CN109956578A - The preprocess method and system of coal-burning power plant's desulfurization wastewater with high salt - Google Patents
The preprocess method and system of coal-burning power plant's desulfurization wastewater with high salt Download PDFInfo
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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
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/442—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/50—Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F2001/5218—Crystallization
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/18—Nature of the water, waste water, sewage or sludge to be treated from the purification of gaseous effluents
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- 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
Abstract
The present invention relates to the field of purification of coal-burning power plant's desulfurization wastewater with high salt, disclose the preprocess method and system of coal-burning power plant's desulfurization wastewater with high salt.The preprocess method includes: (1) to desulfurization wastewater addition lime progress first order reaction, and obtained first order reaction product is separated by solid-liquid separation to obtain level-one clear water and level-one sludge through level-one；(2) level-one clear water is subjected to pH adjusting, obtains the stoste that pH value is 6-8；(3) Xiang Suoshu stoste is added fungicide and carries out filtering processing, obtains filtering and produces water；(4) Xiang Suoshu filtering produces water and antisludging agent and antisludging agent deactivator is added and carries out ion isolation, obtains high concentration salt water and pretreatment produces water；(5) sodium sulphate is added in Xiang Suoshu high concentration salt water, then successively carries out the crystal of calcium sulfate separation under second order reaction and room temperature, obtains second level clear water and secondary sludge；Wherein, the second level clear water is returned and step (3) progress filtering processing is added.Desulphurization for Coal-fired Power Plant Wastewater Pretreatment cost can be effectively reduced.
Description
Technical field
The present invention relates to the field of purification of coal-burning power plant's desulfurization wastewater with high salt, and in particular to coal-burning power plant's desulfurization wastewater with high salt
Preprocess method and system.
Background technique
Overwhelming majority power plant, China, coal plant are using the SO in Wet Limestone Desulfurization technology removing flue gas2, thus produce
Raw desulfurization wastewater becomes one of most intractable waste water in coal-burning power plant because complicated component, pollutant kind.It is domestic at present main
Will be using chemical precipitation method (being commonly called as three headers precipitating) processing desulfurization wastewater, processing water outlet salt content is higher, after direct emission
It is easy to cause secondary pollution.Simultaneously as desulfurization wastewater water is smaller, salt content is high, power plant, coal plant's desulfurization wastewater are into one
The process system long-play of step processing is unstable, and (water inlet microsolubility inorganic salt content is high, leads to the reverse osmosis system of ultrafiltration nanofiltration
Fouling condition of uniting is serious), and operating cost is higher, thus at present without practical application example.But required with Environmental Protection in China
Further strengthen, the exploitation of the further zero discharge treatment technology of desulfurization wastewater is extremely urgent, need reduce process system at
Technological innovation and technological development are carried out in terms of this and raising process system stability.
The prior art is in purification coal-burning power plant desulfurization wastewater with high salt, although the monovalence in waste water, divalent ion can be removed,
But two class ions are mostly to remove together, the salt of formation is that many kinds of substance mixes, and is not effectively separated monovalent ion and divalent
Ion, the compound for being unfavorable for the ion of removing further utilize.The process operation cost of the prior art is also higher simultaneously, increases
The burden of power plant emission processing, the scheme of urgent need to resolve.
Summary of the invention
The purpose of the invention is to overcome removing product of the existing technology impure, process operation higher cost is asked
Topic, provides the preprocess method and system of coal-burning power plant's desulfurization wastewater with high salt, this method and systematic difference can be effectively
The monovalent ion and divalent ion in desulfurization wastewater are separated, and the higher calcium sulfate of purity can be recycled, and coal-burning power plant can be reduced
Desulfurization wastewater with high salt purifies pretreated operating cost.
To achieve the goals above, first aspect present invention provides a kind of pretreatment side of coal-burning power plant's desulfurization wastewater with high salt
Method, comprising:
(1) lime is added to desulfurization wastewater and carries out first order reaction, obtained first order reaction product is separated by solid-liquid separation through level-one
Obtain level-one clear water and level-one sludge；
(2) the level-one clear water is subjected to pH adjusting, obtains the stoste that pH value is 6-8；
(3) Xiang Suoshu stoste is added fungicide and carries out filtering processing, obtains filtering and produces water；
(4) Xiang Suoshu filtering produces water and antisludging agent and antisludging agent deactivator is added and carries out ion isolation, obtains high salt concentration
Water and pretreatment produce water；
(5) sodium sulphate is added in Xiang Suoshu high concentration salt water, then successively carries out the calcium sulfate knot under second order reaction and room temperature
Crystalline substance separation, obtains second level clear water and secondary sludge；
Wherein, the second level clear water is returned and step (3) progress filtering processing is added.
Preferably, in step (1), the additional amount of lime makes the pH 10.5-12 of the first order reaction product.
Preferably, the temperature of the first order reaction is 10-30 DEG C, and the pressure of the first order reaction is 0.02-0.1MPa, institute
The time for stating first order reaction is 60-180min.
Preferably, in step (3), the fungicide is selected from sodium hypochlorite and/or hydrogen peroxide；The addition of the fungicide
Amount is the 1-20 mass ppm of the stoste and the second level clear water total amount.
Preferably, in step (3), the filtering processing is ultrafiltration and/or sand filtration.
Preferably, it is 1 or less that the filtering, which produces the SDI value of water,.
Preferably, in step (4), the antisludging agent is nanofiltration or reverse osmosis membrane antisludging agent, the antisludging agent deactivator choosing
From ferric trichloride and/or hydrogen peroxide.
Preferably, the additional amount of the antisludging agent is the 1-20 mass ppm that the filtering produces water, the antisludging agent deactivator
Additional amount be the filtering produce water 1-20 mass ppm.
Preferably, in step (4), the ion isolation is nanofiltration separation.
Preferably, nanofiltration separation temperature is 10-30 DEG C, and nanofiltration separation pressure is 0.8-1.5MPa, and the pretreatment produces water
Water yield be the filtering produce water 30-70%.
Preferably, in step (5), the additional amount of sodium sulphate makes the total hardness of the second level clear water be 10-40mmol/L.
Preferably, in step (5), the temperature of the second order reaction is 10-30 DEG C, and the pressure of the second order reaction is
0.02-0.1MPa, the time of the second order reaction are 120-360min.
Preferably, the stoste and the weight ratio of the second level clear water are (1.5-3.5): 1.
Second aspect of the present invention provides a kind of system of coal-burning power plant's desulfurization wastewater with high salt, comprising: first order reaction unit 1,
Acidity adjustment unit 2, filtering unit 3, ion isolation unit 4 and second order reaction unit 5；
The first order reaction unit is used to that lime to be added to desulfurization wastewater and carries out first order reaction, and isolated level-one is clear
Water and level-one sludge；
The acidity adjustment unit is used to level-one clear water progress pH being adjusted to second order reaction liquid；
The filtering unit is used to that fungicide to be added to the second order reaction liquid and can be carried out filtering processing, obtains filtering production
Water；
The ion isolation unit is used to produce water to the filtering and antisludging agent and antisludging agent deactivator progress ion point is added
From, obtain high concentration salt water and pretreatment produce water；
The second order reaction unit is used to that sodium sulphate to be added to the high concentration salt water and carries out second order reaction and calcium sulfate
Crystallization Separation obtains second level clear water and secondary sludge；
The second level clear water output of the second order reaction unit is connected to the entrance of the filtering unit, for the second level is clear
Water is passed through the filtering unit and carries out the filtering processing.
Through the above technical solutions, the purification that the present invention takes substep to carry out coal-burning power plant's desulfurization wastewater with high salt pre-processes,
Substep delivering medicament lime and sodium sulphate may be implemented to efficiently separate monovalent ion and high valence ion in desulfurization wastewater, monovalence
Ion enrichment produces in water in finally obtained pretreatment, is further processed removing monovalent ion by downstream process.And two
Valence ion can be deposited in the level-one sludge and secondary sludge that this method obtains, then dirty through corresponding level-one Treatment of Sludge and second level
Mud handles to obtain the higher calcium sulfate byproduct of purity, uses for architecture of high quality or food gypsum, raising desulfurization wastewater are net
The increment effect of change.While efficiently separating the monovalent ion and divalent ion in desulfurization wastewater, method of the invention and it is
Unite the substep operation taken, launch lime and sodium sulphate, the operation of entire technique normal temperature and pressure, reduce the operation of entire technique at
This.
Detailed description of the invention
Fig. 1 is the preprocess method of coal-burning power plant provided by the invention desulfurization wastewater with high salt and the flow diagram of system.
Description of symbols
1, first order reaction unit 2, acidity adjustment unit 3, filtering unit
4, ion isolation unit 5, second order reaction unit 6, level-one sludge treating block
7, secondary sludge processing unit
Specific embodiment
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
First aspect present invention provides a kind of preprocess method of coal-burning power plant's desulfurization wastewater with high salt, comprising:
(1) lime is added to desulfurization wastewater and carries out first order reaction, obtained first order reaction product is separated by solid-liquid separation through level-one
Obtain level-one clear water and level-one sludge；
(2) the level-one clear water is subjected to pH adjusting, obtains the stoste that pH value is 6-8；
(3) Xiang Suoshu stoste is added fungicide and carries out filtering processing, obtains filtering and produces water；
(4) Xiang Suoshu filtering produces water and antisludging agent and antisludging agent deactivator is added and carries out ion isolation, obtains high salt concentration
Water and pretreatment produce water；
(5) sodium sulphate is added in Xiang Suoshu high concentration salt water, then successively carries out the calcium sulfate knot under second order reaction and room temperature
Crystalline substance separation, obtains second level clear water and secondary sludge；
Wherein, the second level clear water is returned and step (3) progress filtering processing is added.
The desulfurization wastewater that the present invention is handled can be the waste water from Desulphurization for Coal-fired Power Plant device, can be through waste-water vortex
The desulfurization wastewater discharged after device eddy flow, wherein including organic matters and the nothings such as a large amount of suspended matter, calcium sulfate, magnesium sulfate, sodium chloride
Machine salt impurity.Wherein, calcium ions and magnesium ions, chloride ion content are high.Method provided by the invention, which can be effectively removed in waste water, to be existed
Above-mentioned impurity, and monovalence and divalent ion in waste water can be separated, such as separate magnesium ion, calcium ion, sulfate ion with
Chloride ion, improves the water quality of the desulfurization wastewater, and obtains the calcium sulfate of purity is high, and has the advantage of low cost.
The preferably manageable desulfurization wastewater of method provided by the invention, composition can be 400- containing concentration
The sodium ion of 1500mg/L, the chloride ion of 4000-15000mg/L, 3000-8000mg/L sulfate ion, 1000-
The calcium ion of 3000mg/L and the magnesium ion of 1500-5000mg/L.
The above-mentioned multistep of method provided by the invention point, and delivering medicament lime and sodium sulphate in two steps, realize the desulfurization
Monovalence and divalent ion in waste water can be effectively separated, and monovalent ion stays in finally obtained pretreatment and produces in water, can
To facilitate technique and the equipment in downstream to isolate monovalent ion.And divalent ion is removed in level-one sludge and secondary sludge,
And the higher calcium sulfate of the available purity of secondary sludge, be conducive to subsequent high value added utilization.
In the present invention, step (1) is mainly used for that the Mg in the desulfurization wastewater can be reduced2+, especially noncarbonate
Mg2+It generates Mg (OH)2Precipitating, while most of Si can also be reduced.Preferably, in step (1), the additional amount of lime makes described
The pH of first order reaction product is 10.5-12.Wherein lime can be added in the form of concentration is the lime solution of 8-12 weight %.
The first order reaction product is solidliquid mixture.
In the present invention, the condition of the first order reaction can complete the precipitating of magnesium ion, can be in the normal of mild condition
It is carried out under normal temperature and pressure；It can be in stirred tank and carry out.Preferably, the temperature of the first order reaction is 10-30 DEG C, and the level-one is anti-
The pressure answered is 0.02-0.1MPa, and the time of the first order reaction is 60-180min.
In the present invention, flocculant and flocculation aid can also be added in (1) in step.It can be flocculation commonly used in the art
Agent and flocculation aid do not have to specific restriction, can be preferably polyacrylamide, Polyferric Sulfate etc..Additional amount reaches the flocculating effect of needs
, can be this field conventional amount used, as flocculant and flocculation aid can distinguish the 1-20 matter that dosage is the desulfurization wastewater
Measure ppm.
The first order reaction product is also subjected to the level-one separation of solid and liquid, isolated method in step (1) of the invention
It can be and stand the first order reaction product and filter, obtaining solid is level-one sludge, wherein it is rich in divalent ion, such as
Mg2+.It can be with Mg in the level-one clear water2+Concentration reduce, such as can be with Mg2+Concentration be 10mg/L or less.
The composition for the level-one clear water that method provided by the invention preferably obtains can be 3500- containing concentration
The sodium ion of 4500mg/L, the chloride ion of 4000-15000mg/L, 5000-6000mg/L sulfate ion, 4000-
The calcium ion of 5000mg/L and the magnesium ion of 20-40mg/L.
In step (2) of the invention, the pH value for the level-one clear water that adjustable step (1) obtains is to be suitble to described two
Order reaction.It is excessive wherein to adjust pH value, is unfavorable for the whole implementation of method of the invention, can not achieve the present invention can be subsequent
Selective Separation calcium ion in step obtains the gypsum of high-quality.Such as pH value is greater than 11, then can also contain sulphur in level-one sludge
Sour calcium precipitate is unfavorable for the gypsum that the secondary sludge that the present invention designs obtains high-quality.Being added can be with for the pH reagent adjusted
Selected from sulfuric acid or hydrochloric acid solution, the concentrated solution or weak solution of sulfuric acid or hydrochloric acid can be.
The step of in the present invention, step (3) can be used for removing suspended matter and colloid in the stoste, be downstream (4)
The ion isolation charging that can be applicable in is provided.Preferably, in step (3), the fungicide is selected from sodium hypochlorite and/or peroxidating
Hydrogen.
In the present invention, participate in step (3) further include being recycled back to from downstream the second level clear water.Preferably, institute
The weight ratio for stating stoste and the second level clear water is (1.5-3.5): 1.It is reduced it is possible thereby to improve and removed by the calcium ion
Ca in the second order reaction liquid2+Effect, be better achieved separation desulfurization waste liquor in divalent ion.Preferably, the sterilization
The additional amount of agent is the 1-20 mass ppm of the stoste and the second level clear water total amount.
In the present invention, the condition of the filtering processing guarantees to obtain the charging for being suitble to the ion isolation.Preferably,
In step (3), the filtering processing is ultrafiltration and/or sand filtration；Preferably, it is 1 or less that the filtering, which produces the SDI value of water,.SDI value
For the pollution index value of water quality indicator, can be measured according to ASTM method 4189-95 using SDI instrument.
In the present invention, step (4) can be used for being additionally separated out the filtering produce in water there is likely to be divalent
Or more ion.Preferably, in step (4), the antisludging agent is nanofiltration or reverse osmosis membrane antisludging agent；The antisludging agent adds
Entering amount is the 1-20 mass ppm that the filtering produces water.The antisludging agent is known substance, can be commercially available, such as nail (unit of length) section
The pc-191 of company, Ondeo Nalco Co. OSM-60.
Preferably, the antisludging agent deactivator is selected from ferric trichloride and/or hydrogen peroxide；The antisludging agent deactivator adds
Entering amount is the 1-20 mass ppm that the filtering produces water.
In the present invention, the condition of the ion isolation completes to separate divalent and the above ion and one in the filtering production water
Valence ion.Preferably, in step (4), the ion isolation is nanofiltration separation；Preferably, nanofiltration separation temperature is 10-30
DEG C, nanofiltration separation pressure is 0.8-1.5MPa, and the pretreatment produces the 30-70% that the water yield of water produces water for the filtering.It is excellent
Selecting the pretreatment to produce the water yield of water is that the filtering produces the 50% of water.The pretreatment can be significantly improved and produce monovalence in water
The rate of recovery of ion.The nanofiltration membrane component that the nanofiltration separation uses is known substance, can be commercially available.Such as GE DL system
Column nanofiltration membrane component, GE SWSR series nanofiltration membrane component, DOW NF270 series nanofiltration membrane component or TCK company, South Korea
NE8040-40 nanofiltration membrane component.Ion isolation through above-mentioned condition, the pretreatment produce water contain total concentration be 1mmol/L with
Under calcium ion and sulfate ion.Meanwhile the high concentration salt water contain total concentration be 90 weight % or more calcium ion and
Sulfate ion.
The composition that the pretreatment that method provided by the invention preferably obtains produces water can be 6500- containing concentration
The sodium ion of 7500mg/L, the chloride ion of 4000-15000mg/L, the sulfate ion of 150-300mg/L, 100-250mg/L
The magnesium ion of calcium ion and 0.1-11mg/L.
In the present invention, step (5) is used to the high concentration salt water further removing divalent ion.By the way that sodium sulphate is added
The Ca in the high concentration salt water can mainly be isolated2+, generate CaSO4.The CaSO generated simultaneously4In high concentration salt water
Solubility reaches supersaturation and crystalline deposit is precipitated from the high concentration salt water, then is separated by solid-liquid separation to obtain second level through the second level
Sludge.The secondary sludge obtained in this way through the available purity of further Treatment of Sludge up to 96.0% or more gypsum, can
Meet for building or food standard, there is higher added value.Preferably, in step (5), the additional amount of sodium sulphate makes institute
The total hardness for stating second level clear water is 10-40mmol/L.Total hardness refers to the total concentration of calcium ion and magnesium ion, and unit conversion is
mmol/L.Wherein sodium sulphate can be added in the form of concentration is the metabisulfite solution of 8-12 weight %.
In the present invention, the second order reaction can carry out at normal temperatures and pressures.Divalent ion in the high concentration salt water,
Predominantly Ca2+It can be isolated in the form of crystal of calcium sulfate.Preferably, in step (5), the temperature of the second order reaction is
10-30 DEG C, the pressure of the second order reaction is 0.02-0.1MPa, and the time of the second order reaction is 120-360min.
In the present invention, a large amount of oversaturated sulfuric acid will be formed in the second order reaction product that obtains by the second order reaction
Calcium separates through the crystal of calcium sulfate under room temperature, calcium sulfate is discharged in secondary sludge, plays the role of removing calcium ion.Herein
Room temperature can be preferably 10-35 DEG C.
Further include that the second level is separated by solid-liquid separation in step (5) of the invention, obtains secondary sludge and second level clear water.Second level is dirty
Mud is rich in Ca2+, and calcium sulfate purity is high, the gypsum product of high-quality can be done.
In the present invention, the second level clear water that step (5) obtains further reduced Ca2+Content, can be with Ca2+Concentration be
1000mg/L or less.
In the present invention, flocculant and flocculation aid can also be added in (5) in step.It can be flocculation commonly used in the art
Agent and flocculation aid do not have to specific restriction, can be preferably polyacrylamide, Polyferric Sulfate etc..Additional amount reaches the flocculating effect of needs
, can be this field conventional amount used, as flocculant and flocculation aid can distinguish the 1-20 that dosage is the high concentration salt water
Quality ppm.
The composition for the second level clear water that method provided by the invention preferably obtains can be 6500- containing concentration
The sodium ion of 7500mg/L, the chloride ion of 4000-15000mg/L, 200-300mg/L sulfate ion, 800-1000mg/L
Calcium ion and 20-40mg/L magnesium ion.
In the present invention, the preprocess method can also include at the level-one sludge and secondary sludge that will be obtained
Reason, prevents secondary pollution.The method of processing, which can be, to be entered grey field for the level-one sludge and secondary sludge blending or admixes stone
In cream semi-finished product.Wherein, the secondary sludge is through handling the gypsum of available 96.0% or more purity.
Second aspect of the present invention provides a kind of system of coal-burning power plant's desulfurization wastewater with high salt, comprising: first order reaction unit 1,
Acidity adjustment unit 2, filtering unit 3, ion isolation unit 4 and second order reaction unit 5；
The first order reaction unit is used to that lime to be added to desulfurization wastewater and carries out first order reaction, and isolated level-one is clear
Water and level-one sludge；
The acidity adjustment unit is used to level-one clear water progress pH being adjusted to second order reaction liquid；
The filtering unit is used to that fungicide to be added to the second order reaction liquid and can be carried out filtering processing, obtains filtering production
Water；
The ion isolation unit is used to produce water to the filtering and antisludging agent and antisludging agent deactivator progress ion point is added
From, obtain high concentration salt water and pretreatment produce water；
The second order reaction unit is used to that sodium sulphate to be added to the high concentration salt water and carries out second order reaction and calcium sulfate
Crystallization Separation obtains second level clear water and secondary sludge；
The second level clear water output of the second order reaction unit is connected to the entrance of the filtering unit, for the second level is clear
Water is passed through the filtering unit and carries out the filtering processing.
In the present invention, the first order reaction unit may include lime adding apparatus, the first reaction vessel and separation equipment,
Such as lime investment adder, pot type are stirred to react settler, sludge remover apparatus etc..
In the present invention, the acidity adjustment unit may include acid solution supply device, pot type stirred reactor.
In the present invention, the second order reaction unit may include sodium sulphate investment adder, pot type be stirred to react settler,
Sludge remover apparatus.
In the present invention, the filtering unit may include fungicide adding apparatus, sand filter, ultrafiltration apparatus.
In the present invention, the ion isolation unit may include scale inhibitor adding apparatus, antisludging agent deactivator adding apparatus,
Nanofiltration membrane separation device.
The present invention can also include level-one sludge treatment equipment 6 and secondary sludge processing unit 7.
It is connected between each unit, device, equipment or the container for including in the present invention by pipeline, to complete coal-burning power plant's height
Salt desulfurization wastewater removes out divalent and the above ion and monovalent ion, obtains satisfactory pretreatment and produces water.
The present invention will be described in detail by way of examples below.
The composition of coal-burning power plant's desulfurization wastewater with high salt is as shown in table 1.
Table 1
Embodiment 1
It is with high salt that coal-burning power plant's desulfurization wastewater (flow 20t/h) with high salt of composition such as table 1 is passed through coal-burning power plant shown in FIG. 1
The system of desulfurization wastewater, in first order reaction unit be added concentration be 10 weight % lime solution, at 25 DEG C, 0.1MPa into
The pH of row first order reaction 120min, the first order reaction product that lime solution additional amount makes reach 10.5；
Then first order reaction product is stood and is obtained by filtration level-one sludge and level-one clear water, the composition of level-one clear water
As shown in table 2；
20% hydrochloric acid solution of concentration adjusting pH value is added in level-one clear water and obtains stoste for 7, while it is anti-that downstream second level is added
Answer isolated second level clear water, the weight ratio of stoste and second level clear water is 1.5:1；
The sodium hypochlorite for the 5 mass ppm that dosage is stoste and second level clear water total amount is added into stoste and second level clear water, and
Ultrafiltration (ultrafiltration apparatus that GE company provides) is carried out, filtering is obtained and produces water, SDI value is 0.5；
Water being produced to filtering, the hydrogen peroxide that dosage is the 20 mass ppm that filtering produces water being added, dosage is that filtering produces the 10 of water
Then quality ppm antisludging agent deactivator pc-191 carries out nanofiltration ion isolation (Tao Shi NF270-2540 film), obtains high salt concentration
Water and pretreatment produce water；Pretreatment produces the 50 weight % that the water yield of water produces water for filtering；Pretreatment produces water composition and 2 institute of table
Show；
The metabisulfite solution that concentration is 8 weight % is added into high concentration salt water, it is anti-that second level is carried out at 10 DEG C, 0.1MPa
360min is answered, and carries out crystal of calcium sulfate precipitating, obtained second order reaction product carries out second level separation of solid and liquid, obtains secondary sludge
With second level clear water, the additional amount of metabisulfite solution keeps the composition of second level clear water as shown in table 2, and wherein the total hardness of second level clear water exists
In the range of 10-40mmol/L；
Second level clear water, which returns, participates in above-mentioned filtering processing, and the composition of second level clear water is as shown in table 2.
Secondary sludge obtains calcium sulfate, purity 97% through processing.
Through cost accounting, processing cost is about 9.02 yuan/ton.
Embodiment 2
It is with high salt that coal-burning power plant's desulfurization wastewater (flow 20t/h) with high salt of composition such as table 1 is passed through coal-burning power plant shown in FIG. 1
The system of desulfurization wastewater, in first order reaction unit be added concentration be 12 weight % lime solution, at 10 DEG C, 0.1MPa into
The pH of row first order reaction 60min, the first order reaction product that lime solution additional amount makes reach 12；
Then first order reaction product is stood and is obtained by filtration level-one sludge and level-one clear water, the composition of level-one clear water
As shown in table 2；
15% sulfuric acid solution of concentration adjusting pH value is added in level-one clear water and obtains stoste for 8, while downstream ion two is added
The weight ratio of the isolated second level clear water of order reaction, stoste and second level clear water is 3.5:1；
The sodium hypochlorite for the 10 mass ppm that dosage is stoste and second level clear water total amount is added into stoste and second level clear water,
And ultrafiltration (ultrafiltration apparatus that Hangzhou water treatment facilities company provides) is carried out, it obtains filtering and produces water, SDI value is 0.8；
Water being produced to filtering, the ferric trichloride that dosage is the 5 mass ppm that filtering produces water being added, dosage is 20 matter that filtering produces water
Ppm antisludging agent deactivator pc-191 is measured, then nanofiltration ion isolation (Tao Shi NF270-2540 film) is carried out, obtains high concentration salt water
Water is produced with pretreatment；Pretreatment produces the 50 weight % that the water yield of water produces water for filtering；Pretreatment produces shown in water composition and table 2；
The metabisulfite solution that concentration is 8 weight % is added into high concentration salt water, it is anti-that second level is carried out at 20 DEG C, 0.1MPa
120min is answered, and carries out crystal of calcium sulfate precipitating, obtained second order reaction product carries out second level separation of solid and liquid, obtains secondary sludge
With second level clear water, the additional amount of metabisulfite solution keeps the composition of second level clear water as shown in table 2, and wherein the total hardness of second level clear water exists
In the range of 10-40mmol/L；
Second level clear water, which returns, participates in above-mentioned filtering processing, and the composition of second level clear water is as shown in table 2.
Secondary sludge obtains calcium sulfate, purity 99.0% through processing.
Through cost accounting, processing cost is about 8.61 yuan/ton.
Embodiment 3
It is with high salt that coal-burning power plant's desulfurization wastewater (flow 20t/h) with high salt of composition such as table 1 is passed through coal-burning power plant shown in FIG. 1
The system of desulfurization wastewater, in first order reaction unit be added concentration be 8 weight % lime solution, at 30 DEG C, 0.1MPa into
The pH of row first order reaction 180min, the first order reaction product that lime solution additional amount makes reach 11；
Then first order reaction product is stood and is obtained by filtration level-one sludge and level-one clear water, the composition of level-one clear water
As shown in table 2；
15% hydrochloric acid solution of concentration adjusting pH value is added in level-one clear water and obtains stoste for 6, while it is anti-that downstream second level is added
Answer isolated second level clear water, the weight ratio of stoste and second level clear water is 2:1；
The hydrogen peroxide for the 5 mass ppm that dosage is stoste and second level clear water total amount is added into stoste and second level clear water, and
Ultrafiltration (ultrafiltration apparatus that GE company provides) is carried out, filtering is obtained and produces water, SDI value is 0.6；
Water being produced to filtering, the ferric trichloride that dosage is the 10 mass ppm that filtering produces water being added, dosage is 5 matter that filtering produces water
Ppm antisludging agent deactivator pc-191 is measured, then nanofiltration ion isolation (Tao Shi NF270-2540 film) is carried out, obtains high concentration salt water
Water is produced with pretreatment；Pretreatment produces the 50 weight % that the water yield of water produces water for filtering；Pretreatment produces shown in water composition and table 2；
The metabisulfite solution that concentration is 8 weight % is added into high concentration salt water, it is anti-that second level is carried out at 30 DEG C, 0.1MPa
240min is answered, and carries out crystal of calcium sulfate precipitating, obtained second order reaction product carries out second level separation of solid and liquid, obtains secondary sludge
With second level clear water, the additional amount of metabisulfite solution keeps the composition of second level clear water as shown in table 2, and wherein the total hardness of second level clear water exists
In the range of 10-40mmol/L；
Second level clear water, which returns, participates in above-mentioned filtering processing, and the composition of second level clear water is as shown in table 2.
Secondary sludge obtains calcium sulfate, purity 98.6% through processing.
Through cost accounting, processing cost is about 11.5 yuan/ton.
Comparative example 1
It is with high salt that coal-burning power plant's desulfurization wastewater (flow 20t/h) with high salt of composition such as table 1 is passed through coal-burning power plant shown in FIG. 1
The system of desulfurization wastewater, in first order reaction unit be added concentration be 10 weight % lime solution, at 25 DEG C, 0.1MPa into
The pH of row first order reaction 120min, the first order reaction product that lime solution additional amount makes reach 10.5；
Then first order reaction product is stood and is obtained by filtration level-one sludge and level-one clear water, the composition of level-one clear water
As shown in table 2；
It is that adjust pH value be 7 to obtain second order reaction liquid to 15% hydrochloric acid solution by level-one clear water addition concentration, while under being added
The weight ratio of the isolated high concentration salt water of free son, second order reaction liquid and high concentration salt water is 1.5:1；
The sodium carbonate liquor that concentration is 8 weight % is added into second order reaction liquid, it is anti-that second level is carried out at 10 DEG C, 0.1MPa
360min is answered, obtained second order reaction product carries out second level separation of solid and liquid, obtains secondary sludge and second level clear water, sodium carbonate liquor
Additional amount be 12kg/t desulfurization wastewater；
The sodium hypochlorite for the 5 mass ppm that dosage is second level clear water is added into second level clear water, and carries out ultrafiltration (Hang Zhoushui
The ultrafiltration apparatus that processing company provides), it obtains filtering and produces water, SDI value is 0.5；
Water being produced to filtering, the hydrogen peroxide that dosage is the 20 mass ppm that filtering produces water being added, dosage is that filtering produces the 10 of water
Then quality ppm antisludging agent deactivator pc-191 carries out nanofiltration ion isolation, obtain high concentration salt water and pretreatment produces water；
High concentration salt water, which returns, participates in above-mentioned second order reaction, and the composition that pretreatment produces water is as shown in table 2.
Secondary sludge obtains calcium carbonate through processing.
Through cost accounting, processing cost is about 26.99 yuan/ton.
Comparative example 2
The stone for being 10 weight % to the middle addition concentration of coal-burning power plant's desulfurization wastewater (flow 20t/h) with high salt of composition such as table 1
Grey solution and concentration are the metabisulfite solution of 8 weight %, and reaction 120min is carried out at 25 DEG C, 0.1MPa, and wherein lime is molten
The pH for the reaction product that liquid additional amount makes reaches 10.5；By the isolated clear water of reaction product and sludge, metabisulfite solution
Additional amount make the hardness of clear water in the range of 10-40mmol/L；
The sodium hypochlorite for the 5 mass ppm that dosage is clear water is added into clear water, and carries out ultrafiltration (GE company provides super
Filter equipment), it obtains filtering and produces water, SDI value is 0.5；
Water being produced to filtering, the hydrogen peroxide that dosage is the 20 mass ppm that filtering produces water being added, dosage is that filtering produces the 10 of water
Then quality ppm antisludging agent deactivator pc-191 carries out nanofiltration ion isolation, obtain high concentration salt water and pretreatment produces water；
High concentration salt water, which returns, participates in above-mentioned reaction, and the weight ratio of desulfurization wastewater and high concentration salt water is 1.5:1；Pretreatment
The composition for producing water is as shown in table 2.
Sludge obtains calcium sulfate, purity 96% through processing.
Through cost accounting, processing cost is about 26.99 yuan/ton.
Table 1
Can be seen that by the result of embodiment, comparative example and table 2 can using the embodiment of method and system of the invention
It to effectively realize the separation of divalent and the above ion and monovalent ion, is removed from desulfurization wastewater step by step, ensure that second level dirt
Mud can be further processed calcium sulfate (gypsum) byproduct for obtaining high-purity, while pre-processing to produce in water and containing monovalent ion,
It can be convenient the purified treatment of subsequent treatment process.And method and system of the invention, take step-by-step processing, substep adding medicine
It is mildly operated under lime and sodium sulphate and normal temperature and pressure, the cost of overall operation can substantially reduce.
In comparative example 1-2, although can also have the bivalent ions effect of removing, the calcium sulfate that cannot be obtained or obtain
Purity is low, and entire process operation is at high cost.
It is described the prefered embodiments of the present invention in detail above in conjunction with attached drawing, still, the present invention is not limited thereto.At this
, can be with various simple variants of the technical solution of the present invention are made in the range of the technology design of invention, including each technical characteristic
It is combined with any other suitable method, these simple variants and combination equally should be considered as in disclosed in this invention
Hold, all belongs to the scope of protection of the present invention.
Claims (10)
1. a kind of preprocess method of coal-burning power plant's desulfurization wastewater with high salt, comprising:
(1) lime is added to desulfurization wastewater and carries out first order reaction, obtained first order reaction product is separated by solid-liquid separation to obtain through level-one
Level-one clear water and level-one sludge；
(2) the level-one clear water is subjected to pH adjusting, obtains the stoste that pH value is 6-8；
(3) Xiang Suoshu stoste is added fungicide and carries out filtering processing, obtains filtering and produces water；
(4) Xiang Suoshu filtering produces water and antisludging agent and antisludging agent deactivator is added and carries out ion isolation, obtain high concentration salt water and
Pretreatment produces water；
(5) sodium sulphate is added in Xiang Suoshu high concentration salt water, then successively carries out the crystal of calcium sulfate point under second order reaction and room temperature
From obtaining second level clear water and secondary sludge；
Wherein, the second level clear water is returned and step (3) progress filtering processing is added.
2. preprocess method according to claim 1, wherein in step (1), the additional amount of lime makes the first order reaction
The pH of product is 10.5-12；
Preferably, the temperature of the first order reaction is 10-30 DEG C, and the pressure of the first order reaction is 0.02-0.1MPa, described one
The time of order reaction is 60-180min.
3. preprocess method according to claim 1, wherein in step (3), the fungicide be selected from sodium hypochlorite and/
Or hydrogen peroxide；The additional amount of the fungicide is the 1-20 mass ppm of the stoste and the second level clear water total amount.
4. preprocess method according to claim 1, wherein in step (3), the filtering processing is ultrafiltration and/or sand
Filter；Preferably, it is 1 or less that the filtering, which produces the SDI value of water,.
5. preprocess method according to claim 1, wherein in step (4), the antisludging agent is nanofiltration or reverse osmosis membrane
Antisludging agent, the antisludging agent deactivator are selected from ferric trichloride and/or hydrogen peroxide；
Preferably, the additional amount of the antisludging agent is the 1-20 mass ppm that the filtering produces water, and the antisludging agent deactivator adds
Entering amount is the 1-20 mass ppm that the filtering produces water.
6. preprocess method according to claim 1, wherein in step (4), the ion isolation is nanofiltration separation；It receives
Filtering separation temperature is 10-30 DEG C, and nanofiltration separation pressure is 0.8-1.5MPa, and the water yield that the pretreatment produces water is the filtering
Produce the 30-70% of water.
7. preprocess method according to claim 1, wherein in step (5), the additional amount of sodium sulphate makes the second level
The total hardness of clear water is 10-40mmol/L.
8. preprocess method according to claim 1, wherein in step (5), the temperature of the second order reaction is 10-30
DEG C, the pressure of the second order reaction is 0.02-0.1MPa, and the time of the second order reaction is 120-360min.
9. preprocess method described in any one of -8 according to claim 1, wherein the stoste and the second level clear water
Weight ratio is (1.5-3.5): 1.
10. a kind of system of coal-burning power plant's desulfurization wastewater with high salt, comprising: first order reaction unit (1), acidity adjustment unit (2), filter
Inventory member (3), ion isolation unit (4) and second order reaction unit (5)；
The first order reaction unit is used to that lime to be added to desulfurization wastewater and carries out first order reaction, and isolated level-one clear water and
Level-one sludge；
The acidity adjustment unit is used to level-one clear water progress pH being adjusted to second order reaction liquid；
The filtering unit is used to that fungicide to be added to the second order reaction liquid and can be carried out filtering processing, obtains filtering and produces water；
The ion isolation unit is used to produce water to the filtering and antisludging agent and antisludging agent deactivator progress ion isolation is added, and obtains
Water is produced to high concentration salt water and pretreatment；
The second order reaction unit is used to that sodium sulphate to be added to the high concentration salt water and carries out second order reaction and crystal of calcium sulfate
Separation, obtains second level clear water and secondary sludge；
The second level clear water output of the second order reaction unit is connected to the entrance of the filtering unit, for leading to the second level clear water
Enter the filtering unit and carries out the filtering processing.
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Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59142894A (en) * | 1983-02-01 | 1984-08-16 | Mitsubishi Heavy Ind Ltd | Process for removing phosphate in liquid |
| JP2002282855A (en) * | 2001-03-29 | 2002-10-02 | Toray Ind Inc | Method and equipment for producing water |
| CN101456635A (en) * | 2008-12-17 | 2009-06-17 | 深圳市能源环保有限公司 | Process and system for treating electric power plant waste water |
| CN201325916Y (en) * | 2008-12-17 | 2009-10-14 | 深圳市能源环保有限公司 | System for treating wastewater from power plant |
| CN104445717A (en) * | 2014-11-13 | 2015-03-25 | 深圳市中金岭南有色金属股份有限公司韶关冶炼厂 | Synchronous fluorine-calcium removal treatment process for reverse osmosis concentrated liquor of waste water from lead-zinc smelting |
| CN105174512A (en) * | 2015-08-24 | 2015-12-23 | 神华集团有限责任公司 | Processing method of salt containing water and salt containing processing system |
| CN105254101A (en) * | 2015-10-29 | 2016-01-20 | 中国能建集团装备有限公司南京技术中心 | Desulfurization waste water zero-discharging treatment technology for coal-fired power plants |
| CN105923822A (en) * | 2016-05-31 | 2016-09-07 | 江苏京源环保股份有限公司 | Mud and salt separation zero-discharge process of desulfurization wastewater |
| CN106082275A (en) * | 2016-06-13 | 2016-11-09 | 神华集团有限责任公司 | A kind of salt extraction process and salt making system |
| CN106115740A (en) * | 2016-06-13 | 2016-11-16 | 神华集团有限责任公司 | A kind of salt extraction process and salt making system |
| CN106746121A (en) * | 2016-12-27 | 2017-05-31 | 山东奥美环境股份有限公司 | A kind of desulfurization wastewater reuse and the processing method of salt resource |
| CN206692458U (en) * | 2017-02-09 | 2017-12-01 | 杭州上拓环境科技股份有限公司 | A kind of power plant desulfurization wastewater pretreatment system |
-
2017
- 2017-12-22 CN CN201711405526.8A patent/CN109956578B/en active Active
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59142894A (en) * | 1983-02-01 | 1984-08-16 | Mitsubishi Heavy Ind Ltd | Process for removing phosphate in liquid |
| JP2002282855A (en) * | 2001-03-29 | 2002-10-02 | Toray Ind Inc | Method and equipment for producing water |
| CN101456635A (en) * | 2008-12-17 | 2009-06-17 | 深圳市能源环保有限公司 | Process and system for treating electric power plant waste water |
| CN201325916Y (en) * | 2008-12-17 | 2009-10-14 | 深圳市能源环保有限公司 | System for treating wastewater from power plant |
| CN104445717A (en) * | 2014-11-13 | 2015-03-25 | 深圳市中金岭南有色金属股份有限公司韶关冶炼厂 | Synchronous fluorine-calcium removal treatment process for reverse osmosis concentrated liquor of waste water from lead-zinc smelting |
| CN105174512A (en) * | 2015-08-24 | 2015-12-23 | 神华集团有限责任公司 | Processing method of salt containing water and salt containing processing system |
| CN105254101A (en) * | 2015-10-29 | 2016-01-20 | 中国能建集团装备有限公司南京技术中心 | Desulfurization waste water zero-discharging treatment technology for coal-fired power plants |
| CN105923822A (en) * | 2016-05-31 | 2016-09-07 | 江苏京源环保股份有限公司 | Mud and salt separation zero-discharge process of desulfurization wastewater |
| CN106082275A (en) * | 2016-06-13 | 2016-11-09 | 神华集团有限责任公司 | A kind of salt extraction process and salt making system |
| CN106115740A (en) * | 2016-06-13 | 2016-11-16 | 神华集团有限责任公司 | A kind of salt extraction process and salt making system |
| CN106746121A (en) * | 2016-12-27 | 2017-05-31 | 山东奥美环境股份有限公司 | A kind of desulfurization wastewater reuse and the processing method of salt resource |
| CN206692458U (en) * | 2017-02-09 | 2017-12-01 | 杭州上拓环境科技股份有限公司 | A kind of power plant desulfurization wastewater pretreatment system |
Non-Patent Citations (1)
| Title |
|---|
| 王淑勤: "《电厂化学技术》", 31 March 2007 * |
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