CN108623034A - A kind of processing method and processing system of high-salt wastewater - Google Patents
A kind of processing method and processing system of high-salt wastewater Download PDFInfo
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- CN108623034A CN108623034A CN201710153042.2A CN201710153042A CN108623034A CN 108623034 A CN108623034 A CN 108623034A CN 201710153042 A CN201710153042 A CN 201710153042A CN 108623034 A CN108623034 A CN 108623034A
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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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- 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
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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
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
- C02F1/5245—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents using basic salts, e.g. of aluminium and iron
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
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- 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
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Abstract
The present invention relates to water treatment fields, disclose a kind of processing method and processing system of high-salt wastewater, and this method includes：(1) high-salt wastewater is mixed at least partly concentrated water from film concentration, mixing is intake and carries out room temperature crystallization treatment, obtain microsolubility inorganic salts and room temperature crystallization water outlet；(2) at least partly described room temperature crystallization water outlet is subjected to filtering processing, obtains filtering water outlet；(3) filtering water outlet is subjected to film concentration as film concentration water inlet, obtains concentrated water and production water, and at least partly concentrated water will be back to the room temperature crystallization treatment.The method of the present invention can be reduced fully to the requirement of upstream high-salt wastewater pretreatment unit water quality index, there is wider applicability to the variation of upstream high-salt wastewater pretreatment unit water quality index, it can be effectively prevent UF membrane element fouling, the investment in fixed assets of entire process system is greatly lowered.
Description
Technical field
The present invention relates to water treatment fields, and in particular, to a kind of processing method and processing system of high-salt wastewater.
Background technology
Overwhelming majority power plant of China, coal plant are using the SO in Wet Limestone Desulfurization technology removing flue gas2, running
The desulfurization wastewater of middle generation becomes one of most intractable waste water in coal-burning power plant because complicated component, pollutant kind.State at present
Interior main using chemical precipitation method (being commonly called as three headers precipitation) processing desulfurization wastewater, processing water outlet salt content is higher, directly arranges
Secondary pollution is be easy to cause after putting.Simultaneously as desulfurization wastewater water is smaller, salt content is high, power plant, coal plant's desulfurization wastewater
The process system long-play that is further processed is unstable, and (water inlet microsolubility inorganic salt content is high, leads to ultrafiltration nanofiltration reverse osmosis
Permeable system fouling condition is serious), and one-time investment is higher, thus at present without practical application example.But with Environmental Protection in China
It is required that further reinforcing, the exploitation of the further zero discharge treatment technology of desulfurization wastewater is extremely urgent, there is an urgent need for improve work
Technological innovation and technological development are carried out in terms of process system stability and reduction process system one-time investment.
CN 101492214A disclose a kind of membrane separation process of lead-zinc smelting wastewater, and processing step is：Lead-zinc smelting
Industrial wastewater pre-processes, most after heavy metal precipitation process qualified discharge by techniques such as more medium filter, ultrafiltration
Enter nanofiltration technique desalting processing afterwards, wherein production water reuse, concentrate qualified discharge after enhanced coagulation is handled.
CN102139169A discloses a kind of settler, method and the system containing the settler.The wherein precipitation
Device includes：The settlement section being placed in container, is formed between the precipitation zone of settlement section and settlement section and container
It is separated by solid-liquid separation region, and the liquid outlet positioned at upper vessel portion, wherein the ratio of container diameter and settlement section is about 1.5
To between 2.8.
CN102815810A discloses a kind of desalination system and method, which includes that membrane separation device and adjustment are single
Member, membrane separation device is acceptable to be included the input fluid of antisludging agent and generates purification fluid and concentrating streams, adjustment unit can
For being adjusted at least part antisludging agent in the concentrating streams from the membrane separation device, adjustment unit effect is
Handled fluid is adjusted into trip temperature adjustment and acid value.
CN 102424455A disclose a kind of Wastewater recycling nanofiltration treatment method and its device, this method step are：Waste water
Reuse nanofiltration processing unit works；Judge whether the nanofiltration device film group in Wastewater recycling nanofiltration processing unit meets cleaning item
Part；Spare nanofiltration device film group is replaced into nanofiltration device film group；Clean the nanofiltration device film group replaced.The device includes adopting
The nanofiltration device run with the sequential manner of cycle arrangement, nanofiltration device includes several nanofiltration device film groups and at least one set can
Replace the spare nanofiltration device film group of nanofiltration device film group.The patent application is waste water nanofiltration treatment process, is by nanofiltration system
The method of operation is combined with influent quality, and nanofiltration device is run using the sequential manner of cycle arrangement.
CN105753018A discloses a kind of device and method for removing the sodium sulphate in demineralized water, which includes film concentration
System and the room temperature crystal system being connected with film concentration systems, film concentration systems are film concentration systems or the opening of closed cycle
Formula film concentration systems, room temperature crystal system include sequentially connected surge tank, delivery pump, heat exchanger and room temperature crystallizer.This is specially
Profit application discloses the method that the sodium sulphate in demineralized water is removed using above equipment.The patent application is dense by the sodium sulphate in brine
It is reduced to supersaturation, by the flow velocity and pressure of adjusting film element surface, the concentration polarization on membrane component surface is preferably minimized, to sulphur
Sour sodium concentrate takes room temperature to crystallize, and directly obtains anhydrous sodium sulfate, obtain can transportation and sale product.The mesh of the patent application
Be brine middle and high concentration sodium sulphate is concentrated to supersaturation using film concentration systems, then take again room temperature crystallize mode
Sodium sulphate is separated.However this method treatment of Power, coal chemical industry high-salt wastewater are used, microsolubility inorganic salts (such as calcium sulfate,
Magnesium hydroxide, calcium carbonate, magnesium sulfate etc.) UF membrane element micro channel can be blocked so that separating film element flux depression, very
To so that UF membrane element is scrapped and has to replace new seperation film again, to increase process system operation and maintenance cost.
Temporarily therefore the method and system without preferable treatment of Power, coal chemical industry high-salt wastewater is researched and developed in art methods
A kind of inexpensive, high resource reuse and treatment method for high-salinity wastewater and processing system that UF membrane element fouling can be prevented,
It has important practical significance and market application value.
Invention content
The purpose of the invention is to overcome the drawbacks described above of the prior art, provide a kind of processing method of high-salt wastewater and
Processing system.
CN105753018A discloses a kind of device and method for removing the sodium sulphate in demineralized water, and the present inventor exists
It is found in research, if the process system for indiscriminately imitating the patent application publication is used for treatment of Power, coal chemical industry high-salt wastewater, due to three
Microsolubility inorganic salts (such as calcium sulfate, magnesium hydroxide, calcium carbonate, magnesium sulfate) contained by waste water handled by header sedimentation basin are
Through being in hypersaturated state, if further being concentrated through film concentration systems again, microsolubility inorganic salts first in concentrated water (such as calcium sulfate,
Magnesium hydroxide, calcium carbonate, magnesium sulfate etc.) degree of supersaturation increase sharply, secondly microsolubility inorganic salts supersaturated solution fouling incline
To relatively with degree of supersaturation metabisulfite solution higher, therefore easily in film concentration systems surface scale, to block UF membrane element
Micro channel so that separating film element flux depression, even more so that UF membrane element is scrapped and has to replace new point again
From film, to increase process system operation and maintenance cost.That is, the microsolubility contained in power plant, coal chemical industrial waste water
Inorganic salts (such as calcium sulfate, magnesium hydroxide, calcium carbonate, magnesium sulfate) have been in hypersaturated state, thus in film concentration systems
Further (the microsolubility inorganic salts of extremely low concentration are molten for concentration generation concentrated water (the microsolubility inorganic salt solution of high concentration) and production water
Liquid) before, there is an urgent need for reducing the inorganic salt solubility of microsolubility in the processing water inlet of film concentration systems, film concentration system is reduced to reach
System surface smut (microsolubility inorganic salts precipitation) content, the purpose for protecting seperation film.
Therefore, to achieve the goals above, the present invention provides a kind of processing method of high-salt wastewater, this method includes：
(1) high-salt wastewater is mixed at least partly concentrated water from film concentration, mixing is intake and carries out room temperature knot
Crystalline substance processing obtains microsolubility inorganic salts and room temperature crystallization water outlet；
(2) at least partly described room temperature crystallization water outlet is subjected to filtering processing, obtains filtering water outlet；
(3) filtering water outlet is subjected to film concentration as film concentration water inlet, obtains concentrated water and production water, and will at least
Part concentrated water is back to the room temperature crystallization treatment.
Second aspect, the present invention provides a kind of processing system of high-salt wastewater, which includes room temperature crystalline element, filter
Clear processing unit and film upgrading unit,
The room temperature crystalline element is for mixing high-salt wastewater at least partly concentrated water from the film upgrading unit
Obtained mixing water inlet carries out room temperature crystallization treatment, obtains microsolubility inorganic salts and room temperature crystallization water outlet；
The filtering processing unit is carried out for that will crystallize water outlet from at least partly room temperature of the room temperature crystalline element
Filtering is handled, and obtains filtering water outlet；
The film upgrading unit is carried out for that will be discharged from the filtering of the filtering processing unit as film concentration water inlet
Film concentration obtains concentrated water and production water, and at least partly concentrated water will be back to the room temperature crystalline element.
The present invention method in, before waste water enters film upgrading unit, first use room temperature crystalline element by film concentrate into
Microsolubility inorganic salts degree of supersaturation reduces in water, and then in film concentration, (can be aided with antisludging agent when necessary) progress film is dense
Contracting is handled, and can achieve the purpose that reduce film upgrading unit surface smut (microsolubility inorganic salts precipitation) content, protection seperation film.
By reducing in film concentration water inlet after microsolubility inorganic salts degree of supersaturation, film upgrading unit further concentrates water inlet and generates concentrated water
(the microsolubility inorganic salt solution of high concentration) and production water (the microsolubility inorganic salt solution of extremely low concentration).Meanwhile at least partly
Concentrated water (the microsolubility inorganic salt solution of high concentration) returns to room temperature crystalline element, will come from three in room temperature crystalline element
Microsolubility inorganic salts degree of supersaturation in the mixing water inlet of the high-salt wastewater of header sedimentation basin and the concentrated water of film upgrading unit reduces.
The processing method and processing system of the high-salt wastewater of the present invention can be reduced fully and be pre-processed to upstream high-salt wastewater
Unit water quality index (referring mainly to microsolubility inorganic salt concentration) requirement, and to upstream high-salt wastewater pretreatment unit water quality index
Variation have wider applicability；It can be effectively prevent UF membrane element fouling, film upgrading unit is greatly lowered (as surpassed
Filter, nanofiltration, reverse osmosis units) water inlet in antisludging agent additive amount, even without addition antisludging agent；Meanwhile in same industry water
Under the conditions for the treatment of capacity, film upgrading unit (such as ultrafiltration, nanofiltration, reverse osmosis units) required membrane module quantity that the present invention uses
It further decreases, to reduce the investment in fixed assets of entire process system.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Description of the drawings
Attached drawing is to be used to provide further understanding of the present invention, an and part for constitution instruction, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings：
Fig. 1 is the processing method schematic diagram of the high-salt wastewater of the embodiment of the present invention 1.
Fig. 2 is the processing method schematic diagram of the high-salt wastewater of the embodiment of the present invention 2.
Fig. 3 is the processing method schematic diagram of the high-salt wastewater of the embodiment of the present invention 3.
Fig. 4 is the processing method schematic diagram of the high-salt wastewater of comparative example 1 of the present invention.
Specific implementation mode
The specific implementation mode of the present invention is described in detail below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
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.
In a first aspect, the present invention provides a kind of processing method of high-salt wastewater, this method includes：
(1) high-salt wastewater is mixed at least partly concentrated water from film concentration, mixing is intake and carries out room temperature knot
Crystalline substance processing obtains microsolubility inorganic salts and room temperature crystallization water outlet；
(2) at least partly described room temperature crystallization water outlet is subjected to filtering processing, obtains filtering water outlet；
(3) filtering water outlet is subjected to film concentration as film concentration water inlet, obtains concentrated water and production water, and will at least
Part concentrated water is back to the room temperature crystallization treatment.
In the method for the present invention, in step (1), for the condition of room temperature crystallization treatment, there is no particular limitation, Ke Yiwei
Various conditions commonly used in the art, under preferable case, room temperature crystallization treatment carries out in the presence of softening agent and flocculant.Wherein,
Room temperature can be 20-35 DEG C.
Preferably, on the basis of the weight of mixing water inlet, the dosage of the softening agent is 0.5-10 weight %.
Preferably, the dosage of the flocculant is 1-100ppm.
Preferably, the softening agent is at least one of sodium carbonate, sodium hydroxide and calcium hydroxide.
Preferably, the flocculant is polyacrylamide and/or ferric trichloride.
In the case of process of the present invention it is preferred, the degree of supersaturation of microsolubility inorganic salts is 100- in the mixing water inlet
350%, further preferably 100-250%.
In the case of process of the present invention it is preferred, the microsolubility inorganic salts be calcium sulfate, magnesium hydroxide, calcium carbonate and
At least one of magnesium sulfate.
In the method for the present invention, room temperature crystallization is discharged visual process system and needs outer row or not outer row.
In the method for the present invention, in step (2), there is no particular limitation for the method handled for filtering, can be ability
The common various methods in domain, as long as organic matter, bacterium, virus and other non-inorganic salt impurities in water inlet can be removed.
Under preferable case, the mode of filtering processing is hyperfiltration treatment.It is further preferred that the condition of hyperfiltration treatment includes：Ultrafiltration fenestra
Diameter is 0.05 μm -10 μm, pressure 0.1-1MPa.In the present invention, unless otherwise instructed, the pressure referred to is gauge pressure.
In the method for the present invention, in step (3), filtering of the film concentration for that will concentrate water inlet as film, which is discharged, to be carried out
The separation of inorganic salts, it is about 0-10% that gained, which produces microsolubility inorganic salts degree of supersaturation in water, and microsolubility is inorganic in gained concentrated water
Salt degree of supersaturation is generally more than 100% (such as 120-500%, concrete numerical value is depending on water flow number in its produced concentrated water), film
Concentrated water obtained by concentration regards process system and needs outer row or not outer row.
Preferably, in step (3), film concentration is nanofiltration separation processing or reverse-osmosis treated.
Preferably, the condition of nanofiltration separation processing includes：Temperature be 20-50 DEG C, pressure 0.5-3MPa, nanofiltration concentrated water with
The volume flow ratio that water is produced in nanofiltration is 0.2-1.5：1, further preferably 0.3-1.2：1；
Preferably, the condition of reverse-osmosis treated includes：Temperature be 20-50 DEG C, pressure 0.5-3MPa, reverse osmosis concentrated water with
The volume flow ratio of reverse osmosis produced water is 0.2-1.5：1, further preferably 0.3-1.2：1.
Preferably, in step (3), the part concentrated water for being back to the room temperature crystallization treatment is obtained with film concentration
Production water volume flow ratio be 0.2-1.2：1, further preferably 0.3-1：1.
Second aspect, the present invention provides a kind of processing system of high-salt wastewater, which includes room temperature crystalline element, filter
Clear processing unit and film upgrading unit,
The room temperature crystalline element is for mixing high-salt wastewater at least partly concentrated water from the film upgrading unit
Obtained mixing water inlet carries out room temperature crystallization treatment, obtains microsolubility inorganic salts and room temperature crystallization water outlet；
The filtering processing unit is carried out for that will crystallize water outlet from at least partly room temperature of the room temperature crystalline element
Filtering is handled, and obtains filtering water outlet；
The film upgrading unit is carried out for that will be discharged from the filtering of the filtering processing unit as film concentration water inlet
Film concentration obtains concentrated water and production water, and at least partly concentrated water will be back to the room temperature crystalline element.
In the processing system of the present invention, for room temperature crystalline element, there is no particular limitation, can be commonly used in the art
Various room temperature crystalline elements, this is well known to those skilled in the art, and details are not described herein.
In the processing system of the present invention, for filtering processing unit, there is no particular limitation, can be commonly used in the art
Various filtering processing units, under preferable case, filtering processing unit includes hyperfiltration membrane assembly；It is further preferred that the ultrafiltration
Ultrafiltration membrane aperture is 0.05 μm -10 μm in membrane module.
In the processing system of the present invention, under preferable case, the film upgrading unit is nanofiltration separation unit or reverse osmosis list
Member.
Preferably, nanofiltration separation unit includes an at least nanofiltration membrane component, and the nanofiltration membrane component is to sodium in water inlet
The rejection of ion is less than 10%, is less than the 10%, retention to sulfate ion in water inlet to the rejection of chlorion in water inlet
Rate is more than 90%, the nanofiltration membrane component to the rejection of calcium ion in water inlet more than 75%；It is further preferred that the nanofiltration point
Include at least two nanofiltration membrane components being used in series from unit.Meeting the nanofiltration membrane component of aforementioned condition can be obtained by commercially available
, such as can be the GE DK4040 of GE companies.
Wherein, for reverse osmosis units, there is no particular limitation, can be various reverse osmosis units commonly used in the art, this
It is well known to those skilled in the art, details are not described herein.
Embodiment
The present invention will be described in detail by way of examples below, but the range being not intended to limit the present invention.Below
In embodiment, unless otherwise instructed, used method is method commonly used in the art.
Embodiment 1
In conjunction with Fig. 1, the present embodiment is used to illustrate the processing method of the high-salt wastewater of the present invention.
(1) by 20T/h, the high-salt wastewater that calcium sulfate degree of supersaturation is 150% and 6.67T/h, sulfuric acid that step (3) obtains
As mixing water inlet (calcium sulfate degree of supersaturation is 212%) with 26.67T/h's after the concentrated water mixing that calcium degree of supersaturation is 400%
Total flow carries out room temperature crystallization treatment, wherein polyacrylamide of the room temperature crystallization treatment in the sodium carbonate and 55ppm of 4 weight %
It is carried out in the presence of (being purchased from Ondeo Nalco Co., trade mark 8103PLUS, similarly hereinafter), obtains calcium sulphate crystal (outer row) and 26.67T/
H, the room temperature crystallization water outlet that calcium sulfate degree of supersaturation is 100%；
(2) it for 6 μm of ultrafiltration membrane at 0.5MPa is 100% by 26.67T/h, calcium sulfate degree of supersaturation to use aperture
Room temperature crystallization water outlet carries out hyperfiltration treatment, obtains 26.67T/h, the filtering that calcium sulfate degree of supersaturation is 100% is discharged；
(3) by 26.67T/h, calcium sulfate degree of supersaturation be 100% filtering water outlet as film concentration water inlet supplied to
Nanofiltration separation unit (being made of 6 putaminas, the two level nanofiltration system of the GE DSL NF8040 nanofiltration membrane components of 4+2 sequences) into
Row nanofiltration separation processing, temperature be 30 DEG C, pressure 0.62MPa, obtain 20T/h, calcium sulfate degree of supersaturation be 0% production water and
6.67T/h, the concentrated water that calcium sulfate degree of supersaturation is 400%, by the 6.67T/h, the concentrated water that calcium sulfate degree of supersaturation is 400%
All it is back to room temperature crystallization treatment.
Embodiment 2
In conjunction with Fig. 2, the present embodiment is used to illustrate the processing method of the high-salt wastewater of the present invention.
(1) by 20T/h, the high-salt wastewater that calcium sulfate degree of supersaturation is 150% and 10T/h, calcium sulfate that step (3) obtains
As mixing water inlet (calcium sulfate degree of supersaturation is 200%) with the total flow of 30T/h after the concentrated water mixing that degree of supersaturation is 300%
Carry out room temperature crystallization treatment, wherein room temperature crystallization treatment exists in the calcium hydroxide of 6 weight % and the polyacrylamide of 65ppm
Lower progress obtains calcium sulphate crystal (outer row) and 30T/h, the room temperature crystallization water outlet that calcium sulfate degree of supersaturation is 100%；
(2) room temperature that 30T/h, calcium sulfate degree of supersaturation are 100% at 0.8MPa for 6 μm of ultrafiltration membrane by aperture is used
Crystallization water outlet carries out hyperfiltration treatment, obtains 30T/h, the filtering that calcium sulfate degree of supersaturation is 100% is discharged；
(3) 30T/h, the filtering water outlet that calcium sulfate degree of supersaturation is 100% are supplied as film concentration water inlet to anti-
Permeation unit (being made of 6 putaminas, the two-stage reverse osmosis system of the DOW BW30FR-400 reverse-osmosis membrane elements of 4+2 sequences) into
Row reverse-osmosis treated, temperature be 30 DEG C, pressure 1.2MPa, obtain 20T/h, calcium sulfate degree of supersaturation be 0% production water and
10T/h, the concentrated water that calcium sulfate degree of supersaturation is 300%, by the 10T/h, the concentrated water whole that calcium sulfate degree of supersaturation is 300%
It is back to room temperature crystallization treatment.
Embodiment 3
In conjunction with Fig. 3, the present embodiment is used to illustrate the processing method of the high-salt wastewater of the present invention.
(1) by 20T/h, the high-salt wastewater that calcium sulfate degree of supersaturation is 150% and 20T/h, calcium sulfate that step (3) obtains
As mixing water inlet (calcium sulfate degree of supersaturation is 175%) with the total flow of 40T/h after the concentrated water mixing that degree of supersaturation is 200%
Carry out room temperature crystallization treatment, wherein room temperature crystallization treatment exists in the sodium hydroxide of 7 weight % and the polyacrylamide of 80ppm
Lower progress obtains calcium sulphate crystal (outer row) and 40T/h, the room temperature crystallization water outlet that calcium sulfate degree of supersaturation is 100%；
(2) room temperature that 40T/h, calcium sulfate degree of supersaturation are 100% at 0.6MPa for 6 μm of ultrafiltration membrane by aperture is used
Crystallization water outlet carries out hyperfiltration treatment, obtains 40T/h, the filtering that calcium sulfate degree of supersaturation is 100% is discharged；
(3) 40T/h, the filtering water outlet that calcium sulfate degree of supersaturation is 100% are supplied as film concentration water inlet to receiving
It filters separative element (with embodiment 1) and carries out nanofiltration separation processing, temperature is 25 DEG C, and pressure 0.8MPa obtains 20T/h, sulfuric acid
The concentrated water that the production water and 20T/h, calcium sulfate degree of supersaturation that calcium degree of supersaturation is 0% are 200%, by the 20T/h, calcium sulfate mistake
The concentrated water that saturation degree is 200% is all back to room temperature crystallization treatment.
Comparative example 1
High-salt wastewater is handled, concrete technology flow process is as follows (in conjunction with Fig. 4)：
(1) by 20T/h, the high-salt wastewater that calcium sulfate degree of supersaturation is 150% and 10T/h, calcium sulfate that step (3) obtains
As mixing water inlet (calcium sulfate degree of supersaturation is 133%) with 30T/h after the room temperature crystallization production water mixing that degree of supersaturation is 100%
Total flow, use aperture to carry out hyperfiltration treatment at 0.5MPa for 6 μm of ultrafiltration membrane, obtain 30T/h, calcium sulfate degree of supersaturation
It is discharged for 133% filtering；
(2) 30T/h, the filtering water outlet that calcium sulfate degree of supersaturation is 133% are supplied to nanofiltration separation unit (by 6 films
Shell composition, 4+2 sequences GE DSL NF8040 nanofiltration membrane components two level nanofiltration system) carry out nanofiltration separation processing, temperature is
30 DEG C, pressure 0.62MPa, obtain the production water and 10T/h, calcium sulfate degree of supersaturation of 20T/h, calcium sulfate degree of supersaturation for 0%
For 400% concentrated water；
(3) 10T/h, the concentrated water that calcium sulfate degree of supersaturation is 400% are subjected to room temperature crystallization treatment, wherein room temperature
Crystallization treatment carries out in the presence of the polyacrylamide of the sodium carbonate of 4 weight % and 55ppm, obtains 10T/h, calcium sulfate supersaturation
Degree produces water and crystal of calcium sulfate salt (outer row) for 100% room temperature crystallization；By 10T/h, calcium sulfate degree of supersaturation be 100% it is normal
Temperature crystallization production water is back to hyperfiltration treatment.
It is now that the related keyword model parameter of embodiment 1-3 and comparative example 1 is as follows, it the results are shown in Table 5.
Table 5
As can be seen from Table 5, the processing method of high-salt wastewater of the invention has following advantage：It can be with from embodiment 1-3
Find out, in the water inlet of film concentration calcium sulfate degree of supersaturation can perseverance maintain 100%, thus the method for the present invention can be abundant
It reduces process system to require upstream Wastewater Pretreatment unit water quality index (referring mainly to microsolubility inorganic salts degree of supersaturation), to upper
The variation for swimming Wastewater Pretreatment unit water quality index has wider applicability；Meanwhile comparative example 1 is compared with Example 1,
Under the conditions of same industry water process amount, in method of the invention under optimum condition at filtering cell processing amount and film upgrading unit
Reason amount declines compared with comparative example 1, thus required membrane module quantity thus reduces, although room temperature knot in the method for the present invention
Brilliant cell processing amount rises, but due to the investment in fixed assets of room temperature crystalline element compared with film unit investment in fixed assets almost
It can ignore, thus the method for the present invention is by reducing film unit treating capacity to reduce the fixed assets of entire process system
Investment cost.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail can carry out a variety of simple variants to technical scheme of the present invention within the scope of the technical concept of the present invention, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (10)
1. a kind of processing method of high-salt wastewater, which is characterized in that this method includes：
(1) high-salt wastewater is mixed at least partly concentrated water from film concentration, mixing is intake and is carried out at room temperature crystallization
Reason obtains microsolubility inorganic salts and room temperature crystallization water outlet；
(2) at least partly described room temperature crystallization water outlet is subjected to filtering processing, obtains filtering water outlet；
(3) filtering water outlet is subjected to film concentration as film concentration water inlet, obtains concentrated water and production water, and will at least partly
Concentrated water is back to the room temperature crystallization treatment.
2. according to the method described in claim 1, wherein, in step (1), the room temperature crystallization treatment is in softening agent and flocculant
In the presence of carry out；
Preferably, on the basis of the weight of mixing water inlet, the dosage of the softening agent is 0.5-10 weight %；
Preferably, the dosage of the flocculant is 1-100ppm；
Preferably, the softening agent is at least one of sodium carbonate, sodium hydroxide and calcium hydroxide；
Preferably, the flocculant is polyacrylamide and/or ferric trichloride.
3. method according to claim 1 or 2, wherein in step (2), the mode of the filtering processing is hyperfiltration treatment；
Preferably, the condition of the hyperfiltration treatment includes：Ultrafiltration membrane aperture is 0.05 μm -10 μm, pressure 0.1-1MPa.
4. according to the method described in any one of claim 1-3, wherein in step (3), the film concentration is nanofiltration
Separating treatment or reverse-osmosis treated；
Preferably, the condition of the nanofiltration separation processing includes：Temperature be 20-50 DEG C, pressure 0.5-3MPa, nanofiltration concentrated water with
The volume flow ratio that water is produced in nanofiltration is 0.2-1.5：1, preferably 0.3-1.2：1；
Preferably, the condition of the reverse-osmosis treated includes：Temperature be 20-50 DEG C, pressure 0.5-3MPa, reverse osmosis concentrated water with
The volume flow ratio of reverse osmosis produced water is 0.2-1.5：1, preferably 0.3-1.2：1.
5. according to the method described in any one of claim 1-4, wherein in step (3), be back at the room temperature crystallization
The volume flow ratio for the production water that the part concentrated water of reason is obtained with film concentration is 0.2-1.2：1, preferably 0.3-1：1.
6. according to the method described in any one of claim 1-5, wherein the mistake of microsolubility inorganic salts in the mixing water inlet
Saturation degree is 100-350%, preferably 100-250%.
7. according to the method described in any one of claim 1-6, wherein the microsolubility inorganic salts are calcium sulfate, hydrogen-oxygen
Change at least one of magnesium, calcium carbonate and magnesium sulfate.
8. a kind of processing system of high-salt wastewater, which is characterized in that the system include room temperature crystalline element, filtering processing unit and
Film upgrading unit,
The room temperature crystalline element is for high-salt wastewater and at least partly concentrated water from the film upgrading unit to be mixed to get
Mixing water inlet carry out room temperature crystallization treatment, obtain microsolubility inorganic salts and room temperature crystallization water outlet；
The filtering processing unit carries out filtering for that will crystallize water outlet from at least partly room temperature of the room temperature crystalline element
Processing obtains filtering water outlet；
The film upgrading unit is dense for film concentration water inlet will to be used as to carry out film from the filtering of filtering processing unit water outlet
Contracting is handled, and obtains concentrated water and production water, and at least partly concentrated water will be back to the room temperature crystalline element.
9. system according to claim 8, wherein the filtering processing unit includes hyperfiltration membrane assembly；
Preferably, ultrafiltration membrane aperture is 0.05 μm -10 μm in the hyperfiltration membrane assembly.
10. system according to claim 8 or claim 9, wherein the film upgrading unit is nanofiltration separation unit or reverse osmosis list
Member；
Preferably, the nanofiltration separation unit includes an at least nanofiltration membrane component, and the nanofiltration membrane component is to sodium in water inlet
The rejection of ion is less than 10%, is less than the 10%, retention to sulfate ion in water inlet to the rejection of chlorion in water inlet
Rate is more than 90%, the nanofiltration membrane component to the rejection of calcium ion in water inlet more than 75%；
It is further preferred that the nanofiltration separation unit includes at least two nanofiltration membrane components being used in series.
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| CN110790351A (en) * | 2019-12-10 | 2020-02-14 | 华电水务工程有限公司 | Calcium sulfate crystallization system for high-salinity wastewater and method for treating high-salinity wastewater |
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| US11046598B1 (en) | 2019-12-18 | 2021-06-29 | Jinzheng Eco-Technology Co. Ltd. | Method and system for treating high salinity water |
| CN113087079A (en) * | 2021-03-31 | 2021-07-09 | 山东润泰环保技术有限公司 | Device for treating supersaturated solution by membrane technology |
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