CN104926008A - Wet desulfurization wastewater zero emission process and device thereof - Google Patents
Wet desulfurization wastewater zero emission process and device thereof Download PDFInfo
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Abstract
The invention discloses a wet desulfurization wastewater zero emission process and a device thereof; desulfurization wastewater behind a gypsum dewatering device is collected and enters a flocculation reactor, the desulfurization wastewater is softened, flocculated and clarified, and sludge is sent to a sludge processing device for dewatering; the clarified water after separation is desalted, the desalted water is reused in a desulfurization system, concentrated water is sent to an evaporation crystallization device, waste heat of a boiler flue gas is used for evaporation crystallization, and high-quality water steam is obtained after evaporation; an evaporated crystallized substance and the water steam are subjected to gas-solid separation, the high-quality water steam is sent into a desulfurization absorption tower for recycling, and the crystallized substance is discharged together with fly ash. The high-quality water steam can be completely recycled in the desulfurization adsorption tower; suspended solids, dissolved solids, heavy metals, high salt, and Ca<2+>, Mg<2+>, Cl<+> and F<-> ions and other substances are cured, separated and collected, the purpose of complete recycling of the desulfurization wastewater is achieved, and zero emissions of the desulfurization wastewater can be achieved. In addition, the method has no effect on other systems of a power plant, and has the advantages of high practicability, low investment, and wide popularization and use value.
Description
Technical field
The present invention relates to thermal power plant's energy, resource recycling, energy-conserving and environment-protective technical field, particularly relate to a kind of heat-engine plant wet desulfurization wastewater technique of zero discharge 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 process without drainage of waste water and device thereof, can to suspended substance, soluble solid, heavy metal, supersalinity, Ca in desulfurization wastewater
2+, Mg
2+, Cl
-, F
-carry out separating treatment, desulfurization wastewater can have been realized and recycle completely.
For reaching above object, technical scheme of the present invention is:
A kind of wet desulphurization process without drainage of waste water method, comprises the following steps:
1), collect the desulfurization wastewater after gypsum dewatering equipment and enter flocculation plant, soften desulfurization wastewater, flocculate, clarify, filter, the primary water meeting tier 2 process entrance criterion after separation, mud is then delivered in sludge dehydration device and is dewatered;
2), through remove calcium, magnesium ion, heavy metal, suspended substance post softening primary water enter ultrafiltration, reverse osmosis concentrated compression apparatus, the desalination water after desalination is back to desulphurization system, realizes desulfurization wastewater minimizing.
3), supercharging is carried out to the condensed water after decrement after, enter evaporated crystallization device and carry out evaporative crystallization, evaporated crystallization device utilizes residual heat from boiler fume to carry out evaporative crystallization, obtains highly purified water vapour;
4), evaporative crystallization thing and water vapour carry out gas solid separation by gas-solid separating device, obtains highly purified water vapour and crystallisate;
5) water vapour, after removing crystallisate enters in desulfuration absorbing tower and all recycles, and crystallisate is together discharged with flyash.
Described step 3) be specially and utilize residual heat from boiler fume to carry out evaporative crystallization to waste water, without the need to other thermal source of power plant, belong to UTILIZATION OF VESIDUAL HEAT IN.
Described flocculation plant adopts electricity flocculation or chemical flocculation device.
A kind of wet desulphurization process without drainage of waste water device, comprising: the desulfurization wastewater that gypsum dehydration system is discharged enters flocculation plant 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 ultrafiltration, reverse osmosis concentrated compression apparatus, and the desalination water after ultrafiltration, reverse osmosis concentrated compression apparatus desalination is back to desulphurization system; The desulfurization wastewater of concentrated minimizing enters evaporated crystallization device, and gas-solid separating device, the pneumatic outlet access desulfuration absorbing tower entrance of gas-solid separating device.
Described evaporated crystallization device utilizes residual heat from boiler fume to carry out evaporative crystallization, the water droplet be atomized in evaporated crystallization device and high-temperature flue gas carry out rapidly conducting heat, mass transfer, evaporation, water enters desulphurization absorption tower system with the water of high-quality (steam) gaseous state, and the system of being desulfurized recycled.Belong to resource recycling.
The ingress of described evaporated crystallization device is provided with flue-gas temperature and flow measurement device.
Described flocculation plant entry checking apparatus table comprises intake pressure, 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 process without drainage of waste water 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 softened, flocculates, clarifies, filtered, remove suspended substance, primary water meeting tier 2 process entrance criterion.Second-stage treatment carries out ultrafiltration to softening primary water, reverse osmosis concentration is separated, and realizes desulfurization wastewater minimizing.Desalination water after desalination is back to desulphurization system; Condensed water after decrement, through evaporated crystallization device, utilizes residual heat from boiler fume to carry out evaporative crystallization to waste water, after gas solid separation, by the soluble solid in primary water, high saliferous, Cl
-, F
-the materials such as ion have carried out solidification crystallization, obtain the water vapor of high-quality, and water vapor is sent in desulfuration absorbing tower and can be recycled completely.High salinity and the separated collection of solid waste, reach desulfurization wastewater and recycle completely, realize zero release.In addition, present method is on other system of power plant without impact, and practical, cost of investment is low, has popularization, use value widely.
Further, present method make use of power plant boiler fume afterheat, carries out evaporative crystallization, effectively make use of power plant boiler fume afterheat, reach the object of resource, heat recovery by power plant boiler high-temperature flue gas waste heat.Desulfurization wastewater minimizing designs, and is conducive to the control to evaporative crystallization.
Present invention also offers a kind of wet desulphurization waste water zero discharge device, by utilizing flocculation plant, clarifying plant, ultrafiltration, reverse osmosis concentrated compression apparatus, the desulfurization wastewater that gypsum dewatering equipment is discharged is softened, flocculates, clarifies, filtered, remove suspended substance, be met the primary water of second-stage treatment entrance criterion, ultrafiltration, reverse osmosis concentrated compression apparatus carry out ultrafiltration, reverse osmosis concentration separation to softening primary water, realize desulfurization wastewater minimizing.Condensed water after decrement carries out evaporative crystallization by evaporated crystallization device, after gas-solid separating device gas solid separation, by the soluble solid in condensed water, heavy metal, high saliferous, Ca
2+, Mg
2+, Cl
-, F
-the materials such as ion have carried out separating treatment respectively according to substance characteristics, obtain the water vapor of high-quality, and this water vapor is sent in desulfuration absorbing tower and can be recycled completely, reaches the object of desulfurization wastewater zero release.This device effectively can remove the impurity in desulfurization wastewater, high salinity, Cl
-, F
-ion, this apparatus structure is simple, and cost of investment is low, on other system of power plant without impact, practical, achieves the recycling completely truly of power plant desulfurization waste water.
Accompanying drawing explanation
Fig. 1 is wet desulphurization waste water zero discharge device process flow diagram of the present invention.
In figure, 1 is desulfuration absorbing tower, 2 is gypsum dewatering equipment, and 3 is softening, flocculation plant, and 4 is clarifying plant, 4-1 is clarifying plant sludge outlet, 4-2 is clarifying plant clear liquor relief outlet, 5 ultrafiltration, reverse osmosis concentrated compression apparatus, and 6 is evaporated crystallization device, 7 is gas-solid separating 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 process without drainage of waste water method, comprise the following steps:
1), collect the desulfurization wastewater after gypsum dewatering equipment and enter flocculation plant, soften desulfurization wastewater, flocculate, clarify, filter, the 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.
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 remove calcium, magnesium ion, heavy metal, suspended substance post softening primary water enter ultrafiltration, reverse osmosis concentrated compression apparatus, the desalination water after desalination is back to desulphurization system.
In this step, the technology of ultrafiltration and reverse osmosis conbined usage is commonly called as---and bi-membrane method, after adopting ultrafiltration and sea water desaltination membrane concentration, fresh water reuse is to desulphurization system, and dense water enters the process of boiler afterheat vapo(u)rization system.Realize desulfurization wastewater minimizing, reduce evaporation and crystallization system capacity, be conducive to the control to evaporative crystallization.
3) after the condensed water, after ultrafiltration, reverse osmosis concentrated compression apparatus decrement carries out supercharging, enter evaporated crystallization device and carry out evaporative crystallization, evaporated crystallization device utilizes residual heat from boiler fume to carry out evaporative crystallization, obtains highly purified water vapour.
In this step, employing residual heat from boiler fume is carried out evaporative crystallization, because boiler smoke funnel temperature is at about 130 ~ 150 DEG C, there is huge thermal capacity, water droplet and the high-temperature flue gas of atomization carry out rapidly conducting heat, mass transfer, evaporation, water enters desulphurization absorption tower system with highly purified water (steam) gaseous state, and the system of being desulfurized utilized.Therefore, the evaporated water that absorption tower is identical can be replaced, reach the object that desulfurization wastewater is recycled completely.
4), crystallisate and water vapour carry out gas solid separation by gas-solid separating device, obtains high-purity water steam and crystallisate;
5) water vapour, after removing crystallisate is sent in desulfuration absorbing tower and is recycled, and crystallisate is together discharged with flyash.
As shown in Figure 1, the invention provides a kind of wet desulphurization waste water zero discharge device, comprise: waste water, flocculation plant (3) that the gypsum dehydration system (2) that system connects successively is discharged, 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 ultrafiltration, reverse osmosis concentrated compression apparatus (5), desalination water after ultrafiltration, reverse osmosis concentrated compression apparatus (5) desalination is back to desulphurization system, condensed water after decrement connects evaporated crystallization device (6) successively, and gas-solid separating device (7), the pneumatic outlet of gas-solid separating device (7) is connected with the entrance of desulfuration absorbing tower (1).
Wherein, evaporated crystallization device (6) adopts residual heat from boiler fume to carry out evaporative crystallization, and evaporated crystallization device (6) ingress is provided with smoke temperature measurement device and flow measurement device, flocculation plant (3) entry checking apparatus table comprises intake pressure, under meter.
In wet desulphurization waste water zero discharge device of the present invention, evaporated crystallization device is primarily of housing, and atomisation unit composition.Evaporated crystallization device utilizes residual heat from boiler fume to carry out evaporative crystallization, boiler smoke funnel temperature is at about 130 ~ 150 DEG C, there is huge thermal capacity, water droplet and the high-temperature flue gas of atomization carry out rapidly conducting heat, mass transfer, evaporation, water enters desulphurization absorption tower system with the water of high-quality (steam) gaseous state, the system of being desulfurized utilized, and can replace the evaporated water that absorption tower is identical, reaches the object that desulfurization wastewater is recycled completely.
Gas-solid separating device adopts electrostatic collection system, primarily of compositions such as housing, positive plate, cathode rays, collection bucket, high-voltage power supplies.Water (steam) enters desulphurization absorption tower system with flue gas by gas-solid separating device.Soluble solid, heavy metal, high saliferous, Ca in water
2+, Mg
2+, Cl
-, F
-after substance crystallization solidification, be captured in gas-solid separating device, together discharge with flyash.
It should be noted that, a whole set of wet desulphurization waste water zero discharge device Controlling System by computer, programmable controller PLC and topworks thereof and measuring instrument composition.Can, according to the load variations of waste water, boiler smoke temperature and set different parameters, make it to reach optimal running effect during use.Measuring instrument comprises intake pressure, feed water flow gauge; Delivery turbidity meter, water outlet salometer, flue-gas temperature, flue gas flow are measured, and evaporated crystallization device temperature controls.
Inventive desulfurization waste water zero discharge device is the high saliferous desulfurization wastewater recovery process of a kind of uniqueness newly developed, this technology make use of cleverly power plant boiler fume afterheat and the desulphurization system water yield evaporation level theory, this technique in optimized mode to suspended substance, soluble solid, heavy metal, high saliferous, Ca
2+, Mg
2+, Cl
-, F
-the materials such as ion have carried out separating treatment respectively according to substance characteristics.The water (steam) of high-quality can be recycled completely, high salinity and the separated collection of solid waste.Complete assembly without impact, is invested less, practical on other system of power plant, has popularization, use value widely.
The application of power plant desulfurization Sewage advanced treatment recovery and utilization technology, thermal power plant for all wet flue gas desulfurization technique provides and realizes desulfurization wastewater after pretreatment, 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, has accomplished wastewater zero discharge.
Claims (9)
1. wet desulphurization process without drainage of waste water and a device thereof, is characterized in that, comprises the following steps:
1), collect the desulfurization wastewater after gypsum dewatering equipment and enter flocculation plant, soften desulfurization wastewater, flocculate, clarify, filter, the primary water meeting tier 2 process entrance criterion after separation, mud is then delivered in sludge dehydration device and is dewatered;
2), through remove calcium, magnesium ion, heavy metal, suspended substance post softening primary water enter ultrafiltration, reverse osmosis concentrated compression apparatus, the desalination water after desalination is back to desulphurization system, realizes desulfurization wastewater minimizing.
3), supercharging is carried out to the condensed water after decrement after, enter evaporated crystallization device and carry out evaporative crystallization, evaporated crystallization device utilizes residual heat from boiler fume to carry out evaporative crystallization, obtains highly purified water vapour;
4), evaporative crystallization thing and water vapour carry out gas solid separation by gas-solid separating device, obtains highly purified water vapour and crystallisate;
5) water vapour, after removing crystallisate enters in desulfuration absorbing tower and all recycles, and crystallisate is together discharged with flyash.
2. wet desulphurization process without drainage of waste water device according to claim 1, is characterized in that, described flocculation plant adopts electricity flocculation or chemical flocculation.
3. a wet desulphurization process without drainage of waste water device, it is characterized in that, comprising: gypsum dehydration system (2), softening, flocculation plant (3), clarifying plant (4), ultrafiltration, reverse osmosis concentrated compression apparatus (5), evaporated crystallization device (6), gas-solid separating device (7), sludge dehydration device (8); The desulfurization wastewater that gypsum dehydration system (2) is discharged enters softening, flocculation plant (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 ultrafiltration, reverse osmosis concentrated compression apparatus (5), desalination water after ultrafiltration, reverse osmosis concentrated compression apparatus (5) desalination is back to desulphurization system, condensed water after decrement is successively through evaporated crystallization device (6), and gas-solid separating device (7), the pneumatic outlet of gas-solid separating device (7) enters the entrance of desulfuration absorbing tower (1).
4. wet desulphurization process without drainage of waste water device according to claim 3, it is characterized in that, described flocculation plant (3), adds alkali, flocculation, clarification, filtration to desulfurization wastewater, soften and go firmly, the primary water meeting tier 2 process entrance criterion after separation.
5. wet desulphurization process without drainage of waste water device according to claim 3, it is characterized in that, described ultrafiltration, reverse osmosis concentrated compression apparatus (5), adopt bi-membrane method to carry out concentrating and separating to softening primary water, the desalination water after desalination is back to desulphurization system; Realize desulfurization wastewater minimizing.
6. wet desulphurization process without drainage of waste water device according to claim 3, is characterized in that, described evaporated crystallization device (6) utilizes residual heat from boiler fume to carry out evaporative crystallization to concentrated waste water.
7. wet desulphurization process without drainage of waste water device according to claim 6, is characterized in that, described evaporated crystallization device (6) ingress is provided with smoke temperature measurement, flow measurement device and evaporated crystallization device temperature-control device.
8. wet desulphurization process without drainage of waste water device according to claim 4, is characterized in that, described flocculation plant (3) ingress arranges the measuring instrument of intake pressure and flow.
9. wet desulphurization process without drainage of waste water device according to claim 3, is characterized in that, the mud that described clarifying plant (4) discharges then is delivered to sludge treatment equipment (8) and dewatered.
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| CN105439358A (en) * | 2015-12-30 | 2016-03-30 | 北京清大国华环境股份有限公司 | Method and device for realizing zero discharge of desulfurization wastewater |
| CN105481157A (en) * | 2015-12-18 | 2016-04-13 | 王辛平 | Method for zero emission treatment of desulfurization waste water based on flue gas waste heat evaporation |
| CN105948364A (en) * | 2016-07-05 | 2016-09-21 | 盛发环保科技（厦门）有限公司 | Desulfurization wastewater zero discharging treatment system based on bypass flue evaporation |
| CN106430794A (en) * | 2016-12-20 | 2017-02-22 | 大唐国际化工技术研究院有限公司 | Resourceful treatment method and treatment system for desulfuration wastewater |
| CN107098423A (en) * | 2017-05-18 | 2017-08-29 | 北京必可测科技股份有限公司 | A kind of method for the high-salinity wastewater zero-emission for making to produce in industrial production |
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