulation, precipitation, medicament softening, filtration, ion exchange and the like. The method has the defects of large medicament softening scale, large medicament adding amount, low medicament efficiency, large sludge wastewater amount, large ion exchange scale and large regenerated wastewater amount, and the residual easy-scaling substances such as calcium, magnesium, silicon, boron and the like still have great scaling risk after subsequent concentration, thereby influencing the stable operation of subsequent membrane concentration and evaporative crystallization.
Disclosure of Invention
The invention aims to provide a moderate stepwise cooperative pretreatment process for mine water treatment, which realizes economical and efficient mine water zero-discharge treatment through precise pretreatment, and has the advantages of strong water quality change adaptability, large operation flexibility, small scale of hardness and softening removal, and low investment and operation cost.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a moderate stepwise cooperative pretreatment process for mine water treatment comprises membrane concentration treatment and evaporative crystallization treatment, and comprises the following steps:
the membrane concentration treatment comprises primary concentration, secondary concentration and tertiary concentration;
the moderate stepwise cooperative pretreatment process for mine water treatment specifically comprises primary pretreatment, primary concentration, secondary pretreatment, secondary concentration, tertiary pretreatment, tertiary concentration and evaporative crystallization in sequence to finally obtain product water and crystal salt,
wherein, the primary pretreatment, the secondary pretreatment and the tertiary pretreatment respectively obtain primary sludge, secondary sludge and tertiary sludge, and product water obtained by primary concentration, secondary concentration, tertiary concentration and evaporative crystallization is combined;
in the primary pretreatment, when the primary membrane concentration treatment is carried out on concentrated water obtained from raw water, the primary membrane concentration recovery rate is controlled within a target value range by controlling the main factors influencing the primary membrane concentration recovery rate to feed back and regulate, wherein the target value range of the primary membrane concentration recovery rate is 50-75%;
in the second-stage pretreatment and the third-stage pretreatment, when the concentrated water obtained by the previous-stage membrane concentration is subjected to the current-stage membrane concentration treatment, the concentration recovery rate of the current-stage membrane is controlled within a target value range by controlling main factors influencing the recovery rate of the current-stage membrane in a feedback adjustment mode, wherein the target value range of the concentration recovery rate of the second-stage membrane is 70-80%, and the target value range of the concentration recovery rate of the third-stage membrane is 50-80%.
The coal mine water zero emission treatment mainly adopts a multi-stage membrane method for concentration and then evaporation crystallization, and the key of success or failure of zero emission treatment is to ensure that the contents of Suspended Substances (SS), organic matters and insoluble salts are in the range required by a reverse osmosis membrane or an electrodialysis membrane in the membrane method treatment process. According to the moderate stepwise cooperative pretreatment process (SPMS2, Synergistic pretreatment of modely and step by step), main factors influencing each level of concentration treatment are determined according to the water quality characteristics of mine water, targeted and directional removal or reduction is carried out, the treatment degree is flexibly adjusted according to requirements, the purpose of meeting the level of concentration treatment is achieved, and excessive treatment is not carried out; sludge generated by the pretreatment of the stage is treated or comprehensively utilized according to components; clear liquid generated by sludge treatment is recycled to the stage for reuse; reducing the scale of chemical softening, hardness and silicon removal treatment, improving the medicament efficiency, reducing the scale of ion exchange, reducing the quantity of regenerated waste liquid and greatly saving the investment and the operating cost.
Preferably, the main factors influencing the primary concentration treatment are a large amount of Suspended Substances (SS) and a small amount of calcium and magnesium, so the primary pretreatment aims to remove the SS and inhibit calcium and magnesium scaling;
the main factors influencing the secondary concentration treatment are usually overhigh calcium, magnesium, silicon and the like after concentration, so the primary goal of the secondary pretreatment is to remove most of calcium, magnesium and silicon;
the main factors influencing the three-stage concentration treatment are usually residual calcium, magnesium, silicon, boron after concentration and the like, so the main aim of the three-stage pretreatment is to completely remove the calcium, the magnesium, the silicon and the boron.
Preferably, the primary pretreatment is to remove SS from mine water raw water by adopting coagulating sedimentation, filtering and ultrafiltration processes, and a scale inhibitor is adopted to inhibit the scaling tendency of calcium and magnesium and eliminate the influence on reverse osmosis;
the second-stage pretreatment adopts chemical softening to remove hard silicon and a filtering process to remove calcium, magnesium, silicon and the like aiming at the concentrated water of the first-stage concentration;
the third-stage pretreatment is to remove calcium, magnesium, silicon and boron by adopting a chemical softening and hardness removal silicon removal and filtration + ion exchange process aiming at the concentrated water of the second-stage concentration, or to remove calcium, magnesium, silicon, boron and the like by adopting an ion exchange process alone.
Preferably, in the primary pretreatment, the coagulating sedimentation adopts a hydraulic circulating clarification tank or a mechanical accelerated clarification tank.
Preferably, in the second-stage pretreatment, one of lime and magnesium agent, lime and caustic soda and magnesium agent, caustic soda and soda ash and magnesium agent is adopted for chemical softening and hard removal, and Tubular Microfiltration (TMF) or a high-density sedimentation tank, sand filtration and ultrafiltration process is adopted for a filtration process.
Preferably, in the three-stage pretreatment, lime, caustic soda and magnesium agent or caustic soda, soda and magnesium agent are adopted for chemical softening and hard silicon removal, Tubular Microfiltration (TMF), high-density sedimentation tank, sand filtration and ultrafiltration are adopted for the filtration process, a weak acid cation resin exchanger or a chelating resin exchanger is adopted for ion exchange, the pH value is adjusted to acidity after the ion exchange, and a decarbonization tower is arranged for blowing off CO2。
Preferably, the process comprises:
the first-stage pretreatment adopts scale inhibitor to inhibit scale, chemical agents such as lime, magnesium agent and the like are not added, and Mg (OH) is not generated2、 CaCO3Chemical precipitation sludge; after the first-stage concentration, the concentration of calcium, magnesium and silicon in the mine water is improved to 3-5 times of the original concentration,
adding chemical agents such as lime, magnesium agent and the like in the secondary pretreatment process to generate Mg (OH)2、CaCO3After chemical precipitation of sludge, controlling the residual calcium, magnesium and silicon in the mine water to be 10-50 mg/L; after the secondary concentration, the concentration of calcium, magnesium and silicon is increased to 50-250mg/L,
chemical agents such as lime, magnesium agents and the like are added in the three-stage pretreatment process to reduce calcium, magnesium and silicon to 10-50mg/L and then ion exchange is carried out or ion exchange is independently adopted, calcium and magnesium ions are reduced to be below 0.03mmol/L and silicon is reduced to be below 20mg/L after the three-stage pretreatment, so that the requirements of subsequent concentration and evaporative crystallization are met.
Preferably, the primary sludge mainly comprises coal powder with the heat value of more than 2000kJ/kg, the water content of the primary sludge is reduced to be below 60 percent after concentration and filter pressing, the primary sludge is used as low-heat-value fuel for comprehensive utilization, and the filter pressing liquid is returned to the primary pretreatment for cyclic treatment and recycling;
the secondary sludge mainly comprises Mg (OH)2、CaCO3After concentration and filter pressing, the water content is reduced to be below 65 percent, the waste is used as common solid waste for landfill treatment, and the filter pressing liquid is returned to the stage of pretreatment for recycling treatment;
the main component of the third-stage sludge is Mg (OH)2、CaCO3The main sludge and the ion exchange regeneration waste liquid are mixed and reacted, the water content of the main sludge and the ion exchange regeneration waste liquid is reduced to be below 65 percent through concentration and filter pressing, the main sludge and the ion exchange regeneration waste liquid are used as common solid waste for landfill treatment, and the filter pressing liquid is returned to the stage of pretreatment for recycling treatment.
Preferably, the process comprises:
removing suspended matters from the mine water through primary pretreatment, adding a scale inhibitor, and performing primary concentration treatment, wherein primary sludge is mainly pulverized coal and is comprehensively utilized as a low-calorific-value fuel;
the first-stage concentrated water enters a second-stage pretreatment, the content of calcium, magnesium and silicon is reduced, and then the second-stage concentrated water enters a second-stage concentration treatment, and the second-stage sludge is Mg (OH)2、CaCO3Mainly used as solid waste for landfill treatment;
the second-level concentrated water enters a third-level pretreatment to remove residual calcium, magnesium and silicon, concentrated boron and the like, and then enters a third-level concentration treatment, and the third-level sludge is treated by Mg (OH)2、CaCO3And ion exchange regeneration waste liquid is mainly used, and after full reaction, mud cakes are formed and are used for landfill treatment.
Compared with the prior art, the invention has the advantages that:
1. compared with the high-efficiency reverse osmosis (HERO) technology, the invention reduces the scale of the treatment of chemical softening, hardness and silicon removal, improves the medicament efficiency, reduces the scale of ion exchange, reduces the quantity of regenerated waste liquid, and greatly saves the investment and the operating cost.
2. Compared with the conventional one-time chemical hardness removal softening, under the conditions that the primary concentration recovery rate is 70% and the secondary concentration recovery rate is 80%, the chemical hardness removal scale is reduced to 30% of the conventional treatment, and the ion exchange scale is reduced to 6% of the conventional treatment; based on the calcium-magnesium ion concentration of 200mg/L of inlet water and the calcium-magnesium concentration of 50mg/L of hardness-removing outlet water, under the condition, the chemical hardness-removing removal rate can be improved to 92.5% from 75%; the quantity, investment and operation cost of the corresponding regeneration waste liquid are greatly reduced.
Drawings
In order to more clearly illustrate the embodiments or technical solutions of the present invention, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained based on these drawings without creative efforts.
FIG. 1 is a schematic process flow diagram of one embodiment of the mild stepwise synergistic pretreatment process for mine water treatment provided by the present invention;
FIG. 2 is a schematic process flow diagram of an embodiment of the present invention.
Detailed Description
The technical solution of the present invention will be further specifically described below by way of specific examples. It is to be understood that the practice of the invention is not limited to the following examples, and that any variations and/or modifications may be made thereto without departing from the scope of the invention.
In the present invention, all parts and percentages are by weight, unless otherwise specified, and the equipment and materials used are commercially available or commonly used in the art. The methods in the following examples are conventional in the art unless otherwise specified. The reagents used in the following examples, unless otherwise specified, were purchased from conventional biochemical reagent stores.
The core of the invention is to provide a moderate stepwise cooperative pretreatment process for mine water treatment, wherein the process flow chart of one specific embodiment is shown in figure 1, which is called as a first specific embodiment, and the method comprises the following steps:
as shown in figure 1, a moderate stepwise cooperative pretreatment process for mine water treatment comprises membrane concentration treatment and evaporative crystallization treatment, and comprises the following steps:
the membrane concentration treatment consists of primary concentration, secondary concentration and tertiary concentration;
the moderate stepwise cooperative pretreatment process for mine water treatment specifically comprises primary pretreatment, primary concentration, secondary pretreatment, secondary concentration, tertiary pretreatment, tertiary concentration and evaporative crystallization in sequence to finally obtain product water and crystal salt,
wherein, the primary pretreatment, the secondary pretreatment and the tertiary pretreatment respectively obtain primary sludge, secondary sludge and tertiary sludge, and product water obtained by primary concentration, secondary concentration, tertiary concentration and evaporative crystallization is combined;
in the primary pretreatment, when the primary membrane concentration treatment is carried out on concentrated water obtained from raw water, the primary membrane concentration recovery rate is controlled within a target value range by controlling the main factors influencing the primary membrane concentration recovery rate to feed back and regulate, wherein the target value range of the primary membrane concentration recovery rate is 50-75%;
in the second-stage pretreatment and the third-stage pretreatment, when the concentrated water obtained by the previous-stage membrane concentration is subjected to the current-stage membrane concentration treatment, the concentration recovery rate of the current-stage membrane is controlled within a target value range by controlling main factors influencing the recovery rate of the current-stage membrane in a feedback adjustment mode, wherein the target value range of the concentration recovery rate of the second-stage membrane is 70-80%, and the target value range of the concentration recovery rate of the third-stage membrane is 50-80%.
By applying the technology of the invention, under the conditions that the primary concentration recovery rate is 70 percent, the secondary concentration recovery rate is 80 percent, the calcium and magnesium ion concentration of the mine water inlet water is 200mg/L, and the calcium and magnesium concentration of the hardness-removing water outlet water is 50mg/L, the chemical hardness-removing scale is reduced to 30 percent of that of the conventional treatment, and the ion exchange scale is reduced to 6 percent of that of the conventional treatment; the chemical hardness removal rate can be improved from 75% to 92.5%; the quantity, investment and operation cost of the corresponding regeneration waste liquid are greatly reduced.
On the basis of the first embodiment, the moderate stepwise cooperative pretreatment process for mine water treatment is further improved to obtain a second embodiment, which is different from the first embodiment in that,
the main factors influencing the primary concentration treatment are a large amount of suspended matters (SS) and a small amount of calcium and magnesium in mine water, so that the primary pretreatment aims at removing the SS and inhibiting calcium and magnesium scaling. The first-stage pretreatment adopts coagulating sedimentation, filtration and ultrafiltration processes to remove SS, adopts a scale inhibitor to inhibit the scaling tendency of calcium and magnesium, and eliminates the influence on reverse osmosis.
The main factors influencing the secondary concentration treatment are overhigh calcium, magnesium, silicon and the like after concentration, and the secondary pretreatment mainly aims at removing most of calcium, magnesium and silicon; the second-stage pretreatment adopts chemical softening to remove hard silicon and a filtering process to remove calcium, magnesium, silicon and the like. The chemical softening and hardness and silicon removal are carried out by adding lime and magnesium agent, lime and caustic soda and magnesium agent, caustic soda and soda ash and magnesium agent and the like to form precipitates with calcium, magnesium and silicon; the filtering process adopts Tubular Microfiltration (TMF), a high-density sedimentation tank, sand filtration, ultrafiltration and the like to realize solid-liquid separation of the mine water and the precipitate.
The main factors influencing the three-stage concentration treatment are residual calcium, magnesium, silicon, boron after concentration and the like, and the main aim of the three-stage pretreatment is to completely remove the calcium, the magnesium, the silicon, the boron and the like; the third-stage pretreatment adopts chemical softening to remove hard silicon, filtering and ion exchange process to remove calcium, magnesium, silicon and boron or adopts ion exchange process to remove calcium, magnesium, silicon, boron and the like. The chemical softening and hardness and silicon removal are carried out by adding lime, caustic soda, magnesium agent, caustic soda, soda ash, magnesium agent and the like to form precipitates with calcium, magnesium and silicon; the filtering process can adopt Tubular Microfiltration (TMF), a high-density sedimentation tank, sand filtration and ultrafiltration to realize solid-liquid separation of the mine water and the precipitate; the ion exchange can be performed by weak acid cation exchange resin or chelating resinExchanging residual trace Ca, Mg, Si and B with exchanger, regulating pH value to acidity after ion exchange, and blowing off CO by decarbonizing tower2。
By applying the technology of the invention, the concentration of the calcium and magnesium ions remained in the concentrated brine can be reduced to below 10mg/L from 40-50mg/L of the conventional technology, the scaling influence of an evaporation crystallization unit is reduced, and the cleaning period of the evaporation crystallization unit is prolonged by more than 20%.
On the basis of the first embodiment, the moderate stepwise cooperative pretreatment process for mine water treatment is further improved to obtain a third embodiment, which is different from the first embodiment in that,
the method comprises the following steps of (1) removing suspended matters such as coal dust, rock dust and the like from mine water containing suspended matters such as calcium, magnesium, silicon and the like through primary pretreatment, wherein the turbidity is less than or equal to 5NTU, adding a proper scale inhibitor according to the total soluble solids in the mine water, controlling the scaling tendency to be less than or equal to 80%, and performing primary concentration treatment; the first-stage sludge is subjected to sludge concentration and filter pressing to form coal mud cakes with the water content of less than or equal to 60 percent, the heat value is more than 2000kJ/kg, the coal mud cakes are comprehensively utilized as low-heat-value fuel, and the filter pressing liquid is returned to the stage of pretreatment for cyclic treatment and recycling.
The concentration of calcium, magnesium and silicon in the concentrated water after the first-stage concentration is increased to 3-5 times of the original concentration, the concentrated water enters a second-stage pretreatment, chemical agents such as lime, magnesium agent and the like are added according to the water quality condition, and Mg (OH) is generated through reaction2、CaCO3Performing solid-liquid separation on the sludge chemically precipitated with silicon through a high-density sedimentation tank, sand filtration and ultrafiltration, a mechanical accelerated clarification tank, sand filtration and ultrafiltration or Tubular Microfiltration (TMF), and performing secondary concentration treatment on the residual calcium, magnesium and silicon in mine water which are reduced to below 50 mg/L; the secondary sludge mainly comprises Mg (OH)2、CaCO3And after concentration and filter pressing, the water content is reduced to be below 65 percent, the solid waste is buried and treated, and the filter pressing liquid is returned to the stage of pretreatment for recycling treatment.
The concentration of calcium, magnesium and silicon in the concentrated water after the second-stage concentration is increased to about 50-250mg/L, and the concentrated water enters a third-stage pretreatment; the third-stage pretreatment adopts chemical softening to remove hardness and silicon and overThe calcium, magnesium, silicon, boron and the like are removed by a filtration and ion exchange process or are removed by a separate ion exchange process. Adding lime, caustic soda, magnesium agent, soda ash and the like to form precipitates with calcium, magnesium and silicon according to the composition of water, and realizing solid-liquid separation by adopting Tubular Microfiltration (TMF), a high-density sedimentation tank, sand filtration, ultrafiltration and the like; removing residual trace calcium, magnesium, silicon and boron completely by weak acid cation resin exchanger or chelating resin exchanger, adjusting pH to acidity, and blowing off CO by decarbonizing tower2And the calcium, magnesium and silicon after treatment are reduced to be below 0.03mmol/L, so that the requirements of subsequent three-stage concentration and evaporative crystallization are met. The tertiary sludge is mainly Mg (OH)2、CaCO3The main sludge and the ion exchange regeneration waste liquid are mixed and reacted, the water content is reduced to below 65 percent through concentration and filter pressing, the mixture is used as solid waste for landfill treatment, and the filter pressing liquid is returned to the stage of pretreatment for recycling treatment. The concentrated produced water of each stage is mixed to be used as high-quality production and domestic water for coal mines.
By applying the technique of the present invention, the amount of sludge to be landfilled is greatly reduced. Because suspended matters in mine water are particles with calorific values such as coal dust and the like, the suspended matters are firstly removed in the step-by-step synergistic pretreatment process of the invention to form fuel without other pollutants and with the calorific value of more than 2000kJ/kg, the fuel can be comprehensively utilized, and certain economic benefits can be brought while the sludge treatment cost is reduced. Compared with the conventional technology, the sludge amount required to be buried is reduced by more than 50%.
Application embodiment mode
FIG. 2 is a schematic process flow diagram of one embodiment of the present invention. The water quantity of the coal mine water is 600t/h, SS is between 155-1032mg/L, TDS is about 3560mg/L, calcium and magnesium contents are medium, and specific indexes are shown in Table 1.
A moderate stepwise cooperative pretreatment process for mine water treatment specifically comprises primary pretreatment, primary concentration, secondary pretreatment, secondary concentration, tertiary pretreatment, tertiary concentration and evaporative crystallization in sequence to finally obtain product water and crystal salt, wherein the primary pretreatment, the secondary pretreatment and the tertiary pretreatment are respectively used for obtaining primary sludge, secondary sludge and tertiary sludge, and the product water obtained by the primary concentration, the secondary concentration, the tertiary concentration and the evaporative crystallization is combined to realize zero emission of mine water.
The primary pretreatment sequentially comprises the working procedures of coagulating sedimentation, quartz sand filtration and ultrafiltration, the solid-liquid separation of the mine water and the precipitate is realized by ultrafiltration, the solid-containing mud water returns to the coagulating sedimentation, the effluent enters the primary concentration, and the concentrated water after the primary concentration enters the secondary pretreatment; the second-stage pretreatment sequentially comprises a medicament hardness removal reaction, a high-density sedimentation tank, quartz sand filtration and an ultrafiltration process, solid-liquid separation is realized between mine water and sediments by ultrafiltration, solid-containing mud water returns to the hardness removal reaction process for continuous treatment, effluent enters second-stage concentration, and concentrated water after second-stage concentration enters third-stage pretreatment; the third-stage pretreatment sequentially comprises the processes of medicament hardness removal reaction, tubular microfiltration, ion exchange and acid addition decarburization, and effluent enters third-stage concentration.
The target value range of the first-stage membrane concentration recovery rate is 50-75%, and reaches 75% in the embodiment; the target value range of the secondary membrane concentration recovery rate is 70-80%, and reaches 76% in the embodiment; the target value range of the concentration recovery rate of the three-stage membrane is 50-80%, and 50% is achieved in the embodiment.
The moderate stepwise cooperative pretreatment process is adopted, and the primary pretreatment process adopts a coagulating sedimentation process, a quartz sand filtration process and an ultrafiltration process. The coagulating sedimentation adopts a hydraulic circulating clarification tank, adding 28.5mg/L of polyaluminium chloride (PAC) and 0.3mg/L of Polyacrylamide (PAM), filtering through a valveless filter after fully mixing and reacting, wherein the turbidity of the outlet water is between 3.5 and 10.5NTU, and then carrying out ultrafiltration, wherein the turbidity of the outlet water is reduced to be below 0.3 NTU. Scale inhibition analysis shows that the easily-scaling components are calcium carbonate and calcium sulfate, and the concentration recovery rate of the first-stage concentration membrane can reach 75% under the condition of adding 2.37mg/L of scale inhibitor. The water content of the first-stage pretreated sludge is 55 percent after concentration and filter pressing, the heat value is about 2750kJ/kg, the first-stage pretreated sludge is used as low heat value fuel for comprehensive utilization, and the filter pressing liquid is returned to the first-stage pretreatment for cyclic treatment and recycling.
After the first-stage concentration, the TDS of the concentrated water is increased to over 14500mg/L, and calcium, magnesium and silicon are respectively increased to over 230mg/L, 80mg/L and 60 mg/L. The secondary pretreatment adopts the processes of medicament reaction, high-density sedimentation tank, quartz sand filtration and ultrafiltration, lime, magnesium and a small amount of liquid alkali are added into the reaction tank, the scale of hardness removal and softening is reduced to 150t/h, the calcium, magnesium and silicon after pretreatment are respectively 19.11mg/L, 19.83mg/L and 18.62mg/L, the removal rates are respectively improved to 92%, 75% and 69%, and the medicament efficiency is greatly improved. And scale inhibitor is not required to be added in the second-stage concentration, and the membrane concentration recovery rate is 76%. The water content of the secondary pretreated sludge is 62 percent after concentration and filter pressing, the secondary pretreated sludge is used as general solid waste for landfill treatment, and the filter pressing liquid is returned to the primary pretreatment for circular treatment and recycling.
After the secondary concentration, the TDS of the concentrated water is increased to more than 51000mg/L, and the calcium, the magnesium, the silicon, the boron and the bicarbonate are respectively concentrated to more than 79mg/L, 73mg/L, 9.98mg/L and 483 mg/L. The three-stage pretreatment adopts a process of medicament reaction, tubular microfiltration, ion exchange and decarburization, lime, a magnesium agent and a small amount of liquid caustic soda are added into a reaction tank, the scale of hardness removal, softening, ion exchange and decarburization is 36t/h, the treated calcium, magnesium, silicon, boron and bicarbonate are respectively reduced to 0.4mg/L, 0.5mg/L, 4.77mg/L, 0.98mg/L and 33mg/L, the removal rate is 99%, 93%, 90% and 93%, and the medicament efficiency is greatly improved. Scale inhibitor is not needed to be added in the three-stage concentration, and the membrane concentration recovery rate is 50%; the tertiary concentrated water directly enters an evaporative crystallization system without being treated again. The water content of the third-stage pretreated sludge is 65 percent after concentration and filter pressing, the third-stage pretreated sludge is used as common solid waste for landfill treatment, and the filter pressing liquid is returned to the primary pretreatment for recycling treatment.
The treatment effect data of the treatment process on the mine water quality indexes are shown in the table 1.
Table 1: water quality indexes of units in coal mine water zero-discharge treatment process
The conventional process for mine water zero-emission treatment (specifically comprises the following steps of): mine water → chemical hardness removal → coagulating sedimentation → filtration → ion exchange → ultrafiltration → primary concentration → secondary concentration → tertiary concentration → evaporative crystallization.
According to the conventional process of mine water zero emission treatment, the concentrations of calcium, magnesium and silicon ions are respectively 60.75mg/L, 20.00mg/L and 15.63mg/L, after direct medicament softening, the concentrations of the calcium, magnesium and silicon ions are respectively reduced to 19.3mg/L, 17.55mg/L and 13.2mg/L, the removal rates are respectively about 68.2%, 12.3% and 15.5%, and the removal rate is extremely low. Meanwhile, because one-time hardness removal and softening are adopted, the residual calcium, magnesium and silicon are continuously concentrated in the subsequent concentration treatment process until the evaporation crystallization units are respectively increased to 445mg/L, 393mg/L and 366mg/L, which are nearly 400 times, 500 times and 40 times of the water quality of the evaporation crystallization units. The scale of the conventional processes such as hardness removal, softening, ion exchange and the like reaches 600 t/h.
In the embodiment, the total scale of hardness removal and softening is 186t/h, and the scale of ion exchange and decarburization is 36t/h, which is only 31 percent and 6 percent of the corresponding unit scale in the conventional process, so that the construction investment and the operating cost are greatly reduced.
The embodiments are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same or similar parts among the embodiments are referred to each other. The device disclosed by the embodiment corresponds to the method disclosed by the embodiment, so that the description is simple, and the relevant points can be referred to the method part for description.
The moderate stepwise cooperative pretreatment process for mine water treatment provided by the invention is described in detail above. The principles and embodiments of the present invention are explained herein using specific examples, which are presented only to assist in understanding the method and its core concepts. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
Claims (9)
1. A moderate stepwise cooperative pretreatment process for mine water treatment comprises membrane concentration treatment and evaporative crystallization treatment, and is characterized by comprising the following steps:
the membrane concentration treatment comprises primary concentration, secondary concentration and tertiary concentration;
the moderate stepwise cooperative pretreatment process for mine water treatment specifically comprises primary pretreatment, primary concentration, secondary pretreatment, secondary concentration, tertiary pretreatment, tertiary concentration and evaporative crystallization in sequence to finally obtain product water and crystal salt,
wherein, the primary pretreatment, the secondary pretreatment and the tertiary pretreatment respectively obtain primary sludge, secondary sludge and tertiary sludge, and product water obtained by primary concentration, secondary concentration, tertiary concentration and evaporative crystallization is combined;
in the primary pretreatment, when the primary membrane concentration treatment is carried out on concentrated water obtained from raw water, the primary membrane concentration recovery rate is controlled within a target value range by controlling the main factors influencing the primary membrane concentration recovery rate to feed back and regulate, wherein the target value range of the primary membrane concentration recovery rate is 50-75%;
in the second-stage pretreatment and the third-stage pretreatment, when the concentrated water obtained by the previous-stage membrane concentration is subjected to the current-stage membrane concentration treatment, the concentration recovery rate of the current-stage membrane is controlled within a target value range by controlling main factors influencing the recovery rate of the current-stage membrane in a feedback adjustment mode, wherein the target value range of the concentration recovery rate of the second-stage membrane is 70-80%, and the target value range of the concentration recovery rate of the third-stage membrane is 50-80%.
2. The moderately stepped synergistic pretreatment process for mine water treatment according to claim 1, characterized in that:
the primary pretreatment aims at removing SS and inhibiting calcium and magnesium scaling;
the main goal of the secondary pretreatment is to remove most of calcium, magnesium and silicon;
the main goal of the three-stage pretreatment is to completely remove calcium, magnesium, silicon and boron.
3. The moderately stepped synergistic pretreatment process for mine water treatment according to claim 1, characterized in that: the primary pretreatment is to remove SS from mine water raw water by adopting coagulating sedimentation, filtration and ultrafiltration processes, and a scale inhibitor is adopted to inhibit the scaling tendency of calcium and magnesium, so that the influence on reverse osmosis is eliminated;
the second-stage pretreatment adopts chemical softening to remove hard silicon and a filtering process to remove calcium, magnesium, silicon and the like aiming at the concentrated water of the first-stage concentration;
the third-stage pretreatment is to remove calcium, magnesium, silicon and boron by adopting a chemical softening and hardness removal silicon removal and filtration + ion exchange process aiming at the concentrated water of the second-stage concentration, or to remove calcium, magnesium, silicon, boron and the like by adopting an ion exchange process alone.
4. The moderately stepped synergistic pretreatment process for mine water treatment according to claim 1, characterized in that: in the first-stage pretreatment, the coagulating sedimentation adopts a hydraulic circulating clarification tank or a mechanical accelerated clarification tank.
5. The moderately stepped synergistic pretreatment process for mine water treatment according to claim 1, characterized in that: in the second-stage pretreatment, one of lime and magnesium agent, lime and caustic soda and magnesium agent, caustic soda and soda ash and magnesium agent is adopted for chemical softening and hardness removal, and a Tubular Microfiltration (TMF) or a high-density sedimentation tank, sand filtration and ultrafiltration process is adopted for a filtration process.
6. The moderately stepped synergistic pretreatment process for mine water treatment according to claim 1, characterized in that: in the three-stage pretreatment, lime, caustic soda and magnesium agent or caustic soda, soda and magnesium agent are adopted for chemical softening and hardness removal, Tubular Microfiltration (TMF), a high-density sedimentation tank, sand filtration and ultrafiltration are adopted for the filtration process, a weak acid cation resin exchanger or a chelating resin exchanger is adopted for ion exchange, the pH value is adjusted to acidity after the ion exchange, and a decarbonization tower is arranged for blowing off CO2。
7. The moderately stepwise synergistic pretreatment process for mine water treatment according to claim 1, characterized in that the process comprises:
first-stage pretreatment adopts the resistanceScale inhibitor scale inhibition, no chemical agents such as lime, magnesium agent and the like are added, and no Mg (OH) is generated2、CaCO3Chemical precipitation sludge; after the first-stage concentration, the concentration of calcium, magnesium and silicon in the mine water is improved to 3-5 times of the original concentration,
adding chemical agents such as lime, magnesium agent and the like in the secondary pretreatment process to generate Mg (OH)2、CaCO3After chemical precipitation of sludge, controlling the residual calcium, magnesium and silicon in the mine water to be 10-50 mg/L; after the secondary concentration, the concentration of calcium, magnesium and silicon is increased to 50-250mg/L,
chemical agents such as lime, magnesium agents and the like are added in the three-stage pretreatment process to reduce calcium, magnesium and silicon to 10-50mg/L and then ion exchange is carried out or ion exchange is independently adopted, calcium and magnesium ions are reduced to be below 0.03mmol/L and silicon is reduced to be below 20mg/L after the three-stage pretreatment, so that the requirements of subsequent concentration and evaporative crystallization are met.
8. The moderately stepped synergistic pretreatment process for mine water treatment according to claim 1, characterized in that:
the main component of the primary sludge is pulverized coal with the heat value of more than 2000kJ/kg, the water content of the primary sludge is reduced to below 60 percent after concentration and filter pressing, the primary sludge is used as low-heat-value fuel for comprehensive utilization, and the filter pressing liquid is returned to the primary pretreatment for cyclic treatment and recycling;
the secondary sludge mainly comprises Mg (OH)2、CaCO3After concentration and filter pressing, the water content is reduced to be below 65 percent, the waste is used as common solid waste for landfill treatment, and the filter pressing liquid is returned to the stage of pretreatment for recycling treatment;
the main component of the third-stage sludge is Mg (OH)2、CaCO3The main sludge and the ion exchange regeneration waste liquid are mixed and reacted, the water content of the main sludge and the ion exchange regeneration waste liquid is reduced to be below 65 percent through concentration and filter pressing, the main sludge and the ion exchange regeneration waste liquid are used as common solid waste for landfill treatment, and the filter pressing liquid is returned to the stage of pretreatment for recycling treatment.
9. The moderately stepwise synergistic pretreatment process for mine water treatment according to claim 1, characterized in that the process comprises:
removing suspended matters from the mine water through primary pretreatment, adding a scale inhibitor, and performing primary concentration treatment, wherein primary sludge is mainly pulverized coal and is comprehensively utilized as a low-calorific-value fuel;
the first-stage concentrated water enters a second-stage pretreatment, the content of calcium, magnesium and silicon is reduced, and then the second-stage concentrated water enters a second-stage concentration treatment, and the second-stage sludge is Mg (OH)2、CaCO3Mainly used as solid waste for landfill treatment;
the second-level concentrated water enters a third-level pretreatment to remove residual calcium, magnesium and silicon, concentrated boron and the like, and then enters a third-level concentration treatment, and the third-level sludge is treated by Mg (OH)2、CaCO3And ion exchange regeneration waste liquid is mainly used, and after full reaction, mud cakes are formed and are used for landfill treatment.
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