CN105461144A - Method and device for treating desulfurization waste water - Google Patents
Method and device for treating desulfurization waste water Download PDFInfo
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- CN105461144A CN105461144A CN201610069562.0A CN201610069562A CN105461144A CN 105461144 A CN105461144 A CN 105461144A CN 201610069562 A CN201610069562 A CN 201610069562A CN 105461144 A CN105461144 A CN 105461144A
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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
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
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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
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
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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
- C02F1/442—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
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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
- C02F1/44—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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- 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
- C02F1/445—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by forward 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
- C02F1/4693—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis electrodialysis
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
Abstract
The invention relates to the technical field of waste water treatment, in particular to a method and device for treating desulfurization waste water. The method for treating the desulfurization waste water includes the following steps that the desulfurization waste water is pretreated, and softened water is obtained; monovalent ions and other ions in the softened water are separated, and separated liquid and concentrated liquid are obtained; the separated liquid is crystallized, and crystal salt is obtained; the concentrated liquid is supplied to a fuel gas desulfurization system, wherein the concentration step is further included for the softened water obtained before the monovalent ions and other ions in the softened water are separated and the separated liquid obtained after the monovalent ions and other ions in the softened water are separated. According to the method for treating the desulfurization waste water, the whole treatment method is simple, and zero emission of the desulfurization waste water is achieved. According to the device for treating the desulfurization waste water, the desulfurization waste water is treated through the treatment device, after treatment of a pretreatment softening device, the ions of different valance states are separated and can be utilized, and finally comprehensive utilization and zero emission of the desulfurization waste water are achieved.
Description
Technical field
The present invention relates to technical field of waste water processing, especially relate to a kind for the treatment of process and device of desulfurization wastewater.
Background technology
At present for most of thermal power plant, flue gas desulphurization system all adopts Limestone-gypsum Wet Flue Gas Desulfurization Process, and flue gas is washed through caustic lime emulsion, the SO in flue gas
2absorbed by solution, generate sulfite solution and carry out oxidation generation calcium sulfate, both gypsum after saturated.The desulfuration efficiency of wet process of FGD is high, needs to consume a large amount of Wingdales and water resources, one of the most unmanageable waste water of desulfurization wastewater Ye Shi power plant of generation.
Containing a large amount of suspended substance, oversaturated sulphite, vitriol and heavy metal in desulfurization wastewater, be all much wherein require the strict first kind pollutent controlled in national environmental standard.Conventional desulfurization wastewater Zero discharging system flow process is complicated, consume more pharmaceutical chemicals and energy, the water after process obtains crystal salt by crystallizer, not only cost of investment and operation cost high, and the carnallite that crystallizer is produced can only remove landfill, really effectively do not recycle resource.
In view of this, special proposition the present invention.
Summary of the invention
The first object of the present invention is the treatment process providing a kind of desulfurization wastewater, removes the impurity of desulfurization wastewater, reclaims the effective constituent in waste water, recycles reluctant waste water simultaneously, realize the discharge of desulfurization wastewater zero.
The second object of the present invention is the treatment unit providing a kind of desulfurization wastewater, and this device is that plurality of devices connects successively, and by desulfurization wastewater step-by-step processing, the waste water after process is recycled respectively, realizes the zero release of desulfurization wastewater.
A treatment process for desulfurization wastewater, comprises the following steps:
(a), desulfurization wastewater is carried out pre-treatment, obtain softening water;
B (), by the monovalent ion in described softening water and other ions separately, obtains the parting liquid containing monovalent ion and contains the concentrated solution of other ions;
(c), described parting liquid is carried out crystallization, obtain crystal salt;
(d), described concentrated solution supply flue gas desulphurization system;
Wherein, in step (b), the softening water before the monovalent ion in described softening water and other ions being separated or parting liquid afterwards also comprise concentrated step.
The treatment process of desulfurization wastewater provided by the invention, first desulfurization wastewater is carried out pre-treatment, remove suspended substance, basicity, hardness, heavy metal, COD etc. a large amount of in water, parting liquid carries out concentrated or pretreated water outlet is first concentrated the separation carrying out different valence state ion again by separation that different valence state ion is first carried out in water outlet again, so that realize the recycling of ion, producing water through concentration process can direct reuse.Particularly, the concentrated parting liquid containing monovalent ion obtains crystal salt through crystallization; The concentrated solution of other ions contains other ions such as sulfate radical, flue gas desulphurization system is mixed into by the moisturizing of pipeline and power plant desulphurization system, the water yield of concentrated solution accounts for the 2-5% of the water inlet of flue gas desulphurization system, can not affect sweetening effectiveness, finally excessive sulfate ion is discharged as gypsum.Whole treatment process is simple, and achieves the zero release of desulfurization wastewater.
In addition, softening water is selected first to concentrate still first to be separated by different valence state ion, and according to the composition of different waste water, integrated economics principle is selected, with cost-saving.
Preferably, in step (b), nanofiltration membrane is adopted the monovalent ion in described softening water and other ions to be separated.
If the amount of passing through concentrated parting liquid is little or saltiness is higher, directly crystallization can be carried out; If the amount of passing through concentrated parting liquid is more or saltiness is lower, then carry out crystallization, with save energy after needing to carry out reconcentration.
Preferably, described concentrated employing reverse osmosis concentration, the water direct reuse produced in described reverse osmosis concentrated compression process, to realize the environment friendly to wastewater treatment.
Preferably, in step (c), described parting liquid also comprises the step of reconcentration before carrying out crystallization, and through described reconcentration, the saltiness in the condensed water obtained is at more than 120000mg/L;
The water direct reuse produced in described reconcentration process.
If the softening water that pre-treatment obtains first carries out the separation of different valence state ion, then follow-uply successively parting liquid is carried out reverse osmosis concentration and reconcentration, the concentrated solution that reconcentration obtains carries out crystallization;
If the softening water that pre-treatment obtains first carries out reverse osmosis concentration, then the follow-up separation successively parting liquid being carried out different valence state ion, then carries out reconcentration by parting liquid, and the concentrated solution that reconcentration obtains carries out crystallization.
Present invention also offers a kind for the treatment of unit of desulfurization wastewater, comprising: pre-treatment softening equipment, nanofiltration equipment and crystallizer;
Described pre-treatment softening equipment and described nanofiltration equipment connection, the separation outlet of described nanofiltration equipment is connected with crystallizer;
Described reverse osmosis equipment exports between described crystallizer between described pre-treatment softening equipment with described nanofiltration equipment or being separated of described nanofiltration equipment.
The treatment unit of desulfurization wastewater provided by the invention, power plant desulfurization island desulfurization wastewater out adopts this treatment facility process, after the process of pre-treatment softening equipment, by by different valence state ion isolation, realize the utilization of different valence state ion, finally realize the zero release of desulfurization wastewater.
Specifically, in certain embodiments, pre-treatment softening equipment is entered by power plant desulfurization island desulfurization wastewater out, first remove suspended substance, basicity, hardness, heavy metal, COD etc. a large amount of in water, water outlet, through nanofiltration device separates monovalent ion and other ions, obtains the parting liquid containing monovalent ion and the concentrated solution containing other ions; The parting liquid of nanofiltration equipment enters reverse osmosis equipment and concentrates, and the rate of recovery is about 60-80%, the saltiness about 30000 ~ 80000mg/L of the reverse osmosis concentrated water obtained, reverse osmosis produced water direct reuse.If reverse osmosis concentrated water-content is less or salts contg is higher, then directly enters crystallizer crystallization and obtain crystal salt.Concentrated solution contains other ions such as sulfate radical, flue gas desulphurization system is mixed into by the moisturizing of pipeline and power plant desulphurization system, the water yield of concentrated solution accounts for the 2-5% of the water inlet of flue gas desulphurization system, and can not affect sweetening effectiveness, finally excessive sulfate ion is discharged as gypsum.
In certain embodiments, pre-treatment softening equipment is entered by power plant desulfurization island desulfurization wastewater out, first remove suspended substance, basicity, hardness, heavy metal, COD etc. a large amount of in water, water outlet first passes into reverse osmosis equipment and concentrates, the rate of recovery is about 60-80%, the saltiness about 30000 ~ 80000mg/L of the reverse osmosis concentrated water obtained, reverse osmosis produced water direct reuse, reverse osmosis concentrated water enters nanofiltration equipment again, monovalent ion in reverse osmosis concentrated water and other ions separate by nanofiltration equipment, obtain the parting liquid containing monovalent ion and the concentrated solution containing other ions.If parting liquid content is less or salts contg is higher, then directly enters crystallizer crystallization and obtain crystal salt.Concentrated solution contains other ions such as sulfate radical, flue gas desulphurization system is mixed into by the moisturizing of pipeline and power plant desulphurization system, the water yield of concentrated solution accounts for the 2-5% of the water inlet of flue gas desulphurization system, and can not affect sweetening effectiveness, finally excessive sulfate ion is discharged as gypsum.
If it is more to be separated liquid measure, then needs parting liquid first to carry out reconcentration, and then carry out crystallization.
Further, reconcentration equipment is also connected with before the described crystallizer of institute.
According to the concentrated effect of parting liquid, one or more reconcentration equipment can be selected to concentrate further.Further, described reconcentration equipment is any one or more in positive penetration equipment, efficient reverse osmosis equipment, electrodialysis appts.
Concentrated parting liquid enters reconcentration equipment by pipeline, reconcentration equipment can be positive penetration equipment, efficient reverse osmosis equipment, electrodialysis appts etc., improve the saltiness of parting liquid to 12000-180000mg/L, the recyclable pure water resource of product water of reconcentration equipment.
Reconcentration equipment filter membrane used can bear higher pressure.The filter membrane that positive penetration equipment adopts is FO film, and the filter membrane that efficient reverse osmosis equipment adopts is RO film.
Further, described device also comprises centrifugation apparatus, and described crystallizer is connected with described centrifugation apparatus.
Concentrated parting liquid or enter pump circulation crystallizer by pipeline through the parting liquid of reconcentration, temperature and pressure in crystallization control device, evaporative crystallization obtains the magma of a sodium chloride-containing, magma obtains pure sodium-chlor crystal salt by whizzer, and the crystallizer mother liquor of minute quantity is used for spraying dry or is used as fixed-end forces.
Preferably, described pre-treatment softening equipment is coagulation clarification system or tubular type ultrafiltration system.
Further, described coagulation clarification system comprises the settling pond, sand filtration apparatus, the ion-exchange unit that connect successively.
Owing to containing a large amount of suspended substances in desulfurization wastewater, basicity, the material such as metal ion and organism, the pre-treatment of desulfurization wastewater is specially: first desulfurization wastewater enters settling pond, settling pond is by feeding lime and sodium carbonate or sodium hydroxide and sodium carbonate, regulate more than the pH to 11.5 of desulfurization wastewater, effectively can remove heavy metal ion and the organism of basicity in waste water and hardness ions and part, the residence time of desulfurization wastewater in settling pond is 1.5 ~ 3h, settling pond water outlet removes suspended substance further through sand filtration apparatus, sand filtration water outlet enters ion-exchange unit and removes hardness ions further as calcium ions and magnesium ions etc., the water outlet of coagulation clarification system obtains softening water.
Further, described tubular type ultrafiltration system comprises the reaction tank, device for ultrafiltration membrane, the ion-exchange unit that connect successively.
According to the situation of water quality, desulfurization wastewater also can carry out pre-treatment in the following ways, particularly: first desulfurization wastewater enters reaction tank, feeding lime and sodium carbonate or sodium hydroxide and sodium carbonate stir, regulate more than the pH to 11.5 of desulfurization wastewater, the residence time is 1.5 ~ 3h, and the mixed solution obtained directly enters tubular ultra-filtration membrane equipment by pump, the water outlet that filtration obtains enters ion-exchange unit and removes hardness ions further, and the water outlet of ion-exchange unit is softening water.
In the present invention, the connection of each equipment as required, undertaken connecting by pipeline.
Preferably, each connection is and is connected by pipeline.
Prior art is compared, and beneficial effect of the present invention is:
1) treatment process of desulfurization wastewater provided by the invention, adopt the pretreated desulfurization wastewater of nanofiltration process, realize the separation of different valence state ion, then by the recycling of different valence state ion, whole treatment process is simple, and achieves the zero release of desulfurization wastewater.
2) present invention also offers the treatment unit of desulfurization wastewater, the power plant desulfurization island each equipment of desulfurization wastewater out in this treatment unit processes, and finally realize the zero release of desulfurization wastewater, whole process save energy, contamination-free produces.
3) present invention also offers two kinds of systems of pre-treatment softening equipment, better to remove containing materials such as a large amount of suspended substance, basicity, metal ion and organism in desulfurization wastewater, for subsequent disposal provides good basis.
Accompanying drawing explanation
In order to be illustrated more clearly in the specific embodiment of the invention or technical scheme of the prior art, be briefly described to the accompanying drawing used required in embodiment or description of the prior art below, apparently, accompanying drawing in the following describes is some embodiments of the present invention, for those of ordinary skill in the art, under the prerequisite not paying creative work, other accompanying drawing can also be obtained according to these accompanying drawings.
The schematic diagram of the treatment unit of the desulfurization wastewater that Fig. 1 provides for the embodiment of the present invention 1;
The schematic diagram of the treatment unit of the desulfurization wastewater that Fig. 2 provides for the embodiment of the present invention 2;
The schematic diagram of the coagulation clarification system that Fig. 3 provides for the embodiment of the present invention 1 and 2;
The schematic diagram of the tubular type ultrafiltration system that Fig. 4 provides for the embodiment of the present invention 1 and 2;
Reference numeral:
1-pre-treatment softening equipment; 2-nanofiltration equipment; 3-reverse osmosis equipment;
4-crystallizer; 5-reconcentration equipment; 6-centrifugation apparatus;
101-settling pond; 102-sand filtration apparatus; 103-ion-exchange unit;
104-reaction tank; 105-tubular ultra-filtration membrane equipment.
Embodiment
Be clearly and completely described technical scheme of the present invention below in conjunction with accompanying drawing, obviously, described embodiment is the present invention's part embodiment, instead of whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art, not making the every other embodiment obtained under creative work prerequisite, belong to the scope of protection of the invention.
In describing the invention, it should be noted that, orientation or the position relationship of the instruction such as term " " center ", " on ", D score, "left", "right", " vertically ", " level ", " interior ", " outward " they be based on orientation shown in the drawings or position relationship; be only the present invention for convenience of description and simplified characterization; instead of instruction or imply the device of indication or element must have specific orientation, with specific azimuth configuration and operation, therefore can not be interpreted as limitation of the present invention.In addition, term " first ", " second ", " the 3rd " only for describing object, and can not be interpreted as instruction or hint relative importance.
In describing the invention, it should be noted that, unless otherwise clearly defined and limited, term " installation ", " being connected ", " connection " should be interpreted broadly, and such as, can be fixedly connected with, also can be removably connect, or connect integratedly; Can be mechanical connection, also can be electrical connection; Can be directly be connected, also indirectly can be connected by intermediary, can be the connection of two element internals.For the ordinary skill in the art, particular case above-mentioned term concrete meaning in the present invention can be understood.
Embodiment 1
As shown in Figure 1, the treatment unit of desulfurization wastewater provided by the invention, comprising: pre-treatment softening equipment 1, nanofiltration equipment 2, reverse osmosis equipment 3 and crystallizer 4;
The water outlet of pre-treatment softening equipment 1 is connected with the water-in of nanofiltration equipment 2, and the separation outlet of nanofiltration equipment 2 is connected with the water-in of reverse osmosis equipment 3, and the concentrated solution outlet of reverse osmosis equipment 3 is connected with crystallizer 4.
Specifically: power plant desulfurization island desulfurization wastewater out enters pre-treatment softening equipment 1, first remove suspended substance, basicity, hardness, heavy metal, COD etc. a large amount of in water, water outlet is separated monovalent ion and other ions through nanofiltration equipment 2, obtains the parting liquid containing monovalent ion and the concentrated solution containing other ions; The parting liquid of nanofiltration equipment enters reverse osmosis equipment 3 and concentrates, and the rate of recovery is about 60-80%, the saltiness about 30000 ~ 80000mg/L of the reverse osmosis concentrated water obtained, reverse osmosis produced water direct reuse.If reverse osmosis concentrated water-content is less or salts contg is higher, then directly enters crystallizer 4 such as crystallizer crystallization and obtain crystal salt.Concentrated solution contains other ions such as sulfate radical, flue gas desulphurization system is mixed into by the moisturizing of pipeline and power plant desulphurization system, the water yield of concentrated solution accounts for the 2-5% of the water inlet of flue gas desulphurization system, and can not affect sweetening effectiveness, finally excessive sulfate ion is discharged as gypsum.
Whole treating processes is simple, achieves the zero release of desulfurization wastewater.
If reverse osmosis concentrated water-content is more or salts contg is lower, reverse osmosis concentrated water enters reconcentration equipment 5, and the reconcentration liquid after reconcentration equipment 5 processes enters crystallizer 4;
Wherein, reconcentration equipment 5 can be any one or more in positive penetration equipment, efficient reverse osmosis equipment, electrodialysis appts;
Parting liquid through reconcentration enters pump circulation crystallizer by pipeline, temperature and pressure in crystallization control device, evaporative crystallization obtains the magma of a sodium chloride-containing, in order to obtain pure sodium-chlor crystal salt, magma also obtains pure sodium-chlor crystal salt by whizzer, and the crystallizer mother liquor of minute quantity is used for spraying dry or is used as fixed-end forces.Therefore, centrifugation apparatus 6 is also connected after crystallizer.
In addition, pre-treatment softening equipment 1 can be coagulation clarification system or tubular type ultrafiltration system;
Wherein, coagulation clarification system as shown in Figure 3, comprises the settling pond 101, sand filtration apparatus 102, the ion-exchange unit 103 that connect successively.
Owing to containing a large amount of suspended substances in desulfurization wastewater, basicity, the material such as metal ion and organism, the pre-treatment of desulfurization wastewater is specially: first desulfurization wastewater enters settling pond 101, settling pond 101 is by feeding lime and sodium carbonate, effectively can remove heavy metal ion and the organism of basicity in waste water and hardness ions and part, the residence time of desulfurization wastewater in settling pond 101 is 1.5 ~ 3h, settling pond 101 water outlet removes suspended substance further through sand filtration apparatus 102, sand filtration water outlet enters ion-exchange unit 103 and removes hardness ions further as calcium ions and magnesium ions etc., the water outlet of coagulation clarification system obtains softening water.
Tubular type ultrafiltration system as shown in Figure 4, comprises the reaction tank 104, device for ultrafiltration membrane 105, the ion-exchange unit 103 that connect successively.
According to the situation of water quality, desulfurization wastewater also can carry out pre-treatment in the following ways, particularly: first desulfurization wastewater enters reaction tank 104, feeding lime and sodium carbonate or sodium hydroxide and sodium carbonate stir, regulate more than pH to 11.5, the residence time is 1.5 ~ 3h, and the mixed solution obtained directly enters tubular ultra-filtration membrane equipment 105 by pump, the water outlet that filtration obtains enters ion-exchange unit 103 and removes hardness ions further, and the water outlet of ion-exchange unit 103 is softening water.
Embodiment 2
As shown in Figure 2, the treatment unit of desulfurization wastewater provided by the invention, comprising: pre-treatment softening equipment 1, nanofiltration equipment 2, reverse osmosis equipment 3 and crystallizer 4;
The water outlet of pre-treatment softening equipment 1 is connected with the water-in of reverse osmosis equipment 3, and the concentrated solution outlet of reverse osmosis equipment 3 is connected with the water-in of nanofiltration equipment 2, and the separation outlet of nanofiltration equipment 2 is connected with crystallizer 4.
Specifically: power plant desulfurization island desulfurization wastewater out enters pre-treatment softening equipment 1, first remove suspended substance, basicity, hardness, heavy metal, COD etc. a large amount of in water, water outlet first passes into reverse osmosis equipment 3 and concentrates, the rate of recovery is about 60-80%, the saltiness about 30000 ~ 80000mg/L of the reverse osmosis concentrated water obtained, reverse osmosis produced water direct reuse, reverse osmosis concentrated water enters nanofiltration equipment again, monovalent ion in reverse osmosis concentrated water and other ions separate by nanofiltration equipment, obtain the parting liquid containing monovalent ion and the concentrated solution containing other ions.If parting liquid content is less or salts contg is higher, then directly enters crystallizer crystallization and obtain crystal salt.Concentrated solution contains other ions such as sulfate radical, flue gas desulphurization system is mixed into by the moisturizing of pipeline and power plant desulphurization system, the water yield of concentrated solution accounts for the 2-5% of the water inlet of flue gas desulphurization system, and can not affect sweetening effectiveness, finally excessive sulfate ion is discharged as gypsum.
Whole treating processes is simple, achieves the zero release of desulfurization wastewater.
If parting liquid content is more or salts contg is lower, parting liquid enters reconcentration equipment 5, and the reconcentration liquid after reconcentration equipment 5 processes enters crystallizer 4;
Wherein, reconcentration equipment 5 can be any one or more in positive penetration equipment, efficient reverse osmosis equipment, electrodialysis appts;
Parting liquid through reconcentration enters pump circulation crystallizer by pipeline, temperature and pressure in crystallization control device, evaporative crystallization obtains the magma of a sodium chloride-containing, in order to obtain pure sodium-chlor crystal salt, magma also obtains pure sodium-chlor crystal salt by whizzer, and the crystallizer mother liquor of minute quantity is used for spraying dry or is used as fixed-end forces.Therefore, centrifugation apparatus 6 is also connected after crystallizer.
In addition, pre-treatment softening equipment 1 can be coagulation clarification system or tubular type ultrafiltration system;
Wherein, coagulation clarification system as shown in Figure 3, comprises the settling pond 101, sand filtration apparatus 102, the ion-exchange unit 103 that connect successively.
Owing to containing a large amount of suspended substances in desulfurization wastewater, basicity, the material such as metal ion and organism, the pre-treatment of desulfurization wastewater is specially: first desulfurization wastewater enters settling pond 101, settling pond 101 is by feeding lime and sodium carbonate, effectively can remove heavy metal ion and the organism of basicity in waste water and hardness ions and part, the residence time of desulfurization wastewater in settling pond 101 is 1.5 ~ 3h, settling pond 101 water outlet removes suspended substance further through sand filtration apparatus 102, sand filtration water outlet enters ion-exchange unit 103 and removes hardness ions further as calcium ions and magnesium ions etc., the water outlet of coagulation clarification system obtains softening water.
Tubular type ultrafiltration system as shown in Figure 4, comprises the reaction tank 104, device for ultrafiltration membrane 105, the ion-exchange unit 103 that connect successively.
According to the situation of water quality, desulfurization wastewater also can carry out pre-treatment in the following ways, particularly: first desulfurization wastewater enters reaction tank 104, feeding lime and sodium carbonate or sodium hydroxide and sodium carbonate stir, regulate more than pH to 11.5, the residence time is 1.5 ~ 3h, and the mixed solution obtained directly enters tubular ultra-filtration membrane equipment 105 by pump, the water outlet that filtration obtains enters ion-exchange unit 103 and removes hardness ions further, and the water outlet of ion-exchange unit 103 is softening water.
Embodiment 3
Desulfurization wastewater adopts following methods to process:
First desulfurization wastewater enters reaction tank 104, feeding lime and sodium carbonate stir, regulate more than pH to 11.5, the residence time is 1.5 ~ 3h, remove suspended substance, basicity, hardness, heavy metal, COD etc. a large amount of in water, the mixed solution obtained directly enters tubular ultra-filtration membrane equipment 105 by pump, and the water outlet that filtration obtains enters ion-exchange unit 103 and removes hardness ions further, and the water outlet of ion-exchange unit 103 is softening water;
Softening water enters nanofiltration equipment 2, the monovalent ion in softening water and other ions is separated, obtain the parting liquid containing monovalent ion and the concentrated solution containing other ions respectively by the nanofiltration membrane of nanofiltration equipment 2;
Concentrated solution contains other ions such as sulfate radical, flue gas desulphurization system is mixed into by the moisturizing of pipeline and power plant desulphurization system, the water yield of concentrated solution accounts for the 2-5% of the water inlet of flue gas desulphurization system, and can not affect sweetening effectiveness, finally excessive sulfate ion is discharged as gypsum;
Parting liquid containing monovalent ion is introduced into reverse osmosis equipment 3 and concentrates, the rate of recovery is about 60-80%, the saltiness about 30000 ~ 80000mg/L of the reverse osmosis concentrated water obtained, reverse osmosis concentrated water by pipeline enter reconcentration equipment 5 as filter membrane be the positive penetration equipment of FO film, filter membrane is efficient reverse osmosis equipment, the electrodialysis appts of RO film, saltiness in the reconcentration water obtained is processed at 120000-180000mg/L through reconcentration equipment 5, wherein, reverse osmosis equipment 3 and reconcentration equipment 5 produce water and directly recycle;
The reconcentration water obtained is entered pump circulation crystallizer by pipeline, temperature and pressure in crystallization control device, evaporative crystallization obtains the magma of a sodium chloride-containing, magma obtains pure sodium-chlor crystal salt by whizzer, and the crystallizer mother liquor of minute quantity is used for spraying dry or is used as fixed-end forces.
Embodiment 4
Desulfurization wastewater adopts following methods to process:
First desulfurization wastewater enters settling pond 101, settling pond 101 is by adding sodium hydroxide and sodium carbonate, regulate more than pH to 11.5, the residence time of desulfurization wastewater in settling pond 101 is 1.5 ~ 3h, the heavy metal ion of the basicity in effective removal waste water and hardness ions and part and organism, settling pond 101 water outlet removes suspended substance further through sand filtration apparatus 102, sand filtration water outlet enters ion-exchange unit 103 and removes hardness ions further as calcium ions and magnesium ions etc., and the water outlet of coagulation clarification system obtains softening water;
Softening water passes into reverse osmosis equipment 3 and concentrates, the rate of recovery is about 60-80%, the saltiness about 30000 ~ 80000mg/L of the reverse osmosis concentrated water obtained, reverse osmosis produced water direct reuse, reverse osmosis concentrated water enters nanofiltration equipment 2 again, monovalent ion in reverse osmosis concentrated water and other ions separate by nanofiltration equipment 2, obtain the parting liquid containing monovalent ion and the concentrated solution containing other ions;
Concentrated solution contains other ions such as sulfate radical, flue gas desulphurization system is mixed into by the moisturizing of pipeline and power plant desulphurization system, the water yield of concentrated solution accounts for the 2-5% of the water inlet of flue gas desulphurization system, and can not affect sweetening effectiveness, finally excessive sulfate ion is discharged as gypsum;
Parting liquid containing monovalent ion by pipeline enter reconcentration equipment 5 as filter membrane be the positive penetration equipment of FO film, filter membrane is efficient reverse osmosis equipment, the electrodialysis appts of RO film, saltiness in the reconcentration water obtained is processed at 120000-180000mg/L through reconcentration equipment 5, wherein, reverse osmosis equipment 3 and reconcentration equipment 5 produce water direct reuse;
The reconcentration water obtained is entered pump circulation crystallizer by pipeline, temperature and pressure in crystallization control device, evaporative crystallization obtains the magma of a sodium chloride-containing, magma obtains pure sodium-chlor crystal salt by whizzer, and the crystallizer mother liquor of minute quantity is used for spraying dry or is used as fixed-end forces.
Last it is noted that above each embodiment is only in order to illustrate technical scheme of the present invention, be not intended to limit; Although with reference to foregoing embodiments to invention has been detailed description, those of ordinary skill in the art is to be understood that: it still can be modified to the technical scheme described in foregoing embodiments, or carries out equivalent replacement to wherein some or all of technical characteristic; And these amendments or replacement, do not make the essence of appropriate technical solution depart from the scope of various embodiments of the present invention technical scheme.
Claims (10)
1. a treatment process for desulfurization wastewater, is characterized in that, comprises the following steps:
(a), desulfurization wastewater is carried out pre-treatment, obtain softening water;
B (), by the monovalent ion in described softening water and other ions separately, obtains the parting liquid containing monovalent ion and contains the concentrated solution of other ions;
(c), described parting liquid is carried out crystallization, obtain crystal salt;
(d), described concentrated solution supply flue gas desulphurization system;
Wherein, in step (b), the softening water before the monovalent ion in described softening water and other ions being separated or parting liquid afterwards also comprise concentrated step.
2. treatment process according to claim 1, is characterized in that, in step (b), adopts nanofiltration membrane the monovalent ion in described softening water and divalent ion to be separated;
Described concentrating preferably adopts reverse osmosis concentration, the water direct reuse produced in described reverse osmosis concentrated compression process.
3. treatment process according to claim 2, is characterized in that, in step (c), described parting liquid also comprises the step of reconcentration before carrying out crystallization, and through described reconcentration, the saltiness in the condensed water obtained is at more than 120000mg/L;
The water direct reuse produced in described reconcentration process.
4. a treatment unit for desulfurization wastewater, is characterized in that, comprising: pre-treatment softening equipment, nanofiltration equipment, reverse osmosis equipment and crystallizer;
Described pre-treatment softening equipment and described nanofiltration equipment connection, the separation outlet of described nanofiltration equipment is connected with crystallizer;
Described reverse osmosis equipment exports between described crystallizer between described pre-treatment softening equipment with described nanofiltration equipment or being separated of described nanofiltration equipment.
5. treatment unit according to claim 4, is characterized in that, is also connected with reconcentration equipment before described crystallizer.
6. treatment unit according to claim 5, is characterized in that, described reconcentration equipment is any one or more in positive penetration equipment, efficient reverse osmosis equipment, electrodialysis appts.
7. treatment unit according to claim 4, is characterized in that, described device also comprises centrifugation apparatus, and described crystallizer is connected with described centrifugation apparatus;
Described pre-treatment softening equipment is coagulation clarification system or tubular type ultrafiltration system.
8. treatment unit according to claim 7, is characterized in that, described coagulation clarification system comprises the settling pond, sand filtration apparatus, the ion-exchange unit that connect successively.
9. treatment unit according to claim 7, is characterized in that, described tubular type ultrafiltration system comprises the reaction tank, tubular ultra-filtration membrane equipment, the ion-exchange unit that connect successively.
10. the treatment unit according to any one of claim 4-9, is characterized in that, each connection is and is connected by pipeline.
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