CN205556348U - Desulfurization waste water zero release processing apparatus - Google Patents

Desulfurization waste water zero release processing apparatus Download PDF

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Publication number
CN205556348U
CN205556348U CN201620115899.6U CN201620115899U CN205556348U CN 205556348 U CN205556348 U CN 205556348U CN 201620115899 U CN201620115899 U CN 201620115899U CN 205556348 U CN205556348 U CN 205556348U
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pond
deliming
water
waste water
demagging
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刘海洋
江澄宇
夏怀祥
李叶红
吴仕宏
夏爽
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Datang Environment Industry Group Co Ltd
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Datang Environment Industry Group Co Ltd
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Abstract

The utility model provides a desulfurization waste water zero release processing apparatus, include: a removal of magnesium removes heavy pond group, the intercommunication removal of magnesium removes one of heavy pond group and removes calcium deposit pond group, the intercommunication remove a nanofiltration system of calcium deposit pond group, include an export of the dense water of a sulphate and a villaumite freshwater outlet, the dense water of sulphate export through a concentrate recirculation pipeline with remove calcium deposit pond group intercommunication, with villaumite freshwater outlet is through a membrane distillation system of concentrated conveying line intercommunication, with an evaporated crystallizer of membrane distillation system's dense water export intercommunication. Can realize the zero release of desulfurization waste water, the salt crystal that the evaporation crystallization obtained can realize whole retrieval and utilizations to operation and treatment cost reduce by a wide margin.

Description

A kind of desulfurization wastewater zero discharge treatment device
Technical field
This utility model relates to environmental protection technical field, is specifically related to a kind of desulfurization wastewater zero discharge treatment device.
Background technology
Coal fired power generation occupies critical role in China's energy resource supply.For environment protection, most of power plant of China in recent years Have employed Limestone-gypsum Wet Flue Gas Desulfurization Process technology, in order to remove the sulfur dioxide in flue gas.Use aforementioned desulfurization technology can produce greatly The desulfurization wastewater of amount, the wet desulphurization waste component of coal-burning power plant is complicated, containing high concentration suspended matter, oversaturated sulphite, Chloride ion, sulfate and various heavy.
At present, desulfurization wastewater mainly uses chemical precipitation method to process, part index number difficulty up to standard, even if after process up to standard, due to Substantial amounts of sulfate and muriatic existence in waste water, water outlet salinity is still up to 2%~4%, is difficult to recycling, after outer row also Surface water and soil ecology can be caused to destroy, cause secondary pollution.Therefore, the research and development of desulfurization wastewater zero discharge treatment technology more come More come into one's own.
Evaporative crystallization method is desulfurization wastewater Zero-discharge treating process currently mainly, and evaporative crystallization method has, and energy consumption is high, equipment is easy The shortcoming that fouling is big with investment.And, it is the highest that evaporative crystallization method processes desulfurization wastewater cost, and ton water processing cost generally to reach More than 60 yuan;In order to reduce processing cost, in some practice of construction, the membrane separation techniques such as RO (reverse osmosis) can be used first Waste water carries out minimizing process, and the dense water that membrance separation produces is evaporated crystallization again, so can effectively reduce evaporative crystallization Process load and save processing cost.But use the membrane separation techniques such as RO to need waste water is carried out strict pretreatment, due to useless In water, calcium and magnesium concentration is high, and calcium sulfate is in hypersaturated state, causes softening pretreatment cost high;It addition, evaporative crystallization produces The mixed salt that salt is sodium chloride and sodium sulfate, it is difficult to utilize, dispose difficulty.
Therefore, in order to avoid environmental pollution and recycle-water resource, in view of the shortcoming and defect of existing desulfurization wastewater technique of zero discharge, Exploiting economy efficient desulfurization wastewater zero discharge treatment treatment technology for Wet Flue Gas Desulfurization Technique field, it is critical that.
Utility model content
For the problems referred to above, the purpose of this utility model is to provide a kind of desulfurization wastewater zero discharge treatment device, it is possible to realize desulfurization Wastewater zero discharge, the crystal salt that evaporative crystallization obtains can realize fully recovering, and operation and processing cost are greatly reduced.
For reaching above-mentioned purpose, the concrete technical scheme that this utility model is taked is:
A kind of desulfurization wastewater zero discharge treatment device, including:
One demagging is except weight pond group;
Connect described demagging except a deliming sedimentation tank group of weight pond group;
Connect a nanofiltration system of described deliming sedimentation tank group, including a dense water out of sulfate and a villaumite water outlet, described The dense water out of sulfate is connected with described deliming sedimentation tank group by a concentrate recirculation pipeline;
Concentrate, by one, the Membrane Materials system that transfer pipeline connects with described villaumite water outlet;
The crystallizing evaporator connected with a dense water out of described Membrane Materials system.
Further, described demagging includes except heavy pond group: a demagging, except weight pond, is provided with one first dosing pipe;With described demagging Except a preliminary sedimentation tank of weight pond connection, bottom it, it is provided with one first spoil disposal pipeline.
Further, described deliming sedimentation tank group includes: the first deliming pond of be sequentially communicated, one or two deliming ponds and or two sink Pond;First deliming pond described in described concentrate recirculation pipeline connection;Described second pond connects with a water inlet of described nanofiltration system; Described first deliming pond is provided with one second dosing pipe;Described secondary deliming pond is provided with one the 3rd dosing pipe;Described first deliming The bottom of pond, secondary deliming pond and second pond all with one second spoil disposal pipeline communication.
Further, a filter it is provided with between described second pond and described water inlet.
Further, described Membrane Materials system is selected from vacuum membrane distillation system, and direct contact membrane distillation system, gas are swept formula film and steamed Evaporate system, gap field orientation system.
Carry out zero emission treatment of desulfured waste water based on aforementioned means, comprise the following steps:
1) desulfurization wastewater enters demagging and removes weight pond group, makes the magnesium ion in desulfurization wastewater and heavy metal ion generate hydroxide precipitation; Obtain demagging except weight waste water;
2) demagging enters deliming sedimentation tank group except weight waste water, makes demagging remove weight waste water and makes calcium ion concentration in waste water be reduced to 10mg/L Hereinafter, mixed salt waste water is obtained;
3) mixed salt waste water enters nanofiltration system;Mixed salt waste water is separated into the dense water of sulfate and villaumite fresh water;
4) the dense water of sulfate is at least partly back to deliming sedimentation tank group;Villaumite fresh water enters Membrane Materials system, obtains distillation condensation Water and the dense water of villaumite;The dense water of villaumite enters crystallizing evaporator, obtains evaporation condensed water and can reuse salt.
Further, step 1) desulfurization wastewater enters demagging except weight pond group, makes the magnesium ion in desulfurization wastewater and heavy metal ion Generate hydroxide precipitation to include:
1-1) desulfurization wastewater enters demagging and removes weight pond, to demagging except adding calcium hydroxide and organic sulfur in weight pond, controls pH in pond It is 9~12, obtains demagging except weight waste water;
1-2) demagging enters preliminary sedimentation tank except weight waste water, carries out mud-water separation, obtains primary sludge and low concentration wastewater.
Further, step 2) demagging enters deliming sedimentation tank group except weight waste water, and make demagging remove weight waste water and make calcium ion in waste water Concentration is reduced to below 10mg/L, including:
2-1) low concentration wastewater enters first deliming pond, sulfate in first deliming pond, makes calcium ion concentration in low concentration wastewater It is reduced to 300~800mg/L, obtains first deliming waste water;
2-2) first deliming waste water enters secondary deliming pond, adds carbonate, flocculant and flocculation aid to secondary deliming pond, makes to give up In water, remaining calcium ion generates precipitation of calcium carbonate, obtains secondary deliming waste water;
2-3) secondary deliming waste water enters second pond, carries out precipitation clarification, makes calcium ion concentration in secondary deliming waste water be reduced to Below 10mg/L.
Further, step 4) in the dense water of sulfate at least partly carry out flue evaporation process and/or be back to a desulfuration absorbing tower.
Further, villaumite fresh water is heated by a heat-exchange system before entering Membrane Materials system, and the thermal source of described heat-exchange system comes From in power plant's heat smoke and/or a heat drain.
By taking technique scheme, sulfate can do deliming with reuse and process, and villaumite is processed by Membrane Materials and evaporative crystallization, Two kinds of salinity other places reason, have that added amount of chemical is few, operating cost is low, produce that water water quality is good, be prone to combine with other technique with And the advantage that Nacl side-product can be reclaimed.Additionally, it is Membrane Materials system heat sources that this utility model may utilize residual heat of electric power plant, no Only can effectively reduce system operation cost, flue-gas temperature can be reduced simultaneously, reduce water consumption in desulfuration absorbing tower, and subtract Few to environmental emission heat.
Accompanying drawing explanation
Fig. 1 is the layout schematic diagram of the desulfurization wastewater zero discharge treatment device in this utility model one embodiment.
Detailed description of the invention
For making features described above of the present utility model and advantage to become apparent, special embodiment below, and coordinate institute's accompanying drawing to make in detail Carefully it is described as follows.
As it is shown in figure 1, in an embodiment, it is provided that a kind of desulfurization wastewater zero discharge treatment device, including demagging remove weight pond 1, Agitating device the 2, first spoil disposal pipeline 3, preliminary sedimentation tank 4, deliming pond 5, agitating device 6, secondary deliming pond 7, agitating device 8, Second pond 9, spoil disposal pipeline 10, water pump 11, filter 12, nanofiltration system 13, concentrate recirculation pipeline 14, concentrated water discharge pipe Road 15, intermediate pool 16, hot working fluid outlet 17, heat exchanger 18, hot working fluid entrance 19, water pump 20, water inlet 21, film Distallation systm 22, condensation-water drain 23, dense water out 24, crystallizing evaporator 25, condensation-water drain 26 and crystal salt outlet 27.Its concrete position relation, annexation and function are as follows:
Magnesium is equipped with agitating device except weight pond 1, deliming pond 5 and secondary deliming pond 7, and magnesium removes weight pond 1, preliminary sedimentation tank 4, deliming pond 5, secondary deliming pond 7, second pond 9 are equipped with sludge bucket and spoil disposal pipeline.
Magnesium removes weight pond 1 and the optional shared spoil disposal pipeline 3 of preliminary sedimentation tank 4;Deliming pond 5, secondary deliming pond 7, second pond 9 are optional common With spoil disposal pipeline 10.
Filter 12 is chosen as more medium filter, it is possible to avoids remaining levitation thing in waste water to affect subsequent film distillation and runs.Specifically Ground, filter 12 is ultrafiltration or microfiltration systems.
Membrane Materials system 22 is vacuum membrane distillation system, direct contact membrane distillation system, sweep gas membrane disillation system, GAP TYPE Membrane Materials system, preferably vacuum membrane distillation system.In described Membrane Materials system, membrane material is PTFE, PVDF, PP or pottery.
When utilizing the method that said apparatus carries out desulfurization wastewater zero discharge treatment, desulfurization wastewater initially enters demagging and removes weight pond, to instead Adding combination medicament A in Ying Chi, including calcium hydroxide and organic sulfur, in control reactor, pH is 9~12, makes the magnesium in waste water Generating hydroxide precipitation with major part heavy metal, hydrargyrum in waste water generates sulfide precipitation, thus remove in waste water magnesium hardness and The heavy metals such as lead, zinc, chromium and hydrargyrum.For strengthening subsequent mud-water separation effect, can to demagging except weight pond in add flocculant and Flocculation aid.
Waste water, after magnesium is except weight, enters preliminary sedimentation tank, and after mud-water separation, in preliminary sedimentation tank water outlet, magnesium density is reduced to 15mg/L Hereinafter, heavy metal realizes qualified discharge, and preliminary sedimentation tank produces mud with demagging except the further thickening of mud of weight pond generation processes, Final security landfill is disposed;Preliminary sedimentation tank supernatant enters deliming pond, and adding medicament B, medicament B in deliming pond is sulfate, It is preferably sodium sulfate, by increasing sulfate radical in waste water concentration, makes oversaturated calcium sulfate in waste water separate out, thus reach to remove The purpose of part calcium ion, in waste water, sodium sulfate dosage is 0.01~0.3mol/L, makes calcium ion concentration in waste water be reduced to 300~800mg/L.
In deliming pond, waste water enters secondary deliming pond, and adds combination medicament C, including carbonate, flocculant and flocculation aid, logical Cross adding of combination medicament C, make remaining calcium ion in waste water generate precipitation of calcium carbonate, be simultaneously introduced flocculant and flocculation aid carries High sludge settling performance;Wherein, carbonate is preferably sodium carbonate.
In secondary deliming pond, waste water enters second pond, after precipitation clarification, makes calcium ion concentration in waste water be reduced to 10mg/L Hereinafter, the mud that second pond, deliming pond, secondary deliming pond produce is discharged into gypsum dehydration machine by spoil disposal pipeline and carries out processed, Comprehensively utilize as gypsum by-product.
Wastewater pH, by adding hydrochloric acid, is adjusted to 6~8, is then entering filter by water pump, entering by the supernatant of second pond One step removes the float in waste water.
Filter water outlet enters nanofiltration system, by point salt action of nanofiltration, makes the divalent ions such as sulfate radical in waste water and chloride ion Separating Deng monovalent ion, sulfate (predominantly sodium sulfate) the dense water that nanofiltration system produces, a part is back to deliming pond, carries For sodium sulfate as softening medicament, dense water is the most optional carries out condensing crystallizing process and/or flue evaporated for another part residue Manage and/or be back in desulfuration absorbing tower.
Wherein, carry out flue evaporation process, dense for sodium sulfate water is sprayed in cleaner unit front end smoke canal, adds steam through high-temperature flue gas After change, the inorganic salt in dense water forms solid crystal, then by being captured with the form of dirt by cleaner unit during follow-up cleaner unit;
The fresh water containing chloride ion that nanofiltration system produces enters intermediate pool, and in intermediate pool, waste water and heat exchanger heat exchange, useless Water is heated up after 35~95 DEG C, enters next step membrane distillation concentration and processes.
In described intermediate pool, heat-exchange system thermal source comes from working medium, heat smoke or the hot water such as power plant's heat smoke or heat drain by thermal technology Matter import (19) enters exchanger (18), hot working fluid outlet (17) discharge.
Wherein, heat-exchange system can be arranged in intermediate pool;Can also be arranged on outside intermediate pool;Its thermal source uses electrical heating Or steam heating.
In intermediate pool, waste water is after heating, enters Membrane Materials system by water pump, by Membrane Materials system by Waste water concentrating extremely Salinity is more than 10%, and the dense water that described Membrane Materials system produces enters crystallizing evaporator and processes;Described Membrane Materials system produces Condensed water, preferentially uses as boiler feedwater as recycle-water in power plant process.
The dense water that Membrane Materials system produces enters crystallizing evaporator, and the recycling condensing water produced in evaporation process, in power plant, produces knot Brilliant salt is sold as outside Nacl side-product;Dense hydromining electrolysis preparing hydrogen sodium oxide, chlorine and the hydrogen that Membrane Materials system produces Side-product.
As a example by a Practical Project, take certain power plant desulfurization waste water, initially enter demagging and remove weight pond, open agitating device, to reaction Adding calcium hydroxide and organic sulfur in pond, in control reactor, pH is about 11.5, makes the magnesium in waste water and major part heavy metal Generation hydroxide precipitates, and the hydrargyrum in waste water generates sulfide precipitation, and then waste water enters preliminary sedimentation tank, at the beginning of after mud-water separation In sinking pool effluent, magnesium density is reduced to below 15mg/L by the 3000gm/L of former water, and heavy metal realizes qualified discharge, preliminary sedimentation tank Producing mud with demagging except the further thickening of mud of weight pond generation processes, final security landfill is disposed.
Preliminary sedimentation tank supernatant enters deliming pond, adds sodium sulfate in deliming pond, and dosage is 0.1mol/L, useless by increasing Sulfate concentration in water, makes oversaturated calcium sulfate in waste water separate out, thus reaches to remove the purpose of part calcium ion, in waste water The dosage of sodium sulfate is 0.01~0.3mol/L, makes calcium ion concentration in waste water be reduced to about 500mg/L by 2500mg/L. Then waste water enters secondary deliming pond, adds sodium carbonate, flocculant and flocculation aid, make remaining calcium ion in waste water in waste water Generating precipitation of calcium carbonate, be simultaneously introduced flocculant and flocculation aid improves sludge settling performance, waste water enters second pond, through precipitation After clarification, calcium ion concentration in waste water is made to be reduced to below 10mg/L, the dirt that second pond, deliming pond, secondary deliming pond produce Mud is discharged into gypsum dehydration machine and carries out processed, comprehensively utilizes as gypsum by-product.
Wastewater pH, by adding hydrochloric acid, is pulled back to 6~8, is then entering filter by water pump by the supernatant of second pond, Remove the float in waste water further.Filter water outlet enters nanofiltration system, by point salt action of nanofiltration, makes sulfur in waste water The monovalent ions such as the divalent ions such as acid group and chloride ion separate, sulfate (predominantly sodium sulfate) the dense water that nanofiltration system produces, A part is back to deliming pond, it is provided that sodium sulfate is as softening medicament, and another part remains the then condensing crystallizing process further of dense water;
The fresh water containing chloride ion that nanofiltration system produces enters intermediate pool, and in intermediate pool, waste water uses dedusting rear pass heat Flue gas, after being warming up to 35~95 DEG C, enters next step membrane distillation concentration and processes.By Membrane Materials system by Waste water concentrating extremely Salinity is more than 10%, and the condensed water that Membrane Materials system produces, preferentially feeds as boiler as recycle-water in power plant process Water uses.The dense water that Membrane Materials system produces enters crystallizing evaporator and is evaporated crystallization treatment, produces condensed water and sodium chloride knot Brilliant salt, recycling condensing water is in power plant, and crystal salt is sold as outside Nacl.
Through adjusting, ton water processing cost is about 20 yuan;Relatively prior art significantly declines, and multi-products produce water can with reuse, Additional income can be increased or reduce respective handling cost.
It should be noted that this utility model, for preferable case study on implementation of the present utility model, is not imposed any restrictions by the above, Every any simple modification, change and equivalent structure change above example made according to this utility model technical spirit, All still fall within the protection domain of technical solutions of the utility model.

Claims (5)

1. a desulfurization wastewater zero discharge treatment device, it is characterised in that including:
One demagging is except weight pond group;
Connect described demagging except a deliming sedimentation tank group of weight pond group;
Connecting a nanofiltration system of described deliming sedimentation tank group, including a dense water out of sulfate and a villaumite water outlet, the dense water out of described sulfate is connected with described deliming sedimentation tank group by a concentrate recirculation pipeline;
Concentrate, by one, the Membrane Materials system that transfer pipeline connects with described villaumite water outlet;
The crystallizing evaporator connected with a dense water out of described Membrane Materials system.
2. desulfurization wastewater zero discharge treatment device as claimed in claim 1, it is characterised in that described demagging includes except weight pond group: a demagging, except weight pond, is provided with one first dosing pipe;The preliminary sedimentation tank connected except weight pond with described demagging, is provided with one first spoil disposal pipeline bottom it.
3. desulfurization wastewater zero discharge treatment device as claimed in claim 1, it is characterised in that described deliming sedimentation tank group includes: the first deliming pond of be sequentially communicated, one or two deliming ponds and a second pond;First deliming pond described in described concentrate recirculation pipeline connection;Described second pond connects with a water inlet of described nanofiltration system;Described first deliming pond is provided with one second dosing pipe;Described secondary deliming pond is provided with one the 3rd dosing pipe;The bottom of described first deliming pond, secondary deliming pond and second pond all with one second spoil disposal pipeline communication.
4. desulfurization wastewater zero discharge treatment device as claimed in claim 3, it is characterised in that be provided with a filter between described second pond and described water inlet.
5. desulfurization wastewater zero discharge treatment device as claimed in claim 1, it is characterised in that described Membrane Materials system is selected from vacuum membrane distillation system, direct contact membrane distillation system, sweep gas membrane disillation system, gap field orientation system.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105712557A (en) * 2016-02-05 2016-06-29 大唐环境产业集团股份有限公司 Desulfurization waste water zero discharging treatment device and method
WO2017133514A1 (en) * 2016-02-05 2017-08-10 大唐环境产业集团股份有限公司 Treatment apparatus and method for softening desulfurization wastewater
CN109133465A (en) * 2017-06-28 2019-01-04 北京朗新明环保科技有限公司 A kind of Waste Heat Reuse vacuum membrane distillation zero discharge treatment device and method

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105712557A (en) * 2016-02-05 2016-06-29 大唐环境产业集团股份有限公司 Desulfurization waste water zero discharging treatment device and method
WO2017133512A1 (en) * 2016-02-05 2017-08-10 大唐环境产业集团股份有限公司 Treatment apparatus and method for zero liquid discharge of desulfurization wastewater
WO2017133514A1 (en) * 2016-02-05 2017-08-10 大唐环境产业集团股份有限公司 Treatment apparatus and method for softening desulfurization wastewater
CN105712557B (en) * 2016-02-05 2019-01-25 大唐环境产业集团股份有限公司 A kind of desulfurization wastewater zero discharge treatment device and method
CN109133465A (en) * 2017-06-28 2019-01-04 北京朗新明环保科技有限公司 A kind of Waste Heat Reuse vacuum membrane distillation zero discharge treatment device and method

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