CN109956578B - Pretreatment method and system for high-salinity desulfurization wastewater of coal-fired power plant - Google Patents

Pretreatment method and system for high-salinity desulfurization wastewater of coal-fired power plant Download PDF

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CN109956578B
CN109956578B CN201711405526.8A CN201711405526A CN109956578B CN 109956578 B CN109956578 B CN 109956578B CN 201711405526 A CN201711405526 A CN 201711405526A CN 109956578 B CN109956578 B CN 109956578B
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clear water
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CN109956578A (en
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李国涛
钟振成
熊日华
霍卫东
程子洪
马瑞
李小端
段亚威
李永龙
卫昶
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China Energy Investment Corp Ltd
National Institute of Clean and Low Carbon Energy
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National Institute of Clean and Low Carbon Energy
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00—Multistage treatment of water, waste water or sewage
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/442—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/50—Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F2001/5218—Crystallization
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/18—Nature of the water, waste water, sewage or sludge to be treated from the purification of gaseous effluents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
    • C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents

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  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
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  • Chemical & Material Sciences (AREA)
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Abstract

The invention relates to the field of purification of high-salt desulfurization wastewater of a coal-fired power plant, and discloses a pretreatment method and a pretreatment system of the high-salt desulfurization wastewater of the coal-fired power plant. The pretreatment method comprises the following steps: (1) Adding lime into the desulfurization wastewater to carry out primary reaction, and carrying out primary solid-liquid separation on the obtained primary reaction product to obtain primary clear water and primary sludge; (2) Adjusting the pH of the first-stage clear water to obtain a stock solution with a pH value of 6-8; (3) Adding a bactericide into the stock solution and carrying out filtering treatment to obtain filtered produced water; (4) Adding a scale inhibitor and a scale inhibitor deactivator into the filtered produced water and carrying out ion separation to obtain high-concentration brine and pretreated produced water; (5) Adding sodium sulfate into the high-concentration brine, and then sequentially carrying out secondary reaction and calcium sulfate crystallization separation at normal temperature to obtain secondary clear water and secondary sludge; and (4) returning the secondary clean water to the step (3) for filtering treatment. The pretreatment cost of the desulfurization wastewater of the coal-fired power plant can be effectively reduced.

Description

Pretreatment method and system for high-salinity desulfurization wastewater of coal-fired power plant
Technical Field
The invention relates to the field of purification of high-salt desulfurization wastewater of a coal-fired power plant, in particular to a pretreatment method and a pretreatment system of the high-salt desulfurization wastewater of the coal-fired power plant.
Background
The SO in the flue gas is removed by limestone wet desulphurization technology in most of power plants and coal chemical plants in China 2 The generated desulfurization wastewater is one of the most difficult wastewater to treat in coal-fired power plants due to complex components and various pollutant types. At present, the chemical precipitation method (commonly called triple-box precipitation) is mainly adopted in China to treat the desulfurization wastewater, the salt content of treated effluent is high, and secondary pollution is easily caused after the treated effluent is directly discharged. Meanwhile, because the desulfurization wastewater has small water amount and high salt content, the process system for further treating the desulfurization wastewater in a power plant and a coal chemical plant is unstable in long-time operation (the scaling condition of the ultrafiltration and nanofiltration reverse osmosis system is serious due to the high content of slightly soluble inorganic salt in the inlet water), and the operation cost is high, no practical application case exists at present. However, with the further enhancement of the environmental protection requirement in our country, the development of the further zero-emission treatment technology of the desulfurization wastewater is urgent, and technical innovation and technical development are urgently needed in the aspects of reducing the cost of the process system and improving the stability of the process system.
In the prior art, when high-salt desulfurization wastewater of a coal-fired power plant is purified, although monovalent and divalent ions in the wastewater can be removed, most of the two ions are removed together, and formed salt is a mixture of various substances, so that monovalent ions and divalent ions cannot be effectively separated, and compounds which are not beneficial to the removal of ions are further utilized. Meanwhile, the process in the prior art is high in operation cost, the burden of emission treatment of a power plant is increased, and a solution is urgently needed.
Disclosure of Invention
The invention aims to overcome the problems of impure removed products and higher process operation cost in the prior art, and provides a pretreatment method and a pretreatment system for high-salt desulfurization wastewater of a coal-fired power plant.
In order to achieve the above object, a first aspect of the present invention provides a pretreatment method of high salinity desulfurization wastewater of a coal fired power plant, comprising:
(1) Adding lime into the desulfurization wastewater, carrying out primary reaction, and carrying out primary solid-liquid separation on the obtained primary reaction product to obtain primary clear water and primary sludge;
(2) Adjusting the pH of the first-stage clear water to obtain a stock solution with a pH value of 6-8;
(3) Adding a bactericide into the stock solution and performing filtration treatment to obtain filtered produced water;
(4) Adding a scale inhibitor and a scale inhibitor deactivator into the filtered produced water and carrying out ion separation to obtain high-concentration brine and pretreated produced water;
(5) Adding sodium sulfate into the high-concentration brine, and then sequentially carrying out secondary reaction and calcium sulfate crystallization separation at normal temperature to obtain secondary clear water and secondary sludge;
and (4) returning the secondary clean water to the step (3) for filtering treatment.
Preferably, in step (1), lime is added in an amount to provide a pH of said first reaction product of from 10.5 to 12.
Preferably, the temperature of the first-stage reaction is 10-30 ℃, the pressure of the first-stage reaction is 0.02-0.1MPa, and the time of the first-stage reaction is 60-180min.
Preferably, in step (3), the bactericide is selected from sodium hypochlorite and/or hydrogen peroxide; the addition amount of the bactericide is 1-20 mass ppm of the total amount of the stock solution and the secondary clear water.
Preferably, in step (3), the filtration treatment is ultrafiltration and/or sand filtration.
Preferably, the filtered produced water has an SDI value of 1 or less.
Preferably, in the step (4), the scale inhibitor is a nanofiltration or reverse osmosis membrane scale inhibitor, and the scale inhibitor deactivator is selected from ferric trichloride and/or hydrogen peroxide.
Preferably, the addition amount of the scale inhibitor is 1-20 mass ppm of the filtration produced water, and the addition amount of the scale inhibitor deactivator is 1-20 mass ppm of the filtration produced water.
Preferably, in step (4), the ion separation is nanofiltration separation.
Preferably, the nanofiltration separation temperature is 10-30 ℃, the nanofiltration separation pressure is 0.8-1.5MPa, and the water yield of the pretreatment water is 30-70% of the filtered water yield.
Preferably, in the step (5), the sodium sulfate is added in an amount to ensure that the total hardness of the secondary clear water is 10-40mmol/L.
Preferably, in the step (5), the temperature of the secondary reaction is 10-30 ℃, the pressure of the secondary reaction is 0.02-0.1MPa, and the time of the secondary reaction is 120-360min.
Preferably, the weight ratio of the stock solution to the secondary clear water is (1.5-3.5): 1.
the second aspect of the present invention provides a system for high-salinity desulfurization wastewater from coal-fired power plants, comprising: the device comprises a first-stage reaction unit 1, an acidity adjusting unit 2, a filtering unit 3, an ion separating unit 4 and a second-stage reaction unit 5;
the primary reaction unit is used for adding lime into the desulfurization wastewater, performing primary reaction and separating to obtain primary clear water and primary sludge;
the acidity adjusting unit is used for adjusting the pH of the primary clear water into a secondary reaction liquid;
the filtering unit is used for adding a bactericide into the secondary reaction liquid and carrying out filtering treatment to obtain filtered water;
the ion separation unit is used for adding a scale inhibitor and a scale inhibitor deactivator into the filtered produced water for ion separation to obtain high-concentration brine and pretreated produced water;
the secondary reaction unit is used for adding sodium sulfate into the high-concentration brine, performing secondary reaction and calcium sulfate crystallization separation to obtain secondary clear water and secondary sludge;
and a secondary clear water outlet of the secondary reaction unit is communicated with an inlet of the filtering unit and is used for introducing the secondary clear water into the filtering unit for filtering treatment.
According to the technical scheme, the purification pretreatment of the high-salt desulfurization wastewater of the coal-fired power plant is carried out step by step, and the agents of lime and sodium sulfate are put in step by step, so that monovalent ions and high-valence ions in the desulfurization wastewater can be effectively separated, the monovalent ions are enriched in the finally obtained pretreatment product water, and the monovalent ions are further treated and removed through a downstream process. Divalent ions can be remained in the primary sludge and the secondary sludge obtained by the method, and calcium sulfate byproducts with higher purity can be obtained by corresponding primary sludge treatment and secondary sludge treatment, and can be used for high-quality building or food gypsum to improve the value-added effect of desulfurization wastewater purification. While the monovalent ions and the divalent ions in the desulfurization wastewater are effectively separated, the method and the system adopt the step-by-step operation, the lime and the sodium sulfate are added, and the whole process is operated at normal temperature and normal pressure, so that the operation cost of the whole process is reduced.
Drawings
FIG. 1 is a schematic flow diagram of a pretreatment method and system for high-salt desulfurization wastewater of a coal-fired power plant provided by the invention.
Description of the reference numerals
1. A first-stage reaction unit 2, an acidity adjusting unit 3 and a filtering unit
4. An ion separation unit 5, a secondary reaction unit 6 and a primary sludge treatment unit
7. Secondary sludge treatment unit
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a pretreatment method of high-salinity desulfurization wastewater of a coal-fired power plant, which comprises the following steps:
(1) Adding lime into the desulfurization wastewater, carrying out primary reaction, and carrying out primary solid-liquid separation on the obtained primary reaction product to obtain primary clear water and primary sludge;
(2) Adjusting the pH of the primary clear water to obtain a stock solution with a pH value of 6-8;
(3) Adding a bactericide into the stock solution and carrying out filtering treatment to obtain filtered produced water;
(4) Adding a scale inhibitor and a scale inhibitor deactivator into the filtered produced water and carrying out ion separation to obtain high-concentration brine and pretreated produced water;
(5) Adding sodium sulfate into the high-concentration brine, and then sequentially carrying out secondary reaction and calcium sulfate crystallization separation at normal temperature to obtain secondary clear water and secondary sludge;
and (4) returning the secondary clear water to the step (3) for filtering treatment.
The desulfurization wastewater treated by the method can be wastewater from a desulfurization device of a coal-fired power plant, can be desulfurization wastewater discharged after being swirled by a wastewater swirler, and contains a large amount of suspended matters, calcium sulfate, magnesium sulfate, sodium chloride and other organic matters and inorganic salt impurities. Wherein, the contents of calcium, magnesium ions and chloride ions are high. The method provided by the invention can effectively remove the impurities in the wastewater, can separate monovalent and divalent ions in the wastewater, such as magnesium ions, calcium ions, sulfate ions and chloride ions, improves the water quality of the desulfurization wastewater, obtains calcium sulfate with high purity, and has the advantage of low cost.
The method provided by the invention is preferably used for treating the desulfurization waste water, and the composition of the desulfurization waste water can contain sodium ions with the concentration of 400-1500mg/L, chloride ions with the concentration of 4000-15000mg/L, sulfate ions with the concentration of 3000-8000mg/L, calcium ions with the concentration of 1000-3000mg/L and magnesium ions with the concentration of 1500-5000 mg/L.
The method provided by the invention is divided into the steps and the reagents of lime and sodium sulfate are added in two steps, so that monovalent ions and divalent ions in the desulfurization wastewater can be effectively separated, monovalent ions are remained in the finally obtained pretreatment product water, and the monovalent ions can be conveniently separated by downstream processes and equipment. And divalent ions are removed into the primary sludge and the secondary sludge, and the secondary sludge can obtain calcium sulfate with higher purity, thereby being beneficial to subsequent high-added-value utilization.
In the present invention, the step (1) is mainly used for reducing Mg in the desulfurization waste water 2+ Especially non-carbonate Mg 2+ Formation of Mg (OH) 2 Precipitation and at the same time reduction of the bulk of the Si. Preferably, in step (1), lime is added in an amount to provide a pH of said first reaction product of from 10.5 to 12. Wherein the lime can be added in the form of a lime solution with a concentration of 8-12% by weight. The first-stage reaction product is a solid-liquid mixture.
In the invention, the condition of the first-stage reaction can finish the precipitation of magnesium ions, and the first-stage reaction can be carried out at normal temperature and normal pressure with mild conditions; can be carried out in a stirred tank. Preferably, the temperature of the first-stage reaction is 10-30 ℃, the pressure of the first-stage reaction is 0.02-0.1MPa, and the time of the first-stage reaction is 60-180min.
In the invention, flocculating agent and coagulant aid can also be added in the step (1). There may be used flocculants and coagulant aids conventionally used in the art, and without particular limitation, polyacrylamide, polyferric, and the like may be preferable. The addition amount is only required to achieve the required flocculation effect, and can be the conventional amount in the field, for example, the flocculant and the coagulant aid can be respectively used in 1-20 mass ppm of the desulfurization wastewater.
In the step (1), the first-stage reaction product is further subjected to first-stage solid-liquid separation, wherein the first-stage reaction product can be kept stand and filtered to obtain solid, namely first-stage sludge, which is rich in divalent ions such as Mg 2+ . The first grade clear water can be Mg 2+ In a reduced concentration, e.g. Mg 2+ The concentration of (B) is 10mg/L or less.
The first-grade clear water obtained by the method preferably has the composition of sodium ions with the concentration of 3500-4500mg/L, chloride ions with the concentration of 4000-15000mg/L, sulfate ions with the concentration of 5000-6000mg/L, calcium ions with the concentration of 4000-5000mg/L and magnesium ions with the concentration of 20-40 mg/L.
In the step (2) of the present invention, the pH of the primary clear water obtained in the step (1) may be adjusted to suit the secondary reaction. The pH value is adjusted too much, which is not beneficial to the whole implementation of the method of the invention, and the invention can not realize that calcium ions can be selectively separated in the subsequent steps to obtain high-quality gypsum. For example, if the pH value is more than 11, the primary sludge also contains calcium sulfate precipitate, which is not beneficial to the secondary sludge designed by the invention to obtain high-quality gypsum. The agent added for pH adjustment may be selected from sulfuric acid or hydrochloric acid solution, and may be a concentrated or diluted solution of sulfuric acid or hydrochloric acid.
In the present invention, step (3) can be used to remove suspended matter and colloid in the stock solution, and provide a suitable ion separation feed for the downstream step (4). Preferably, in step (3), the bactericide is selected from sodium hypochlorite and/or hydrogen peroxide.
In the invention, the step (3) also comprises the secondary clear water from the downstream circulation loop. Preferably, the weight ratio of the stock solution to the secondary clear water is (1.5-3.5): 1. thereby improving the reduction of Ca in the secondary reaction liquid by the removal of calcium ions 2+ The effect of (2) is to better separate divalent ions in the desulfurization waste liquid. Preferably, the addition amount of the bactericide is 1-20 mass ppm of the total amount of the stock solution and the secondary clear water.
In the present invention, the conditions of the filtration treatment are such that a feed suitable for the ion separation is obtained. Preferably, in the step (3), the filtration treatment is ultrafiltration and/or sand filtration; preferably, the filtered produced water has an SDI value of 1 or less. The SDI value is a pollution index value of a water quality index and can be measured by using an SDI meter according to ASTM method 4189-95.
In the present invention, step (4) may be used to further separate divalent and higher ions that may also be present in the filtered product water. Preferably, in the step (4), the scale inhibitor is a nanofiltration or reverse osmosis membrane scale inhibitor; the addition amount of the scale inhibitor is 1-20 mass ppm of the filtered produced water. The scale inhibitor is a known substance and is commercially available, for example, pc-191 from Nalacco, OSM-60 from Nalacco.
Preferably, the scale inhibitor deactivating agent is selected from ferric trichloride and/or hydrogen peroxide; the addition amount of the scale inhibitor deactivator is 1-20 mass ppm of the filtered produced water.
In the invention, the ion separation condition is only required to separate divalent ions and monovalent ions in the filtered produced water. Preferably, in step (4), the ion separation is nanofiltration separation; preferably, the nanofiltration separation temperature is 10-30 ℃, the nanofiltration separation pressure is 0.8-1.5MPa, and the water yield of the pretreatment water is 30-70% of the filtered water yield. Preferably, the pre-treatment produced water has a produced water amount of 50% of the filtered produced water. The recovery rate of monovalent ions in the pretreatment produced water can be obviously improved. Nanofiltration membrane elements used in the nanofiltration separation are known substances and are commercially available. Such as GE DL series nanofiltration membrane elements, GE SWSR series nanofiltration membrane elements, DOW NF270 series nanofiltration membrane elements, or NE8040-40 nanofiltration membrane elements of the korean TCK company. Through the ion separation under the conditions, the pretreated produced water contains calcium ions and sulfate ions with the total concentration of less than 1 mmol/L. Meanwhile, the high-concentration brine contains calcium ions and sulfate ions at a total concentration of 90 wt% or more.
The composition of the pre-treatment produced water preferably obtained by the method provided by the invention can contain 6500-7500mg/L of sodium ions, 4000-15000mg/L of chloride ions, 150-300mg/L of sulfate ions, 100-250mg/L of calcium ions and 0.1-11mg/L of magnesium ions.
In the present invention, step (5) is used to further remove divalent ions from the high-concentration brine. Ca in the high-concentration brine can be mainly separated out by adding sodium sulfate 2+ To generate CaSO 4 . Simultaneous production of CaSO 4 And crystallizing, precipitating and separating out the high-concentration brine when the solubility of the sludge in the high-concentration brine reaches supersaturation, and then carrying out secondary solid-liquid separation to obtain secondary sludge. The secondary sludge obtained in the way can obtain gypsum with the purity of more than 96.0 percent through further sludge treatment, can meet the standards for buildings or food, and has higher added value. Preferably, in the step (5), the sodium sulfate is added in an amount to ensure that the total hardness of the secondary clear water is 10-40mmol/L. The total hardness is the total concentration of calcium ions and magnesium ions, and the unit is converted into mmol/L. Wherein the sodium sulfate may be present in a concentration of 8-12% by weightIs added as a sodium sulfate solution.
In the present invention, the secondary reaction may be carried out at normal temperature and pressure. Divalent ions, mainly Ca, in the high-concentration brine 2+ Can be separated in the form of calcium sulfate crystals. Preferably, in the step (5), the temperature of the secondary reaction is 10-30 ℃, the pressure of the secondary reaction is 0.02-0.1MPa, and the time of the secondary reaction is 120-360min.
In the invention, a large amount of supersaturated calcium sulfate is formed in the secondary reaction product obtained by the secondary reaction, the calcium sulfate is crystallized and separated at normal temperature, and the calcium sulfate is discharged from the secondary sludge to play a role in removing calcium ions. The ordinary temperature here may preferably be 10 to 35 ℃.
The step (5) of the invention also comprises the secondary solid-liquid separation to obtain secondary sludge and secondary clear water. The secondary sludge is rich in Ca 2+ And the calcium sulfate has high purity, and can be used as a high-quality gypsum product.
In the invention, the secondary clear water obtained in the step (5) further reduces Ca 2+ In a content of Ca 2+ The concentration of (B) is 1000mg/L or less.
In the invention, flocculating agent and coagulant aid can also be added in the step (5). There may be used flocculants and coagulant aids conventionally used in the art, and without particular limitation, polyacrylamide, polyferric, and the like may be preferable. The addition amount is only required to achieve the required flocculation effect, and can be the conventional amount in the field, for example, the flocculant and the coagulant aid can be respectively used in the amount of 1-20 mass ppm of the high-concentration saline water.
The composition of the secondary clear water preferably obtained by the method provided by the invention can contain 6500-7500mg/L sodium ions, 4000-15000mg/L chloride ions, 200-300mg/L sulfate ions, 800-1000mg/L calcium ions and 20-40mg/L magnesium ions.
In the invention, the pretreatment method can also comprise the step of treating the obtained primary sludge and secondary sludge to prevent secondary pollution. The treatment method can be to mix the primary sludge and the secondary sludge into an ash yard or mix the primary sludge and the secondary sludge into a gypsum semi-finished product. Wherein the secondary sludge is treated to obtain gypsum with the purity of more than 96.0 percent.
The second aspect of the present invention provides a system for high-salinity desulfurization wastewater from coal-fired power plants, comprising: the device comprises a first-stage reaction unit 1, an acidity adjusting unit 2, a filtering unit 3, an ion separating unit 4 and a second-stage reaction unit 5;
the first-stage reaction unit is used for adding lime into the desulfurization wastewater, performing first-stage reaction, and separating to obtain first-stage clear water and first-stage sludge;
the acidity adjusting unit is used for adjusting the pH of the primary clear water into a secondary reaction liquid;
the filtering unit is used for adding a bactericide into the secondary reaction liquid and carrying out filtering treatment to obtain filtered water;
the ion separation unit is used for adding a scale inhibitor and a scale inhibitor deactivator into the filtered produced water for ion separation to obtain high-concentration brine and pretreated produced water;
the secondary reaction unit is used for adding sodium sulfate into the high-concentration brine, performing secondary reaction and calcium sulfate crystallization separation to obtain secondary clear water and secondary sludge;
and a secondary clear water outlet of the secondary reaction unit is communicated with an inlet of the filtering unit and is used for introducing the secondary clear water into the filtering unit for filtering treatment.
In the present invention, the primary reaction unit may include a lime adding device, a first reaction vessel, and a separation apparatus, such as a lime input adder, a tank-type stirred reaction settler, a sludge removal apparatus, and the like.
In the present invention, the acidity adjustment unit may include an acid solution dispenser, a tank-type stirred reactor.
In the invention, the secondary reaction unit can comprise a sodium sulfate feeding adder, a tank type stirring reaction settler and sludge removal equipment.
In the present invention, the filtering unit may include a bactericide adding apparatus, a sand filter, and an ultrafiltration device.
In the invention, the ion separation unit can comprise a scale inhibitor adding device, a scale inhibitor deactivator adding device and a nanofiltration membrane separation device.
The invention can also comprise a primary sludge treatment device 6 and a secondary sludge treatment device 7.
All units, devices, equipment or containers included in the invention are communicated through pipelines so as to remove divalent ions and monovalent ions from the high-salt desulfurization wastewater of the coal-fired power plant and obtain pretreated produced water meeting the requirements.
The present invention will be described in detail below by way of examples.
The composition of the high-salt desulfurization wastewater of the coal-fired power plant is shown in Table 1.
TABLE 1
Figure BDA0001520249120000101
Example 1
Introducing high-salt desulfurization wastewater (flow rate 20 t/h) of a coal-fired power plant with the composition shown in table 1 into a system of the high-salt desulfurization wastewater of the coal-fired power plant shown in fig. 1, adding a lime solution with the concentration of 10 wt% into a primary reaction unit, and carrying out primary reaction for 120min at 25 ℃ and 0.1MPa, wherein the lime solution is added in an amount to ensure that the pH of an obtained primary reaction product reaches 10.5;
then standing and filtering the first-stage reaction product to obtain first-stage sludge and first-stage clear water, wherein the composition of the first-stage clear water is shown in Table 2;
adding a 20% hydrochloric acid solution into the primary clear water to adjust the pH value to 7 to obtain a stock solution, and simultaneously adding secondary clear water obtained by downstream secondary reaction separation, wherein the weight ratio of the stock solution to the secondary clear water is 1.5;
adding sodium hypochlorite with the amount of 5 mass ppm of the total amount of the stock solution and the second-stage clear water into the stock solution and the second-stage clear water, and performing ultrafiltration (ultrafiltration equipment provided by GE company) to obtain filtered produced water with an SDI value of 0.5;
adding 20 mass ppm of hydrogen peroxide and 10 mass ppm of scale inhibitor deactivator pc-191 into the filtered produced water, and then performing nanofiltration ion separation (a Dow NF270-2540 membrane) to obtain high-concentration brine and pretreated produced water; the water yield of the pretreatment water is 50 wt% of the filtered water; the composition of the pretreated produced water is shown in table 2;
adding a sodium sulfate solution with the concentration of 8 weight percent into high-concentration saline water, carrying out secondary reaction for 360min at the temperature of 10 ℃ and under the pressure of 0.1MPa, carrying out calcium sulfate crystallization and precipitation, carrying out secondary solid-liquid separation on an obtained secondary reaction product, and obtaining secondary sludge and secondary clear water, wherein the addition amount of the sodium sulfate solution enables the composition of the secondary clear water to be shown in table 2, and the total hardness of the secondary clear water is within the range of 10-40 mmol/L;
the second clear water is returned to participate in the above-mentioned filtration treatment, and the composition of the second clear water is shown in table 2.
The secondary sludge is treated to obtain calcium sulfate with the purity of 97 percent.
The cost is calculated, and the treatment cost is about 9.02 yuan/ton.
Example 2
Introducing high-salt desulfurization wastewater (flow rate 20 t/h) of a coal-fired power plant with the composition shown in table 1 into a system of the high-salt desulfurization wastewater of the coal-fired power plant shown in fig. 1, adding a lime solution with the concentration of 12 wt% into a primary reaction unit, and carrying out primary reaction for 60min at 10 ℃ and 0.1MPa, wherein the lime solution is added in an amount to ensure that the pH of an obtained primary reaction product reaches 12;
then standing and filtering the primary reaction product to obtain primary sludge and primary clear water, wherein the composition of the primary clear water is shown in a table 2;
adding a 15% sulfuric acid solution into the primary clear water to adjust the pH value to 8 to obtain a stock solution, and simultaneously adding secondary clear water obtained by secondary reaction and separation of downstream ions, wherein the weight ratio of the stock solution to the secondary clear water is 3.5;
adding sodium hypochlorite with the amount of 10 mass ppm of the total amount of the stock solution and the secondary clear water into the stock solution and the secondary clear water, and performing ultrafiltration (ultrafiltration equipment provided by Hangzhou water treatment equipment company) to obtain filtered produced water with an SDI value of 0.8;
adding ferric trichloride with the amount of 5 mass ppm of the filtered produced water and scale inhibitor deactivator pc-191 with the amount of 20 mass ppm of the filtered produced water into the filtered produced water, and then carrying out nanofiltration ion separation (a Dow NF270-2540 membrane) to obtain high-concentration brine and pretreated produced water; the water yield of the pretreatment produced water is 50 wt% of the filtered produced water; the composition of the pretreated produced water is shown in table 2;
adding a sodium sulfate solution with the concentration of 8 weight percent into high-concentration saline water, carrying out secondary reaction for 120min at 20 ℃ and 0.1MPa, carrying out calcium sulfate crystallization and precipitation, carrying out secondary solid-liquid separation on the obtained secondary reaction product to obtain secondary sludge and secondary clear water, wherein the addition amount of the sodium sulfate solution enables the composition of the secondary clear water to be shown in table 2, and the total hardness of the secondary clear water is within the range of 10-40 mmol/L;
the second clear water is returned to participate in the above-mentioned filtration treatment, and the composition of the second clear water is shown in table 2.
The secondary sludge is treated to obtain calcium sulfate with the purity of 99.0 percent.
The cost is calculated, and the treatment cost is about 8.61 yuan/ton.
Example 3
Introducing high-salt desulfurization wastewater (flow rate 20 t/h) of a coal-fired power plant with the composition shown in table 1 into a system of the high-salt desulfurization wastewater of the coal-fired power plant shown in fig. 1, adding a lime solution with the concentration of 8 wt% into a primary reaction unit, and carrying out primary reaction for 180min at 30 ℃ and 0.1MPa, wherein the lime solution is added in an amount to ensure that the pH of an obtained primary reaction product reaches 11;
then standing and filtering the primary reaction product to obtain primary sludge and primary clear water, wherein the composition of the primary clear water is shown in a table 2;
adding a 15% hydrochloric acid solution into the primary clear water to adjust the pH value to 6 to obtain a stock solution, and simultaneously adding secondary clear water obtained by downstream secondary reaction separation, wherein the weight ratio of the stock solution to the secondary clear water is 2;
adding hydrogen peroxide with the amount of 5 mass ppm of the total amount of the stock solution and the second-stage clear water into the stock solution and the second-stage clear water, and performing ultrafiltration (ultrafiltration equipment provided by GE company) to obtain filtered produced water with an SDI value of 0.6;
adding ferric trichloride with the amount of 10 mass ppm of the filtered produced water and scale inhibitor deactivator pc-191 with the amount of 5 mass ppm of the filtered produced water into the filtered produced water, and then carrying out nanofiltration ion separation (a Dow NF270-2540 membrane) to obtain high-concentration brine and pretreated produced water; the water yield of the pretreatment produced water is 50 wt% of the filtered produced water; the composition of the pretreated produced water is shown in table 2;
adding a sodium sulfate solution with the concentration of 8 weight percent into high-concentration saline water, carrying out secondary reaction for 240min at 30 ℃ and 0.1MPa, carrying out calcium sulfate crystallization precipitation, carrying out secondary solid-liquid separation on the obtained secondary reaction product to obtain secondary sludge and secondary clear water, wherein the addition amount of the sodium sulfate solution enables the composition of the secondary clear water to be shown in table 2, and the total hardness of the secondary clear water is within the range of 10-40 mmol/L;
the second grade clear water is returned to participate in the above-mentioned filtration treatment, and the composition of the second grade clear water is shown in table 2.
The secondary sludge is treated to obtain calcium sulfate with the purity of 98.6 percent.
The cost is calculated, and the treatment cost is about 11.5 yuan/ton.
Comparative example 1
Introducing high-salt desulfurization wastewater (flow rate 20 t/h) of a coal-fired power plant with the composition shown in table 1 into a system of the high-salt desulfurization wastewater of the coal-fired power plant shown in fig. 1, adding a lime solution with the concentration of 10 wt% into a primary reaction unit, and carrying out primary reaction for 120min at 25 ℃ and 0.1MPa, wherein the lime solution is added in an amount to ensure that the pH of an obtained primary reaction product reaches 10.5;
then standing and filtering the primary reaction product to obtain primary sludge and primary clear water, wherein the composition of the primary clear water is shown in a table 2;
adding a 15% hydrochloric acid solution into the primary clear water to adjust the pH value to 7 to obtain a secondary reaction liquid, and simultaneously adding high-concentration brine obtained by downstream ion separation, wherein the weight ratio of the secondary reaction liquid to the high-concentration brine is 1.5;
adding a sodium carbonate solution with the concentration of 8 weight percent into the secondary reaction liquid, carrying out secondary reaction for 360min at the temperature of 10 ℃ and under the pressure of 0.1MPa, and carrying out secondary solid-liquid separation on the obtained secondary reaction product to obtain secondary sludge and secondary clear water, wherein the addition amount of the sodium carbonate solution is 12kg/t of desulfurization wastewater;
adding sodium hypochlorite with the amount of 5 mass ppm of the second clear water into the second clear water, and performing ultrafiltration (ultrafiltration equipment provided by Hangzhou water treatment company) to obtain filtered water with SDI value of 0.5;
adding 20 mass ppm of hydrogen peroxide in the amount of the filtered produced water and 10 mass ppm of scale inhibitor deactivator pc-191 in the amount of the filtered produced water into the filtered produced water, and then carrying out nanofiltration ion separation to obtain high-concentration brine and pretreated produced water;
the high concentration brine is returned to participate in the second-order reaction, and the composition of the pretreated produced water is shown in Table 2.
And treating the secondary sludge to obtain calcium carbonate.
The cost is calculated, and the treatment cost is about 26.99 yuan/ton.
Comparative example 2
Adding a lime solution with the concentration of 10 weight percent and a sodium sulfate solution with the concentration of 8 weight percent into the high-salt desulfurization wastewater (the flow rate is 20 t/h) of the coal-fired power plant with the composition shown in the table 1, and carrying out a reaction for 120min at the temperature of 25 ℃ and under the pressure of 0.1MPa, wherein the lime solution is added in an amount to ensure that the pH of the obtained reaction product reaches 10.5; separating the reaction product to obtain clear water and sludge, wherein the addition amount of the sodium sulfate solution enables the hardness of the clear water to be within the range of 10-40 mmol/L;
adding sodium hypochlorite with the amount of 5 mass ppm of the clear water into the clear water, and performing ultrafiltration (ultrafiltration equipment provided by GE company) to obtain filtered produced water with the SDI value of 0.5;
adding 20 mass ppm of hydrogen peroxide in the amount of the filtered produced water and 10 mass ppm of scale inhibitor deactivator pc-191 in the amount of the filtered produced water into the filtered produced water, and then carrying out nanofiltration ion separation to obtain high-concentration brine and pretreated produced water;
returning the high-concentration brine to participate in the reaction, wherein the weight ratio of the desulfurization wastewater to the high-concentration brine is 1.5; the composition of the pretreated produced water is shown in table 2.
The sludge is treated to obtain calcium sulfate with the purity of 96 percent.
The cost is calculated, and the treatment cost is about 26.99 yuan/ton.
TABLE 1
Figure BDA0001520249120000151
It can be seen from the results of the examples, comparative examples and table 2 that the examples of the method and system of the present invention can effectively realize the separation of divalent and higher ions from monovalent ions, and remove from the desulfurization wastewater step by step, thereby ensuring that the secondary sludge can be further treated to obtain high-purity calcium sulfate (gypsum) byproduct, and meanwhile, the pretreated product water contains monovalent ions, which can facilitate the purification treatment of the subsequent treatment process. The method and the system adopt step-by-step treatment, step-by-step addition of the medicament lime and the sodium sulfate and mild operation at normal temperature and normal pressure, and the integral operation cost can be greatly reduced.
In comparative examples 1-2, although divalent ions could be removed, calcium sulfate could not be obtained or obtained had a low purity, and the entire process was costly to run.
The preferred embodiments of the present invention have been described in detail above with reference to the accompanying drawings, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.

Claims (11)

1. A pretreatment method of high-salt desulfurization wastewater of a coal-fired power plant comprises the following steps:
(1) Adding lime into the desulfurization wastewater, carrying out primary reaction, and carrying out primary solid-liquid separation on the obtained primary reaction product to obtain primary clear water and primary sludge, wherein the primary sludge is rich in Mg 2+ The concentration of magnesium ions contained in the first-stage clear water is 20-40mg/L;
(2) Adjusting the pH of the primary clear water to obtain a stock solution with a pH value of 6-8;
(3) Adding a bactericide into the stock solution and carrying out filtering treatment to obtain filtered produced water; the raw material participating in the step (3) also comprises secondary clear water recycled from the downstream, and the weight ratio of the stock solution to the secondary clear water is (1.5-3.5): 1;
(4) Adding a scale inhibitor and a scale inhibitor deactivator into the filtered produced water and carrying out ion separation to obtain high-concentration brine and pretreated produced water; the water yield of the pretreatment produced water is 50% of the filtered produced water; wherein the addition amount of the scale inhibitor is 1-20 mass ppm of the filtered produced water, and the addition amount of the scale inhibitor deactivator is 1-20 mass ppm of the filtered produced water;
(5) Adding sodium sulfate into the high-concentration brine, and then sequentially carrying out secondary reaction and calcium sulfate crystallization separation at normal temperature to obtain secondary clear water and secondary sludge;
returning the secondary clear water to the step (3) for filtering treatment;
the desulfurization wastewater to be treated contains sodium ions with the concentration of 400-1500mg/L, chloride ions with the concentration of 4000-15000mg/L, sulfate ions with the concentration of 3000-8000mg/L, calcium ions with the concentration of 1000-3000mg/L and magnesium ions with the concentration of 1500-5000 mg/L.
2. The pretreatment method according to claim 1, wherein lime is added in step (1) in an amount such that the pH of the first-order reaction product is 10.5 to 12.
3. The pretreatment method according to claim 1, wherein in the step (1), the temperature of the primary reaction is 10 to 30 ℃, the pressure of the primary reaction is 0.02 to 0.1MPa, and the time of the primary reaction is 60 to 180min.
4. The pretreatment method according to claim 1, wherein in the step (3), the bactericide is selected from the group consisting of sodium hypochlorite and/or hydrogen peroxide; the addition amount of the bactericide is 1-20 mass ppm of the total amount of the stock solution and the secondary clear water.
5. The pretreatment method according to claim 1, wherein in the step (3), the filtration treatment is ultrafiltration and/or sand filtration.
6. The pretreatment method according to claim 5, wherein in the step (3), the SDI value of the filtered produced water is 1 or less.
7. The pretreatment method according to claim 1, wherein in the step (4), the scale inhibitor is a nanofiltration or reverse osmosis membrane scale inhibitor, and the scale inhibitor deactivator is selected from ferric trichloride and/or hydrogen peroxide.
8. The pretreatment method according to claim 1, wherein, in the step (4), the ion separation is a nanofiltration separation; the nanofiltration separation temperature is 10-30 ℃, the nanofiltration separation pressure is 0.8-1.5MPa, and the water yield of the pretreatment water is 30-70% of the filtered water yield.
9. The pretreatment method according to claim 1, wherein in the step (5), sodium sulfate is added in an amount such that the total hardness of the secondary clear water is 10-40mmol/L.
10. The pretreatment method according to claim 1, wherein in the step (5), the temperature of the secondary reaction is 10 to 30 ℃, the pressure of the secondary reaction is 0.02 to 0.1MPa, and the time of the secondary reaction is 120 to 360min.
11. A system for high salt desulfurization waste water of a coal fired power plant, comprising: the device comprises a primary reaction unit (1), an acidity adjusting unit (2), a filtering unit (3), an ion separating unit (4) and a secondary reaction unit (5);
the first-stage reaction unit is used for adding lime into the desulfurization wastewater, performing first-stage reaction, and separating to obtain first-stage clear water and first-stage sludge;
the acidity adjusting unit is used for adjusting the pH of the primary clear water into a secondary reaction liquid;
the filtering unit is used for adding a bactericide into the secondary reaction liquid and carrying out filtering treatment to obtain filtered water;
the ion separation unit is used for adding a scale inhibitor and a scale inhibitor deactivator into the filtered produced water for ion separation to obtain high-concentration brine and pretreated produced water;
the secondary reaction unit is used for adding sodium sulfate into the high-concentration brine, performing secondary reaction and calcium sulfate crystallization separation to obtain secondary clear water and secondary sludge;
and a secondary clear water outlet of the secondary reaction unit is communicated with an inlet of the filtering unit and is used for introducing the secondary clear water into the filtering unit for filtering treatment.
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