CN107244773A - The technique of zero discharge and equipment of desulfurization wastewater Treatment and recovery - Google Patents

The technique of zero discharge and equipment of desulfurization wastewater Treatment and recovery Download PDF

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Publication number
CN107244773A
CN107244773A CN201710381140.1A CN201710381140A CN107244773A CN 107244773 A CN107244773 A CN 107244773A CN 201710381140 A CN201710381140 A CN 201710381140A CN 107244773 A CN107244773 A CN 107244773A
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water
tmf
waste water
softening
pump
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陈阳波
翁欲晓
张未来
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Wuhan Shang Yuanxin Energy Environment Co Ltd
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Wuhan Shang Yuanxin Energy Environment Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00Multistage treatment of water, waste water, or sewage
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/42Treatment of water, waste water, or sewage by ion-exchange
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/44Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/46Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F2001/007Processes including a sedimentation step
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/18Nature of the water, waste water, sewage or sludge to be treated from the purification of gaseous effluents
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2301/00General aspects of water treatment
    • C02F2301/08Multistage treatments, e.g. repetition of the same process step under different conditions
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2303/00Specific treatment goals
    • C02F2303/22Eliminating or preventing deposits, scale removal, scale prevention
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F5/00Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
    • C02F5/02Softening water by precipitation of the hardness
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F5/00Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
    • C02F5/02Softening water by precipitation of the hardness
    • C02F5/06Softening water by precipitation of the hardness using calcium compounds

Abstract

The invention discloses a kind of technique of zero discharge of desulfurization wastewater Treatment and recovery, step is followed successively by oil removal, removes magnesium ion and sulfate ion in waste water, the calcium ion removed in waste water, tubular membrane separation of solid and liquid, ion exchange resin except residual harness, light electrolysis bipolar membrane device desalination sodium chloride concentrated water, finally obtains limestone slurry of desulfurization system configuration water and acid and sodium hydroxide commodity;Its equipment is also disclosed, the device and part installed by water (flow) direction include wastewater collection pond, High-speed clarification separator, one-level softening plant, secondary softening device, TMF concentrated waters case, TMF elevator pumps, TMF systems, TMF water producing tanks, exchange elevator pump, Di, middle water producing tank, electrolysis feed pump, light electrolysis bipolar membrane device and product water tank;The material of pollutant will be belonged in other field in desulphurization system according to desulfurization waste water quality feature, the requirement of desulphurization system water and become useful resources, operating cost is less than other technique of zero discharge and equipment.

Description

The technique of zero discharge and equipment of desulfurization wastewater Treatment and recovery
Technical field
The invention belongs to desulfurization wastewater zero-emission and resource treatment technique field, and in particular to a kind of desulfurization wastewater processing And the technique of zero discharge and its equipment of recycling, according to desulfurization waste water quality feature, desulphurization system water requirement will be in desulfurization system Useful resources can be become in other field by belonging to the material of pollutant in system, and operating cost is significantly less than other technique of zero discharge And equipment.
Background technology
It is existing to be had the following disadvantages for desulfurization wastewater treatment technology:
1st, wet process of FGD is a kind of ripe, efficient sulfur removal technology of sulphur atmosphere pollution processing, is widely used in various flue gases Desulfurizer;In order to maintain the balance of desulfurizer serum recycle system material, prevent that soluble fraction i.e. cl concn surpasses in flue gas Cross setting and ensure gypsum quality, it is necessary to a certain amount of waste water is discharged from system, containing substantial amounts of outstanding in this effluent part Float, calcium and magnesium hardness, activated silica, heavy metal, COD, sodium chloride, high salt amount and other particular matters;Desulfurization wastewater base at this stage It is discharge after simple process on this, such waste water resource is main that very big influence is brought on environment;So, how General Office Reuse desulfurization wastewater is managed, wastewater zero discharge is reached and is allowed to a kind of trend that reuse is desulfurization wastewater processing, while being also one Technical barrier.
2nd, the existing technical research on desulfurization wastewater processing, method and principle be present:
It is CN104743732A in China Patent No.《A kind of method of power plant desulfurization wastewater Zero-discharge reuse》, CN104843927A《Desulfurization wastewater technique of zero discharge and system》、CN105110543A《A kind of thermal power plant coal unit takes off Sulphur wastewater zero discharge system》、CN105502792A《A kind of zero emission treatment of desulfured waste water》、CN105254101A《It is a kind of Desulphurization for Coal-fired Power Plant waste water zero discharge treatment process》And China Patent No. is 201110076844《Desulfurization wastewater zero discharge treatment Method and system》, also China Patent No. is 201110204147《Method for treating desulfurized wastewater》It is de- in correlation etc. prior art In sulphur Sewage treatment research on utilization, the characteristics of they are common is:Medicament is added in desulfurization wastewater, by suspension and a part huge sum of money Category precipitation is separated, and then discharges the water of processing;Or steam the water after processing by atomising device and electrostatic precipitator It is dry to reach zero-emission.The shortcoming of above-mentioned technical matters is:1)Water does not carry out reuse;2)The desulfurization wastewater discharged after simple process, Wherein salt content and other pollutants such as heavy metal ion, calcium and magnesium hardness ions, silicon, COD and other polluters are all discharged into In environment, the pollution of new paragon is caused to environment;3)It is also last higher using investment, operating cost even if reaching zero-emission Crystallizing evaporator carry out zero discharge treatment, finally divide salt to obtain Nacl.
Main desulphurization system waste discharge is because containing substantial amounts of chlorion in waste water(Cl-), sulfate ion (SO4 2-)With magnesium ion (Mg2+);Chlorion(Cl-)When too high, the corrosion of desulfurization process equipment, sulfate ion are caused(SO4 2-) It is too high to suppress desulfurized effect, and magnesium ion (Mg2+) it is too high can form catalyst poisoning, influence desulfurized effect;So desulfurization The factor of these three in journey is reached after finite concentration with regard to discharge unit waste water;Based on this, demagging and sulfate radical are gone using agent-feeding treatment Ion, reselection removes removing chloride using the method for light electrolysis, removes the waste water recycling after these three influence factors to desulfurization work Skill water distribution, reaches the purpose of desulfurization wastewater zero-emission.And existing desulfurization wastewater zero-discharge technology is all by the pollutant of waste water After removal, using the method for crystallizing evaporator or film concentration+crystallizing evaporator, water evaporation is come out, salinity is born in and becomes carnallite Or purification obtains Nacl, it is invested and operating cost is very high, and has secondary solid waste(Carnallite)Produce.
The content of the invention
An object of the present invention is according to the deficiencies in the prior art, according to wet desulfurization system water and desulfurization wastewater The characteristics of and require there is provided a kind of lime stone slurry water distribution of desulfurization wastewater microelectrolysis processing reuse into desulphurization system to reach Wastewater zero discharge and by the technique of changing waste into resources, it is invested is significantly less than other technique of zero discharge with operating cost.
The technical solution adopted for the present invention to solve the technical problems is:The zero-emission work of desulfurization wastewater Treatment and recovery Skill, comprises the following steps
A, waste water quality regulation:Desulfurization wastewater is discharged into wastewater collection pond, the waste water for making variation water quality big is adjusted to uniform water Matter;
Suspension in B, separation waste water:The suspension flocculation in desulfurization wastewater is formed a team and quick by High-speed clarification separator Separation, and suspension is compressed into by mud cake by sludge dehydration device;
C, once soften:Supernatant in step B is put into one-level softening plant, removed by adding calcium hydroxide in water body Magnesium and sulfate ion, until chlorion is reduced to below 1000mg/l in water body, sulfate ion be reduced to 1500mg/l with Under, magnesium ion is reduced to below 150mg/l, and pH reaches 10.0~11.5;
D, secondary softening:Supernatant after step C is handled is put into secondary softening device, is combined by carbon dioxide and catalyst The calcium ion in waste water is removed, until the concentration of calcium ion drops to below 100mg/L, solid particle is after natural subsidence, feeding Sludge dehydration device dewater treatment is into mud cake;
E, filtering:The supernatant after D step process is filtered by tubular membrane filter device, by solid suspension from water Separate, the concentrated water after filtering returns to secondary softening device, and solid particle is after natural subsidence, dewater treatment;
F, removal hardness:The aqueous after step E processing is handled by Di, removed remaining in waste water Hardness;
G, light electrolysis dechlorination:The sodium chloride fortified aqueous after step E processing is desalinated by light electrolysis bipolar membrane device, made The concentration of waste water is reduced to below 1000mg/L, and water outlet disclosure satisfy that the water distribution requirement of lime stone slurry in desulphurization system, simultaneously Obtain acid and sodium hydroxide solution;
H, reuse:Step H desalination after waste water recycling into desulphurization system as lime stone slurry configuration water, so as to reach zero Discharge.
The second object of the present invention is to provide a kind of desulfurization wastewater microelectrolysis processing reuse lime stone into desulphurization system Slurries water distribution is to reach wastewater zero discharge and by the equipment of changing waste into resources.
The technical solution adopted for the present invention to solve the technical problems is:A kind of zero-emission of desulfurization wastewater Treatment and recovery Equipment is put, the device and part installed by water (flow) direction order include wastewater collection pond, High-speed clarification separator, one-level and softened Device, secondary softening device, TMF concentrated waters case, TMF elevator pumps, TMF systems, TMF water producing tanks, exchange elevator pump, amberlite Fat device, middle water producing tank, electrolysis feed pump, light electrolysis bipolar membrane device and product water tank;Described wastewater collection pond is by receiving Ji Chi and in collecting pit immersible pump composition, submersible pump outlet simultaneously with High-speed clarification separator and one-level softening plant Entrance be connected;The supernatant outlet of the High-speed clarification separator is connected with the entrance of one-level softening plant;Described one Level softening plant has at least one chemicals dosing plant, one-level softening plant supernatant outlet and the entrance phase of secondary softening device Even;The supernatant outlet of described secondary softening device is connected with TMF concentrated water tank inlets;Described High-speed clarification separator, The bottom drain of one-level softening plant and TMF concentrated water casees connects sludge pump simultaneously, and sludge pump connects the entrance of plate and frame filter press, The outlet connection wastewater collection pond of plate and frame filter press;The outlet of the TMF concentrated waters case is connected with TMF elevator pumps;Described TMF is carried Pump is risen with the water inlet of TMF systems to be connected;The concentrated water of the TMF systems returns to TMF concentrated water casees, the production mouth of a river of TMF systems and TMF Water producing tank is connected;The delivery port of the TMF water producing tanks is connected with exchanging elevator pump;Described exchange elevator pump and amberlite The water inlet of fat device is connected;The delivery port of the Di is connected with middle water producing tank;Production water in the middle of described The outlet of case is connected with electrolysis feed pump;Described electrolysis feed pump is connected with the water inlet of light electrolysis bipolar membrane device;It is described Light electrolysis bipolar membrane device product water tank is connected by neutral delivery port, light electrolysis bipolar membrane device passes through acidic effluent respectively Mouth and alkaline delivery port are connected with acid solution case and lye tank.
A kind of zero-emission equipment of described desulfurization wastewater, its High-speed clarification separator supernatant outlet softens with one-level Reaction tank and filtering ponds are also sequentially connected between the entrance of device.
The beneficial effects of the invention are as follows:One is that can quickly remove the suspension in desulfurization wastewater, and two be to remove in waste water The magnesium ion and sulfate ion of desulfurized effect are influenceed, three be that the calcium ion in waste water is removed using carbon dioxide and catalyst, Four be that pretreated high salinity waste water is desalinated using light electrolysis bipolar membrane device, the waste water of processing is met reuse To the lime stone slurry water distribution of desulphurization system, desulfurization wastewater zero-emission is reached, five be light electrolysis bipolar membrane device desalination waste water During produce acid and sodium hydroxide commodity, six be that operating cost is low, and not only desulfurization wastewater reaches zero-emission, is also produced extra Economic value(Acid and sodium hydroxide commodity).
In summary, principle of the invention be remove influence desulphurization system in desulfurized effect magnesium and sulfate ion and Corrode the chlorion of desulphurization plant into desulfurization wastewater, for this purpose and the purpose of pollutant resources can be realized, in addition it is also necessary to Calcium ion in waste water is removed, waste water recycling to the desulphurization system of final process prepares lime stone slurry, so as to reach waste water zero-emission Put, while acid and sodium hydroxide product can be produced during removing chloride, reach the purpose of recycling.Handling process letter Single, equipment operation and energy consumption are very low.
Brief description of the drawings
Fig. 1 is the schematic flow sheet of present invention process;
Fig. 2 is the structural representation of present device.
Each reference is entitled in figure:1-wastewater collection pond, 2-High-speed clarification separator, the softening of 3-one-level Device, 4-secondary softening device, 5-TMF concentrated water casees, 6-sludge pump, 7-plate and frame filter press, 8-TMF elevator pumps, 9-TMF System, 10-TMF water producing tanks, 11-exchange elevator pump, 12-Di, 13-centre water producing tank, 14-electricity Solve feed pump, 15-light electrolysis bipolar membrane device, 16-acid solution case, 17-lye tank, 18-final product water tank.
Embodiment
The present invention is described in further detail below in conjunction with the accompanying drawings.
Shown in reference picture 1, the technique of zero discharge of desulfurization wastewater Treatment and recovery comprises the following steps
A, waste water quality regulation
Desulfurization wastewater is discharged into wastewater collection pond, desulfurization wastewater is interim draining, and variation water quality is big, and uniform water is adjusted herein Matter.
Suspension in B, separation waste water
The suspension flocculation in desulfurization wastewater is formed a team by High-speed clarification separator, and the quick separation from waste water, and lead to Cross sludge dehydration device and suspension is compressed into mud cake.
C, once soften
Supernatant in step B is put into one-level softening plant, by adding magnesium and sulfate radical in calcium hydroxide removal water body Ion, up to chlorion is reduced to below 1000mg/l in the water body after processing, sulfate ion is reduced to below 1500mg/l, Magnesium ion is reduced to below 150mg/l, and pH is reached the magnesium and sulfate radical in water body after 10.0~11.5, agent-feeding treatment from ion State is converted into solid particles, and solid particle is after natural subsidence, by sludge dehydration device dewater treatment into mud cake.
D, secondary softening
Supernatant after step C is handled is put into secondary softening device, by carbon dioxide and catalyst combined removal waste water Calcium ion, until the concentration of calcium ion drops to below 100mg/L, solid particle is after natural subsidence, feeding sludge dewatering dress Dewater treatment is put into mud cake.
E, filtering
The supernatant after D step process is filtered by tubular membrane filter device, solid suspension is separated from the water out Come, the concentrated water after filtering returns to secondary softening device, and solid particle is after natural subsidence, dewater treatment.
F, removal hardness
The aqueous after step E processing is handled by Di, waste water is removed by ion exchange resin Middle remaining hardness.
G, light electrolysis dechlorination
The waste water of hardness is eliminated, its ion component is mostly sodium chloride, after being handled by light electrolysis bipolar membrane device step E Sodium chloride fortified aqueous desalinated, waste water TDS concentration is reduced to below 1000mg/L, water outlet disclosure satisfy that desulfurization system The water distribution requirement of lime stone slurry in system, while obtaining acid and sodium hydroxide solution.
H, reuse
Step H desalination after waste water recycling into desulphurization system as lime stone slurry configuration water, so as to reach zero-emission.
Inventive principle
Main desulphurization system waste discharge is because containing substantial amounts of chlorion in waste water(Cl-), sulfate ion(SO4 2-) With magnesium ion (Mg2+);Chlorion(Cl-)When too high, the corrosion of desulfurization process equipment, sulfate ion are caused(SO4 2-)Too high meeting Suppression desulfurized effect, and magnesium ion (Mg2+) it is too high can form catalyst poisoning, influence desulfurized effect;So this in sweetening process Three factors are reached after finite concentration with regard to discharge unit waste water;Based on this, demagging and sulfate ion are gone using agent-feeding treatment, then Selection removes removing chloride using the method for light electrolysis, removes the waste water recycling after these three influence factors to sulfur removal technology water distribution, Reach the purpose of desulfurization wastewater zero-emission.
As a kind of specific embodiment, as shown in Fig. 2 the High-speed clarification separator 2 that the present invention is used sets for a middle part Putting sludge dehydration device, top sets supernatant outlet, bottom to set the depositing reservoir of mud discharging mouthful;The one-level of interconnection is soft Makeup puts 3 and secondary softening device 4 is the casing reacted for softening agent, and the entrance connection of one-level softening plant 3 is quick respectively Chemicals dosing plant, the bottom connection sludge of one-level softening plant 3 are provided with clarified separation device 2 and immersible pump, one-level softening plant 3 Pump 6;TMF systems 9 are tubular membrane filter device, can select the CN201410561118.1 patents of applicant affiliated company application Equipment disclosed in " a kind of tube type filter membrance production equipment ";Di 12 passes through anion and cation exchange resin pair Various anions and canons in water enter line replacement;Light electrolysis bipolar membrane device 15 is by bipolar membrane electrodialysis method to sodium chloride concentrated water Solution is desalinated.
The technique of inventive desulfurization wastewater zero discharge, is to remove suspension in desulfurization wastewater, is softened subsequently into one-level Device, adds calcium hydroxide, adjusts pH to 10.0~11.5, the magnesium and sulfate radical in water body are converted into solid from ionic state Grain state, supernatant enters back into secondary softening device, adds proprietary catalyst in secondary softening device and is passed through carbon dioxide, Calcium ion in waste water is changed into calcium carbonate to remove, the suspensions such as various solid particles are removed by tubular membrane;The production of tubular membrane Water is made a return journey remaining hardness in water removal through ion exchange resin again, and the waste water finally softened enters light electrolysis bipolar membrane device, The sodium chloride containing high concentration desalinates into the sodium chloride waste water of low concentration in waste water, makes the waste water after processing can be with reuse to desulfurization Lime stone slurry configuration water in system, so as to reach zero-emission;During other light electrolysis bipolar membrane device desalination waste water, The acid and sodium hydroxide solution of generation, realize the purpose of recycling.
In the present invention calcium hydroxide is added in one-level softening plant;Can so remove magnesium ion and sulfate radical from Son, is that subsequent treatment lays the first stone.
Calcium ion is removed in secondary softening device in the present invention, the present invention uses the side of carbon dioxide and catalyst Method, is different from traditional plus sodium carbonate method, possibility is provided for follow-up recycling;
Light electrolysis bipolar membrane device in the present invention, can desalinate into the sodium chloride containing high concentration in waste water the chlorination of low concentration Sodium, make the waste water after processing can with reuse into desulphurization system lime stone slurry configuration water;
Acid and sodium hydroxide product can be obtained in the present invention.
In summary, principle of the invention is to remove the magnesium of desulfurized effect and sulfate radical and entrance in influence desulphurization system Corrode the chlorion of desulphurization plant in desulfurization wastewater, for this purpose and the purpose of pollutant resources can be realized, in addition it is also necessary to remove Calcium ion in waste water, waste water recycling to the desulphurization system of final process prepares lime stone slurry, so as to reach wastewater zero discharge, together When can be produced during removing chloride acid and sodium hydroxide product, reach the purpose of recycling.The handling process is simple, equipment Operation and energy consumption are very low.
Shown in reference picture 2, the invention also discloses a kind of zero-emission equipment of desulfurization wastewater Treatment and recovery, by current The device and part that direction order is installed include the wastewater collection pond 1 with desulfurization wastewater water UNICOM, High-speed clarification separator 2nd, one-level softening plant 3, secondary softening device 4, TMF concentrated waters case 5, TMF elevator pumps 8, TMF systems 9, TMF water producing tanks 10, exchange Elevator pump 11, Di 12, middle water producing tank 13, electrolysis feed pump 14, light electrolysis bipolar membrane device 15 and most Whole product water tank 18;Immersible pump of the described wastewater collection pond 1 by collecting pit and in collecting pit is constituted, submersible pump outlet It is connected simultaneously with the entrance of High-speed clarification separator 2 and one-level softening plant 3;The supernatant of the High-speed clarification separator 2 Liquid outlet is connected with the entrance of one-level softening plant 3, the supernatant outlet of High-speed clarification separator 2 and one-level softening plant 3 Also reaction tank one, reaction tank two and filtering ponds successively between entrance;Described one-level softening plant 3 is filled with least one dosing Put, the supernatant outlet of one-level softening plant 3 is connected with the entrance of secondary softening device 4;The supernatant of described secondary softening device 4 Liquid outlet is connected with the entrance of TMF concentrated waters case 5;Described High-speed clarification separator 2, one-level softening plant 3 and TMF concentrated waters case 5 Bottom drain connect sludge pump 6 simultaneously, sludge pump 6 connects the entrance of plate and frame filter press 7, and the outlet of plate and frame filter press 7 connects Connect and arranged outside wastewater collection pond 1, the mud cake that plate and frame filter press 7 is produced, its pressing filtering liquid returns to wastewater collection pond 1;The TMF concentrated waters case 5 outlet is connected with TMF elevator pumps 8;Described TMF elevator pumps 8 are connected with the water inlet of TMF systems 9;The TMF systems 9 Concentrated water returns to TMF concentrated waters case 5, and the production mouth of a river of TMF systems 9 is connected with TMF water producing tanks 10;The delivery port of the TMF water producing tanks 10 It is connected with exchanging elevator pump 11;Described exchange elevator pump 11 is connected with the water inlet of Di 12;It is described from The delivery port of sub-exchange resin device 12 is connected with middle water producing tank 13;The outlet of the middle water producing tank 13 and electrolysis feed pump 14 are connected;Described electrolysis feed pump 14 is connected with the water inlet of light electrolysis bipolar membrane device 15;Described light electrolysis Bipolar Membrane Device 15 connects final product water tank 18 by neutral delivery port, and light electrolysis bipolar membrane device 15 passes through acidic effluent mouthful respectively It is connected with alkaline delivery port with acid solution case 16 and lye tank 17.
The technique of the present invention, is to remove suspension in desulfurization wastewater, subsequently into one-level softening plant, adds hydroxide Calcium, adjusts pH to 10.0~11.5, the magnesium and sulfate radical in water body is converted into solid particles from ionic state, supernatant enters again Enter secondary softening device, add proprietary catalyst in secondary softening device and be passed through carbon dioxide, by calcium ion in waste water Calcium carbonate removal is changed into, the suspensions such as various solid particles are removed by tubular membrane;The production water of tubular membrane is again through ion exchange Resin is made a return journey remaining hardness in water removal, and the waste water finally softened enters light electrolysis bipolar membrane device, highly concentrated containing in waste water The sodium chloride of degree desalinates into the sodium chloride waste water of low concentration, make the waste water after processing can with reuse into desulphurization system limestone slurry Liquid configuration water, so as to reach zero-emission;During other light electrolysis bipolar membrane device desalination waste water, the acid and hydrogen-oxygen of generation Change sodium solution, realize the purpose of recycling.
The present invention adds calcium hydroxide in one-level softening plant;Magnesium ion and sulfate ion can be so removed, is Subsequent treatment lays the first stone;
Calcium ion is removed in secondary softening device in the present invention, the present invention is using the method for carbon dioxide and catalyst, area Do not add sodium carbonate method in traditional, possibility is provided for follow-up recycling;
Light electrolysis bipolar membrane device in the present invention, can desalinate into the sodium chloride containing high concentration in waste water the chlorination of low concentration Sodium, make the waste water after processing can with reuse into desulphurization system lime stone slurry configuration water;
Acid and sodium hydroxide product can be obtained in the present invention.
The above-described embodiments merely illustrate the principles and effects of the present invention, and the embodiment that part is used, for For one of ordinary skill in the art, without departing from the concept of the premise of the invention, can also make it is some deformation and Improve, these belong to protection scope of the present invention.

Claims (3)

1. the technique of zero discharge of desulfurization wastewater Treatment and recovery, it is characterised in that:Comprise the following steps
A, waste water quality regulation
Desulfurization wastewater is discharged into wastewater collection pond, the waste water for making variation water quality big is adjusted to uniform water quality;
Suspension in B, separation waste water
The suspension flocculation in desulfurization wastewater is formed a team and quick separating by High-speed clarification separator, and passes through sludge dewatering Suspension is compressed into mud cake by device;
C, once soften
Supernatant in step B is put into one-level softening plant, by adding magnesium and sulfate radical in calcium hydroxide removal water body Ion, until chlorion is reduced to below 1000mg/l in water body, sulfate ion is reduced to below 1500mg/l, magnesium ion drop It is low to reach 10.0~11.5 to below 150mg/l, pH;
D, secondary softening
Supernatant after step C is handled is put into secondary softening device, by carbon dioxide and catalyst combined removal waste water Calcium ion, until the concentration of calcium ion drops to below 100mg/L, solid particle is after natural subsidence, feeding sludge dewatering dress Dewater treatment is put into mud cake;
E, filtering
The supernatant after D step process is filtered by tubular membrane filter device, solid suspension is separated from the water out Come, the concentrated water after filtering returns to secondary softening device, and solid particle is after natural subsidence, dewater treatment;
F, removal hardness
The aqueous after step E processing is handled by Di, hardness remaining in waste water is removed;
G, light electrolysis dechlorination
The sodium chloride fortified aqueous after step E processing is desalinated by light electrolysis bipolar membrane device, the concentration of waste water is dropped Low to below 1000mg/L, water outlet disclosure satisfy that the water distribution requirement of lime stone slurry in desulphurization system, while obtaining acid and hydrogen-oxygen Change sodium solution;
H, reuse
Step H desalination after waste water recycling into desulphurization system as lime stone slurry configuration water, so as to reach zero-emission.
2. a kind of equipment for the technique of zero discharge of desulfurization wastewater Treatment and recovery described in claim 1, it is characterised in that The device and part installed by water (flow) direction order include
Wastewater collection pond(1), High-speed clarification separator(2), one-level softening plant(3), secondary softening device(4), TMF concentrated waters Case(5), TMF elevator pumps(8), TMF systems(9), TMF water producing tanks(10), exchange elevator pump(11), Di (12), middle water producing tank(13), electrolysis feed pump(14), light electrolysis bipolar membrane device(15)With product water tank(18);
Described wastewater collection pond(1)Immersible pump by collecting pit and in collecting pit is constituted, submersible pump outlet simultaneously with it is fast Fast clarified separation device(2)With one-level softening plant(3)Entrance be connected;
The High-speed clarification separator(2)Supernatant outlet and one-level softening plant(3)Entrance be connected;
Described one-level softening plant(3)With at least one chemicals dosing plant, one-level softening plant(3)Supernatant outlet with two grades Softening plant(4)Entrance be connected;
Described secondary softening device(4)Supernatant outlet and TMF concentrated water casees(5)Entrance is connected;Described High-speed clarification point From device(2), one-level softening plant(3)With TMF concentrated water casees(5)Bottom drain simultaneously connect sludge pump(6), sludge pump (6)Connect plate and frame filter press(7)Entrance, plate and frame filter press(7)Outlet connection wastewater collection pond(1);
The TMF concentrated waters case(5)Outlet and TMF elevator pumps(8)It is connected;
Described TMF elevator pumps(8)With TMF systems(9)Water inlet be connected;
The TMF systems(9)Concentrated water return to TMF concentrated water casees(5), TMF systems(9)The production mouth of a river and TMF water producing tanks(10)Phase Even;
The TMF water producing tanks(10)Delivery port with exchanging elevator pump(11)It is connected;
Described exchange elevator pump(11)With Di(12)Water inlet be connected;
The Di(12)Delivery port and middle water producing tank(13)It is connected;
The middle water producing tank(13)Outlet with electrolysis feed pump(14)It is connected;
Described electrolysis feed pump(14)With light electrolysis bipolar membrane device(15)Water inlet be connected;
Described light electrolysis bipolar membrane device(15)Final product water tank is connected by neutral delivery port(18), light electrolysis is bipolar Film device(15)Pass through acidic effluent mouthful and alkaline delivery port and acid solution case respectively(16)And lye tank(17)It is connected.
3. the zero-emission equipment of a kind of desulfurization wastewater Treatment and recovery according to claim 2, it is characterised in that described High-speed clarification separator(2)Supernatant outlet and one-level softening plant(3)Entrance between be also sequentially connected reaction tank and Filtering ponds.
CN201710381140.1A 2017-05-25 2017-05-25 The technique of zero discharge and equipment of desulfurization wastewater Treatment and recovery Pending CN107244773A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108059255A (en) * 2017-12-27 2018-05-22 大唐(北京)水务工程技术有限公司 Dispensing system and method in a kind of processing applied to high magnesium desulfurization wastewater
CN109607830A (en) * 2018-12-28 2019-04-12 新疆环境工程技术有限责任公司 A kind of high rigidity waste water chemistry-film coupling softening method

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108059255A (en) * 2017-12-27 2018-05-22 大唐(北京)水务工程技术有限公司 Dispensing system and method in a kind of processing applied to high magnesium desulfurization wastewater
CN109607830A (en) * 2018-12-28 2019-04-12 新疆环境工程技术有限责任公司 A kind of high rigidity waste water chemistry-film coupling softening method

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