CN105314773A - Wet desulphurization wastewater recycling method and apparatus thereof - Google Patents
Wet desulphurization wastewater recycling method and apparatus thereof Download PDFInfo
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- CN105314773A CN105314773A CN201410327752.9A CN201410327752A CN105314773A CN 105314773 A CN105314773 A CN 105314773A CN 201410327752 A CN201410327752 A CN 201410327752A CN 105314773 A CN105314773 A CN 105314773A
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Abstract
The invention discloses a wet desulphurization wastewater recycling method and an apparatus thereof. Collected desulphurization wastewater from a gypsum dehydration device enters a flocculation reactor and is pretreated, the desulphurization wastewater is neutralized, flocculated, softened and clarified, and sludge is sent to a sludge treatment device and is dehydrated; separated clarified water undergoes two-stage ultrafiltration, nanofiltration and reverse osmosis desalting, and desalted water returns to a desulphurization system or other water systems. Desalted concentrated water is a high concentrate salt (NaCl) solution, and the high concentrate salt (NaCl) solution goes through a sodium hypochlorite generator to directly electrolyze salt-containing water in order to prepare a sodium hypochlorite solution, and the sodium hypochlorite solution can be used for sterilizing and disinfecting water to realize effective utilization, changing of wastes into valuables and recycling of the desulphurization wastewater, realize complete recycling of the desulphurization wastewater and realize resource recycling. Further, the method has the advantages of no influences on other systems in a power plant, strong practicality, low investment, realization of resource recycling, and wide popularization and use values.
Description
Technical field
The present invention relates to electric power, metallurgy, wastewater from chemical industry, resource recycling, energy-conserving and environment-protective technical field, be specifically related to a kind of wet desulphurization waste water reclamation Application way and device thereof.
Background technology
Wet desulphurization is the desulfurization method of unique large-scale commercial application in the world at present, is the technical way controlling coal-burning power plant's sulfur dioxide emissions.The desulfurization of Wingdale one gypsum wet is current domestic and international most popular a kind of fume desulphurization method.
The flue gas that boiler produces enters wet desulfurization system after electric precipitator dedusting, in absorption tower, complete washing desulphurization, after mist eliminator removing droplet, enter air by chimney.Along with flue gas washing constantly carries out in absorption tower, absorption agent effective constituent constantly consumes, the calcium sulfite generated generates gypsum through forced oxidation, and the muriate when absorption tower washing flue gas in flue gas is also dissolved by washing and the chlorion that enters of sulfur removal technology water-band and produce chlorion enrichment in absorption liquid.Increasing of chlorine ion concentration brings two adverse influences: a pH value being reduction of absorption liquid, thus causes decline and the CaSO of desulfurization degree
4the increase of fouling tendency, gypsum is difficult to dehydration; Two is can produce serious etching problem to desulfurizer.The desulfurization wastewater that desulphurization system periodic exhaustion is certain, controls at (20000mg/l) below with the concentration maintaining chlorion in the slurries of absorption tower.The water quality characteristics of desulfurization wastewater: 1. acid, general pH value is 4 ~ 6; 2. turbidity of wastewater is high, suspension content large (gypsum particle, SiO
2, Al and Fe oxyhydroxide), concentration can reach several ten thousand ppm.Most particulate matter viscosity is low: 3. containing plurality of heavy metal, as Cr, As, Cd, Pb, Hg, Cu etc.; 4. saltiness is high, containing a large amount of Cl in waste water
-, F
-, SO
3 2-, SO
4 2-, Ca
2+, Mg
2+.Wherein chlorion Cl
-concentration is up to ~ 20000mg/l.So desulfurization wastewater has very strong corrodibility to desulphurization system pipeline, various metallic substance and associated power equipment, cause the process of desulfurization supersalinity waste water and recycle very difficult.
The process of desulfurization wastewater must consider the removal degree of following index: 1. pH value; 2. suspended solids composition and content: 3. heavy metal content; 4. Ca
2+, Mg
2+ion fouling tendency, high saltiness and high Cl-concentration.
Desulfurization wastewater processing mode conventional at present both at home and abroad mainly contains:
Chemical flocculation process: most domestic power plant wet desulphurization waste water adopts the methods such as neutralization, flocculation, reaction, precipitation, separation to carry out pre-treatment to desulfurization wastewater at present, mud carries out press filtration outward transport, the general qualified discharge of the desulfurization wastewater after process or the simple reuse such as dry ash humidification, grey field spray.The program is from current operating performance, and complex treatment process, medicine system is huge, does not substantially all reach emission standard.The high saltiness of waste water after process and high Cl-concentration, extremely strong to the corrodibility of metal and equipment, cause the desulfurization wastewater after processing cannot be back to other system.For the difficult point problem that the overwhelming majority's domestic power plant desulfurization Sewage advanced treatment technology and reuse are wastewater treatments, it is the technology that electric power enterprise is unable to reach always.
Evaporation: individual power plants is attempted desulfurization wastewater and adopted secondary pretreatment technology, greatly reduce the content of suspended substance in waste water, the water outlet penetration depth treatment system again of pretreatment system: comprise evaporation+crystallization processes, desulfurization wastewater can be made to be separated into water (steam) and the solid waste of high-quality by evaporation and drying installation, desulfurization wastewater thoroughly achieves innoxious.Such as Heyuan system for treating wastewater from power plant has started the beginning of China's desulfurization wastewater treatment technology, it is the power plant that domestic first hand adopts desulfurization wastewater " pre-treatment+evaporation+crystallization " technique, desulfurization wastewater treatment capacity is about 20t/h, invest about ~ 8,000 ten thousand yuan, but there is the higher drawback of cost of investment and running cost, energy consumption in the method, this technology fails extensively to promote.
Summary of the invention
For above-mentioned defect or deficiency, the object of the present invention is to provide a kind of wet desulphurization waste water reclamation Application way and device thereof, can to suspended substance, soluble solid, heavy metal, supersalinity, Ca in desulfurization wastewater
2+, Mg
2+, Cl
-, F
-ion, according to different qualities, different process is adopted to carry out processing respectively, desalination water after final reverse osmosis desalination is recycled, concentrated rear Halite water is prepared into qualified clorox final mean annual increment solution, can be used for the sterilization of water body, sterilization, the effective utilization reaching desulfurization wastewater, the object turning waste into wealth, recycle, can realize desulfurization wastewater and recycle completely.
For reaching above object, technical scheme of the present invention is:
A kind of wet desulphurization waste water reclamation Application way, comprises the following steps:
1) desulfurization wastewater after, collecting gypsum dewatering equipment enters neutralization, flocculation pretreatment unit, desulfurization wastewater is neutralized, flocculate, soften, clarify, filter, primary water meeting tier 2 process entrance criterion after separation, mud is then delivered in sludge dehydration device and is dewatered;
2), enter two-pass reverse osmosis through the primary water of removal heavy metal, suspended substance, calcium, magnesium ion post softening and carry out desalination.Adopt nanofiltration, reverse osmosis membrane processing device, the desalination water after reverse osmosis desalination is back to desulphurization system or other water system, realizes desulfurization wastewater minimizing.
3), nanofiltration membrane is adopted to realize softening further water to the selection of different valence state ion through characteristic, nanofiltration can retain the ion of more than divalence and other particles, institute through the ion (as sodium, potassium, chlorion) only having water molecules and some monovalencies.
4) condensed water, after reverse osmosis membrane processing is high salt concentration (NaCl) solution, reverse osmosis concentrated shrink enters hypochlorite generator, Direct Electrolysis brackish water is prepared into clorox final mean annual increment solution, can be used for the sterilization of water body, sterilization, realizes the recycle of resource.
Described step 1) in and flocculation plant adopt electricity flocculation or chemical flocculation pretreatment unit.
A kind of wet desulphurization waste water reclamation utilizes device, comprising: the desulfurization wastewater that gypsum dehydration system is discharged enters neutralization, flocculation, softening installation successively, and clarifying plant, and the mud of clarifying plant is delivered to sludge dehydration device and dewaters.The clear liquor of clarifying plant enters nanofiltration, reverse osmosis membrane processing device, and the desalination water after nanofiltration, reverse osmosis membrane processing device desalination is back to desulphurization system; The desulfurization wastewater of reverse osmosis concentration enters hypochlorite generator, and Direct Electrolysis brackish water is prepared into clorox final mean annual increment solution, can be used for the sterilization of water body, sterilization, realizes the recycling of resource.
Described nanofiltration device adopts nanofiltration membrane to realize softening further water to the selection of different valence state ion through characteristic, nanofiltration membrane can retain the ion of more than divalence and other particles, institute through the ion (as sodium, potassium, chlorion) only having water molecules and some monovalencies.
Described reverse osmosis unit adopts reverse osmosis membrane to carry out desalination, and the desalination water after desalination is back to desulphurization system, realizes desulfurization wastewater minimizing.The high saliferous condensed water of reverse osmosis concentration, based on high salt concentration (NaCl), can be used for electrolytic process and prepares chlorine bleach liquor.
Described hypochlorite generator's device, the high saliferous condensed water of reverse osmosis concentration utilizes hypochlorite generator's device, can be prepared into clorox final mean annual increment solution by Direct Electrolysis brackish water, can be used for the sterilization of water body, sterilization, realize the recycle of resource.
Described flocculation plant entry checking apparatus table comprises intake pressure, under meter.
Described hypochlorite generator's device portal arranges the measuring instrument such as conductivitimeter, under meter.
The mud of described clarifying plant discharge is then delivered to sludge treatment equipment and is dewatered.
Compared with the prior art, beneficial effect of the present invention is:
The invention provides a kind of wet desulphurization waste water reclamation Application way and device thereof, this processing method in optimized mode to suspended substance, soluble solid, heavy metal, supersalinity, Ca in desulfurization wastewater
2+, Mg
2+, Cl
-, F
-separating treatment has been carried out respectively according to substance characteristics Deng material.First the desulfurization wastewater that gypsum dewatering equipment is discharged is neutralized, flocculates, softens, clarifies, filtered, remove suspended substance, primary water meeting tier 2 process entrance criterion.Second-stage treatment adopts reverse osmosis to carry out desalination, and second-stage treatment carries out nanofiltration, reverse osmosis membrane except Ficus caricaL to softening primary water, realizes desulfurization wastewater minimizing.Desalination water after reverse osmosis desalination is back to desulphurization system; Condensed water after reverse osmosis decrement is high salt concentration (NaCl) solution, reverse osmosis concentrated shrink enters hypochlorite generator, Direct Electrolysis brackish water is prepared into clorox final mean annual increment solution, can be used for the sterilization of water body, sterilization, realizes the recycling of resource.The separated collection of solid waste, Halite water reclaims and is prepared into clorox final mean annual increment solution, reaches desulfurization wastewater and recycles completely, realize desulfurization wastewater without discharge.
In addition, present method is on other system of power plant without impact, and practical, this device technique is simple, and cost of investment is low, realizes the recycling of resource, thoroughly solves high slat-containing wastewater and recycles problem, has popularization, use value widely.
Accompanying drawing explanation
Fig. 1 is present invention process FB(flow block).
In figure, 1 is desulfuration absorbing tower, 2 is gypsum dewatering equipment, and 3 is neutralization, flocculation plant, and 4 is clarifying plant, 4-1 is clarifying plant sludge outlet, 4-2 is clarifying plant clear liquor relief outlet, 5 ultra-filtration equipment, 6 reverse osmosis membrane processing devices, 7 is hypochlorite generator's device, and 8 is sludge dehydration device.
Embodiment
Below in conjunction with accompanying drawing, the present invention is described in detail.
The invention provides a kind of wet desulphurization waste water reclamation Application way, comprise the following steps:
1) desulfurization wastewater after, collecting gypsum dewatering equipment enters neutralization, flocculation pretreatment unit, desulfurization wastewater is neutralized, flocculate, soften, clarify, filter, primary water meeting tier 2 process entrance criterion after separation, mud is then delivered in sludge dehydration device and is dewatered;
By adding alkali, complexing agent, flocculation agent, coagulant aids, adjusted to ph in flocculation plant, suspended substance in waste water, heavy metal, softening water body, regulating water quality can be removed.
By adding neutralizing agent, part acid group, halogen family ion are neutralized as corresponding inorganic salt, to part heavy metal be precipitated out completely with the form of colloid, the weakly alkaline atmosphere after waste water neutralize, be conducive to carrying out complexing and crystalline deposit for heavy metal ion further.
Do not introduce hardness positively charged ion, the temporary hardness in water can be removed simultaneously.
Wherein, described flocculation plant adopts electricity flocculation or chemical flocculation device.Concrete, electrocoagulation flocculates also known as electricity, is exactly under external voltage effect, utilizes soluble anode to produce a large amount of positively charged ion, carries out coagulative precipitation to colloid waste water.Usually select iron or aluminium as anode material, metal electrode (as aluminium) is placed in processed water, then passes to direct current, now metal anode generation oxidizing reaction.The aluminum ion produced is hydrolyzed, is polymerized in water, and generate a series of multinuclear hydrolysate and play cohesion, its process is substantially identical with chemical coagulation process with mechanism.Meanwhile, the hydrogen of the nascent state in electrocoagulation device, negative electrode produced, its reducing power is very strong, can play reduction reaction with the pollutent in waste water, or generates hydrogen.Anode also may there is oxygen release.Hydrogen and oxygen occur with the form of microbubble, contact can obtain good adhesion property in water treatment procedure with suspended particle, thus improve water treatment efficiency.In a word, the former water and waste water of electrocoagulation process is the synergy of various procedures, and suspended substance is easily removed under these effects.Mud is then delivered in sludge dehydration device and is dewatered.
2), through neutralization, flocculation pre-treatment (neutralization, except heavy, except solid) waste water after coagulation, in its water, the impurity such as pH value, SS, heavy metal has been removed completely, and water intermediate ion is based on chlorion and sodium ion.Through the primary water meeting tier 2 process entrance criterion of removal heavy metal, suspended substance, calcium, magnesium ion post softening, enter nanofiltration, reverse osmosis unit, second-stage treatment adopts reverse osmosis to carry out desalination.Desalination water after reverse osmosis desalination is back to desulphurization system.
In this step, the technology of nanofiltration and reverse osmosis conbined usage is commonly called as---bi-membrane method, nanofiltration device adopts nanofiltration membrane to realize softening further water to the selection of different valence state ion through characteristic, nanofiltration membrane can retain the ion of more than divalence and other particles, institute through the ion (as sodium, potassium, chlorion) only having water molecules and some monovalencies.Adopt reverse osmosis membrane to carry out desalination, the ratio of desalinization of reverse osmosis membrane to sodium ion, potassium ion, chlorion has exceeded 98%.After reverse osmosis membrane desalination, fresh water reuse is to desulphurization system.Condensed water after reverse osmosis membrane processing is high salt concentration (NaCl) solution, and reverse osmosis concentrated shrink enters hypochlorite generator and processes.
3) condensed water, after nanofiltration, reverse osmosis concentrated compression apparatus decrement, for high salt concentration (NaCl) solution, condensed water enters hypochlorite generator, Direct Electrolysis brackish water is prepared into qualified clorox final mean annual increment solution, can be used for the sterilization of water body, sterilization, realize the recycling of resource.Reach the object that desulfurization wastewater is recycled completely.
In this step, hypochlorite generator, adds into electrolyzer by weak brine metering, connects the electrolysis of anode and cathode direct supply generate clorox by silicon rectifier.
As shown in Figure 1, the invention provides a kind of wet desulphurization waste water reclamation and utilize device, comprise: the waste water that the gypsum dehydration system (2) that system connects successively is discharged, neutralization, flocculation, softening installation (3), and clarifying plant (4), sludge outlet (4-1) mud of clarifying plant (4) enters sludge dehydration device (8) and dewaters; The clear liquor relief outlet (4-2) of clarifying plant (4) enters nanofiltration device (5), reverse osmosis membrane processing device (6), desalination water after reverse osmosis membrane processing device (6) desalination is back to desulphurization system, reverse osmosis concentrated shrink enters hypochlorite generator's device (7), and Direct Electrolysis brackish water is prepared into qualified clorox final mean annual increment solution.
Wherein, neutralization, flocculation plant (3) entry checking apparatus table comprise intake pressure, under meter, water inlet pH value, water inlet conductivitimeter; Hypochlorite generator's device (7) entrance arranges the measuring instrument such as conductivitimeter, under meter.
It should be noted that, a whole set of wet desulphurization waste water reclamation utilizes apparatus control system by computer, programmable controller PLC and topworks thereof and measuring instrument composition.Can, according to the salinity of the load variations of waste water, waste water, turbidity and set different parameters, make it to reach optimal running effect during use.Measuring instrument comprises intake pressure, feed water flow gauge; The measuring units such as delivery turbidity meter, water outlet salometer, specific conductivity.
In sum
A kind of wet desulphurization of the present invention waste water reclamation utilizes device to be the high saliferous desulfurization wastewater recovery process method of a kind of uniqueness newly developed, and this processing method is for suspended substance, soluble solid, heavy metal, supersalinity, Ca in wet desulphurization waste water
2+, Mg
2+, Cl
-, F
-ion, according to different qualities, different process is adopted to carry out processing respectively, desalination water after final reverse osmosis desalination is recycled, concentrated rear Halite water is prepared into qualified clorox final mean annual increment solution, can be used for the sterilization of water body, sterilization, the effective utilization reaching desulfurization wastewater, the object turning waste into wealth, recycle, can realize desulfurization wastewater and recycle completely.Complete assembly without impact, is invested less, practical on other system of power plant, has popularization, use value widely.
The application of wet desulphurization Sewage advanced treatment recovery and utilization technology, desulfurization wastewater is realized after pretreatment for all Wet Fgd By Limestone technique provides, the waste water high-efficiency low cost desalting treatment technology of supersalinity, high chloride ion, achieves the recycling completely truly of power plant desulfurization waste water, discharges without desulfurization wastewater.
Claims (10)
1. wet desulphurization waste water reclamation Application way and a device thereof, is characterized in that, comprises the following steps:
1) desulfurization wastewater after, collecting gypsum dewatering equipment enters neutralization, flocculation pretreatment unit, desulfurization wastewater is neutralized, flocculate, soften, clarify, filter, primary water meeting tier 2 process entrance criterion after separation, mud is then delivered in sludge dehydration device and is dewatered;
2), enter two-pass reverse osmosis through the primary water of removal heavy metal, suspended substance, calcium, magnesium ion post softening and carry out desalination.Adopt nanofiltration, reverse osmosis membrane processing device, the desalination water after reverse osmosis desalination is back to desulphurization system or industrial water system, realizes desulfurization wastewater minimizing.
3), nanofiltration membrane is adopted to realize softening further water to the selection of different valence state ion through characteristic, nanofiltration can retain the ion of more than divalence and other particles, institute through the ion (as sodium, potassium, chlorion) only having water molecules and some monovalencies.
4) desalination water, after reverse osmosis desalination is back to desulphurization system or industrial water system, condensed water after reverse osmosis membrane processing is high salt concentration (NaCl) solution, reverse osmosis concentrated shrink enters hypochlorite generator, Direct Electrolysis brackish water is prepared into clorox final mean annual increment solution, can be used for the sterilization of water body, sterilization, realize the recycle of resource.
2. wet desulphurization waste water reclamation according to claim 1 utilizes device, it is characterized in that, described flocculation plant adopts electricity flocculation or chemical flocculation.
3. a wet desulphurization waste water reclamation utilizes device, it is characterized in that, comprising: gypsum dehydration system (2), neutralization, flocculation, softening installation (3), clarifying plant (4), nanofiltration device (5), reverse osmosis membrane processing device (6), hypochlorite generator's device (7), sludge dehydration device (8); The desulfurization wastewater that gypsum dehydration system (2) is discharged enters neutralization, flocculation, softening installation (3), then carry out solid-liquid separation by clarifying plant (4), sludge outlet (4-1) mud of clarifying plant (4) enters sludge dehydration device (8) and dewaters; The clear liquor relief outlet (4-2) of clarifying plant (4) enters nanofiltration device (5), salt solution after nanofiltration is softening further enters reverse osmosis membrane processing device (6), desalination water after reverse osmosis membrane processing device (6) desalination is back to desulphurization system (1), the high saliferous condensed water of reverse osmosis enters hypochlorite generator's device (7), be prepared into qualified chlorine bleach liquor's finished product, can be used for the sterilization of water body, sterilization.
4. wet desulphurization waste water reclamation according to claim 3 utilizes device, it is characterized in that, described flocculation plant (3), neutralizes desulfurization wastewater, flocculates, clarifies, filters, softening removal hardness, the primary water meeting tier 2 process entrance criterion after separation.
5. wet desulphurization waste water reclamation according to claim 3 utilizes device, it is characterized in that, described clarifying plant (4), adopts mechanical accelerating purifying pool or other pattern settling pond, carries out solid-liquid separation.
6. wet desulphurization waste water reclamation according to claim 3 utilizes device, it is characterized in that, described nanofiltration device (5), employing nanofiltration membrane realize softening further water to the selection of different valence state ion through characteristic, nanofiltration membrane can retain the ion of more than divalence and other particles, institute through the ion (as sodium, potassium, chlorion) only having water molecules and some monovalencies.
7. wet desulphurization waste water reclamation according to claim 3 utilizes device, it is characterized in that, reverse osmosis membrane processing device (6), reverse osmosis membrane is adopted to carry out desalination to the primary water through nanofiltration post softening, desalination water after desalination is back to desulphurization system, realizes desulfurization wastewater minimizing.The high saliferous condensed water of reverse osmosis concentration, based on high salt concentration (NaCl), can be used for electrolytic process and prepares chlorine bleach liquor.
8. wet desulphurization waste water reclamation according to claim 3 utilizes device, it is characterized in that, hypochlorite generator's device (7), the high saliferous condensed water of reverse osmosis concentration utilizes hypochlorite generator's device, can be prepared into clorox final mean annual increment solution.
9. wet desulphurization waste water reclamation according to claim 4 utilizes device, it is characterized in that, described flocculation plant (3) ingress arranges the measuring instrument of intake pressure and flow, water inlet pH value, water inlet conductivitimeter; Hypochlorite generator's device (7) entrance arranges the measuring instrument such as conductivitimeter, under meter.
10. wet desulphurization waste water reclamation according to claim 3 utilizes device, it is characterized in that, the mud that described clarifying plant (4) discharges then is delivered to sludge treatment equipment (8) and dewatered.Sludge treatment equipment (8) adopts plate and frame(type)filter press or centrifuge.
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