CN105502792B - A kind of zero emission treatment of desulfured waste water - Google Patents

A kind of zero emission treatment of desulfured waste water Download PDF

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CN105502792B
CN105502792B CN201610054012.1A CN201610054012A CN105502792B CN 105502792 B CN105502792 B CN 105502792B CN 201610054012 A CN201610054012 A CN 201610054012A CN 105502792 B CN105502792 B CN 105502792B
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effect
evaporating
desulfurization wastewater
concentration
waste water
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CN105502792A (en
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赵齐
吴学良
郭桦
刘汉强
吕洲
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GUODIAN NEW ENERGY TECHNOLOGY INSTITUTE
Chengdu Rui Si Green Technology Limited-Liability Co
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GUODIAN NEW ENERGY TECHNOLOGY INSTITUTE
Chengdu Rui Si Green Technology Limited-Liability Co
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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
    • C02F1/02Treatment of water, waste water, or sewage by heating
    • C02F1/04Treatment of water, waste water, or sewage by heating by distillation or evaporation
    • 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
    • C02F1/52Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/5236Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
    • C02F1/5245Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents using basic salts, e.g. of aluminium and iron
    • 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
    • C02F1/52Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/54Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
    • C02F1/56Macromolecular compounds
    • 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
    • C02F2101/00Nature of the contaminant
    • C02F2101/10Inorganic compounds
    • C02F2101/20Heavy metals or heavy metal compounds
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2201/00Apparatus for treatment of water, waste water or sewage
    • C02F2201/002Construction details of the apparatus
    • 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

Abstract

The invention discloses a kind of zero emission treatment of desulfured waste water, comprise the following steps:Desulfurization wastewater is through one-level chemical precipitation processing system(1)After processing, sodium carbonate is added into desulfurization wastewater to be reacted, then desulfurization wastewater is precipitated, filter after be sent into multi-effect evaporating device and be evaporated, the concentration of the scale-forming ion of mother liquor reaches before fouling concentration in multi-effect evaporating device or corrosive ions concentration reaches the partial mother liquid in multi-effect evaporating device is introduced into one-level chemical precipitation processing system before corrosion heat exchanger tube concentration(1)Processing.The beneficial effects of the invention are as follows:Reduce desulfurization wastewater fouling tendency, avoid fouling and influence heat transfer, corrosive ions to vaporization chamber heat exchanger tube cause corrosion phenomena such as generation;Desulfurization wastewater is changed into solute as the solution system based on NaCl simultaneously, multiple-effect vacuum evaporating, concentrating and crystallizing is carried out to desulfurization wastewater using coal fired power plant exhaust steam, and produces two level industrial goods salt byproduct, realizes desulfurization wastewater zero-emission.

Description

A kind of zero emission treatment of desulfured waste water
Technical field
The present invention relates to field technical field of waste water processing, in particular it relates to a kind of zero emission treatment of desulfured waste water.
Background technology
Coal fired power plant is during wet fuel gas desulfurizing technology, in order to maintain the balance of desulfurizer serum recycle system, Timing is needed from absorption tower waste discharge, i.e. desulfurization wastewater.Compared with coal fired power plant in general industrial wastewater, water-quality ratio is more special for it Very, wherein many materials are the first pollutant for requiring strictly to control in national environmental standard, it is mainly manifested in following Aspect:(1)Waste water is in faintly acid, and PH is 4 ~ 6;(2)Suspension content is high, and particle is small, and main component is gypsum, secondly also has and Calcium carbonate and calcium sulfite for being added in flying dust, sweetening process from flue gas etc.;(3)In waste water containing soluble chloride, Fluoride etc.;(4)It is containing heavy metal element, wherein mosts such as Pb, Cd, Cr, Ni, Hg, Co, Cu, Al, Zn, Mn in waste water The linear sewage drainage standard of thermal power plant(GB8978-1996)The heavy metal element of middle limitation.(5)In terms of water quality index, desulfurization is given up Chemical oxygen consumption (COC) in water(COD)And one of transnormal itemses.
Domestic most common method for treating desulfurized wastewater is chemical precipitation method at present, and this method is to utilize physics, chemistry side Method is by neutralizing, settling, the means such as clarification of flocculating remove most suspended substances, heavy metal ion etc. in desulfurization wastewater makes desulfurization Waste water reaches the existing discharge standard of country.Still containing the Ca being dissolved in waste water in waste water after treatment by using the treatment method2+、 Mg2+ 、Cl-、SO4 2-Etc. the salinity of high concentration, if directly discharge length can have a strong impact on to surrounding water generation for a long time.
The content of the invention
The technical problems to be solved by the invention be to provide it is a kind of desulfurization wastewater is carried out multiple-effect vacuum evaporating, concentrating and crystallizing, The desulfurization for reclaiming moisture and producing industrial goods salt and can effectively avoiding fouling or corrosion from impacting vaporization chamber heat exchanger tube is given up Water zero discharge processing method.
Technical scheme is used by the present invention solves the above problems:
A kind of zero emission treatment of desulfured waste water, comprises the following steps:Desulfurization wastewater is through one-level chemical precipitation processing system System processing after, into desulfurization wastewater add sodium carbonate reacted, then desulfurization wastewater is precipitated, filter after be sent into multiple-effect evaporation Device is evaporated, and the steam for evaporating output obtains condensed water after heat exchange, and the salt slurry for evaporating output enters equipment for separating liquid from solid Carry out separation of solid and liquid, obtain solid salt, in multi-effect evaporating device the concentration of the scale-forming ion of mother liquor reach before fouling concentration or Corrosive ions concentration introduces the partial mother liquid in multi-effect evaporating device at one-level chemical precipitation before reaching corrosion heat exchanger tube concentration The processing of reason system, the partial mother liquid are handled through chemical precipitation processing system, reduce scale-forming ion concentration and corrosive ions in mother liquor After concentration, it is again introduced into multi-effect evaporating device and is evaporated.
The present invention in the waste water after being handled through chemical precipitation method by adding Na2CO3Solution carries out second order reaction processing, With CO3 2-Precipitate Ca therein2+、Mg2+Ion, reduce the Ca in water2+、Mg2+Ion concentration, the fouling for reducing desulfurization wastewater are inclined To;Desulfurization wastewater is changed into solute as the solution system based on NaCl simultaneously.Desulfurization wastewater after second order reaction is handled, it is right It carries out multiple-effect vacuum evaporating, concentrating and crystallizing, moisture in desulfurization wastewater is separated with salinity, and moisture recycles, and produces main Composition is NaCl two level industrial goods salt byproduct, realizes the processing system of desulfurization wastewater zero-emission.The processing system is main The clear water for producing high-purity recycles, while produces the two level industrial goods salt byproduct that main component is NaCl, creates additional Value.The concentration of scale-forming ion in multi-effect evaporating device in mother liquor reaches before fouling concentration or corrosive ions concentration reaches corrosion The partial mother liquid in multi-effect evaporating device is introduced into one-level chemical precipitation processing system before heat exchanger tube concentration, steamed so as to reduce multiple-effect The ion concentration of mother liquor in concentration and crystallization device is sent out, avoids the generation of fouling or corrosion.
Further, in addition to by separation of solid and liquid the mother liquor obtained is introduced to the step of multi-effect evaporating device is evaporated.
Further, the scale-forming ion concentration for being additionally included in the mother liquor that separation of solid and liquid obtains reaches before fouling concentration or corroded Before ion concentration reaches corrosion heat exchanger tube concentration, the mother liquor is introduced into the step of one-level chemical precipitation processing system is handled.Avoid The mother liquor with high concentration scale-forming ion and corrosive ions enters multiple-effect evaporation concentration and crystallization device, and then avoids high concentration Scale-forming ion can on vaporization chamber heat exchanger tube fouling and influence heat transfer, the corrosive ions of high concentration can be to evaporation after enrichment method Room heat exchanger tube causes the generation of phenomena such as corrosion.
Further, in addition to by condensed water caused by multi-effect evaporating device to the desulfurization before entering multi-effect evaporating device give up The step of water is preheated.So as to which desulfurization wastewater is gone before multi-effect evaporating device is entered to scale-forming ion and corrosive ions Remove.
Preferably, the exhaust steam that multi-effect evaporating device is sent using power station is used as heating steam, using exhaust steam of electric power plant to desulfurization Waste water carries out multiple-effect vacuum evaporating, concentrating and crystallizing, moisture in desulfurization wastewater is separated with salinity.It is weary so as to take full advantage of power plant The heat energy of vapour, saves resource, avoids the waste of heat energy.
Further, the step of described desulfurization wastewater is evaporated into multi-effect evaporating device be:
Desulfurization wastewater advection enters multiple evaporating, concentrating and crystallizing devices of multi-effect evaporating device, head effect evaporating, concentrating and crystallizing dresses The heating steam put is provided by external steam source, and indirect steam caused by previous effect enters next effect evaporating, concentrating and crystallizing device, Dense salt slurry is using material mode is turned, and the mother liquor that salinity is improved through previous effect enters next effect evaporating, concentrating and crystallizing device, and end effect is steamed The mother liquor of hair concentration and crystallization device enters equipment for separating liquid from solid.
Further, in each effect evaporating, concentrating and crystallizing device, the condensed water that heating steam is formed flows into level of condensation weighing apparatus Bucket, condensed water balance caused flash-off steam in bucket and return to heating chamber, condensed water caused by previous effect evaporating, concentrating and crystallizing device Using condensed water balance bucket collect after deliver to it is latter effect condensed water balance bucket, with it is latter effect heating chamber caused by condensed water mix sudden strain of a muscle Next effect condensed water balance bucket is delivered to after hair some vapor.
Preferably, it is more to entering to introduce preheater for the condensed water in the condensed water balance bucket of end effect evaporating, concentrating and crystallizing device Desulfurization wastewater before effect vaporising device is preheated.
Further, the steam of the vaporization chamber of last effect evaporating, concentrating and crystallizing device enters vapour condensation device.
Further, the step of described desulfurization wastewater is handled through one-level chemical precipitation processing system uses existing conventional skill Art, generally comprise the steps:Desulfurization wastewater is introduced and neutralizes case, aqua calcis regulation pH value is added in case to neutralizing, Make Mg simultaneously2+、Pb2+、Cr3+、Cd2+Plasma is precipitated out with hydroxide form, the F in waste water-Ion is with CaF2Form is sunk Drop is come out, and neutralizes the waste water for completing to react in case and enters flow tank, and organic sulfur is added into flow tank, makes remnants Pb2+、 Cr3+、Cd2+It is precipitated out etc. heavy metal ion with sulphided form, the waste water that reaction is completed in flow tank enters flocculation tanks, to Flocculant is added in flocculation tanks(Chloro sulphuric acid iron)And/or flocculation aid(PAM)Sediment is set to combine sedimentation, through flocculation tanks discharge After the clarified device clarification of waste water, the processing of one-level chemical precipitation processing system is completed.
Using the concentration of two ways control system internal corrosive ion and fouling tendency type ion in treatment method In limits:1)Multi-effect evaporating device mother liquor reflux pipe is set to front end chemical precipitation processing system;2)Separation of solid and liquid fills Caused mother liquor reflux is put to chemical precipitation processing system.
To sum up, the beneficial effects of the invention are as follows:
1st, solve the directly pollution of discharge to surrounding water etc. of the salinity in the desulfurization wastewater after chemical precipitation method processing to ask Topic;Multiple-effect vacuum evaporating, concentrating and crystallizing is carried out to desulfurization wastewater using coal fired power plant exhaust steam, makes moisture and salinity in desulfurization wastewater Separation, water utilization is reclaimed, and produce the two level industrial goods salt byproduct that main component is NaCl, realize the zero-emission of desulfurization wastewater Put.
Using the present invention, for the water for the desulfurization wastewater that need to be handled, with reference to the desulfurization wastewater for different disposal amount, meter Required heat exchange area is calculated, the zero-emission of desulfurization wastewater is realized with reference to the suitable middle effect quantity of the selections such as investment.
2nd, the concentration of the scale-forming ion in vaporization chamber feed liquid reaches before fouling concentration or corrosive ions concentration reaches corrosion Before heat exchanger tube concentration, the feed liquid of discharge part vaporization chamber avoids the scale-forming ion meeting of high concentration to chemical precipitation processing system The fouling on vaporization chamber heat exchanger tube and influence heat transfer, the corrosive ions of high concentration can cause to vaporization chamber heat exchanger tube after enrichment method The generation of phenomena such as corrosion.
3rd, heating steam of the indirect steam as next effect caused by evaporation, steam are repeatedly utilized, and have saved the energy.
4th, the scale-forming ion concentration in mother vat in mother liquor reaches before fouling concentration or corrosive ions concentration reaches corrosion Before heat exchanger tube concentration, decomposition mother solution inside mother vat is introduced into one-level chemical precipitation processing system, avoided with high concentration fouling The mother liquor of ion and corrosive ions enters multiple-effect evaporation concentration and crystallization device, and the scale-forming ion for avoiding high concentration can be in vaporization chamber Fouling on heat exchanger tube and influence heat transfer, the corrosive ions of high concentration can cause corrosion etc. existing to vaporization chamber heat exchanger tube after enrichment method The generation of elephant.
5th, vaporization chamber form uses forced-circulation evaporation room, and each vaporization chamber of imitating is configured with forced circulation pump, increases desulfurization and gives up Flow velocity of the water in vaporization chamber heat exchanger tube, vaporization chamber heat transfer coefficient is improved, reduce equipment investment, while reduce salinity in heat exchanger tube Upper fouling possibility.
6th, multi-effect evaporation system feeding manner is fed using advection, reduces fouling tendency.
7th, respectively the salt of effect vaporization chamber output goes to middle effect from head effects, goes to end effect successively, is discharged from end effect, reduces discharge Salt slurry temperature, system heat loss is reduced, reduce steam consumption, save the energy.
8th, steam condensate (SC) is collected with condensed water balance bucket, and shwoot goes out some vapor as heating steam, reduces steam and uses Amount, save the energy.
9th, desulfurization wastewater is preheated using steam condensate (SC), raising enters vaporization chamber desulfurization wastewater temperature, reduces and steams Vapour dosage, save the energy.
The 10th, vavuum pump is set, the incoagulable gas in extraction system, improve end effect vacuum, improve effective heat transfer temperature difference, Steam consumption is reduced, saves the energy.
Brief description of the drawings
Fig. 1 is the structural representation of the present invention.
Mark and corresponding parts title in accompanying drawing:
1- one-level chemical precipitation processing systems, 2- second order reaction casees, 3- Secondary clarifiers, 4- filters, 5- preheaters, 6- Circulating pump, 7- heating chambers, 8- vaporization chambers, 9- condensed waters balance bucket, 10- thickeners, 11- centrifuges, 12- mother vats, 13- surfaces Condenser, 14- condensed water buckets, 15- vavuum pumps.
Embodiment
The present invention will now be described in further detail with reference to the accompanying drawings and the accompanying drawings, but embodiments of the present invention Not limited to this.
Embodiment:
As shown in figure 1, a kind of zero emission treatment of desulfured waste water, comprises the following steps:Desulfurization wastewater is through one-level chemistry After the processing of precipitation process system 1, into desulfurization wastewater adding sodium carbonate is reacted, after then desulfurization wastewater is precipitated, filter It is sent into multi-effect evaporating device to be evaporated, the steam for evaporating output obtains condensed water after heat exchange, and the salt slurry for evaporating output enters Equipment for separating liquid from solid carries out separation of solid and liquid, obtains solid salt, the concentration of the scale-forming ion of mother liquor reaches in multi-effect evaporating device Before fouling concentration or corrosive ions concentration reach corrosion heat exchanger tube concentration before by multi-effect evaporating device partial mother liquid introduce one Level chemical precipitation processing system 1 is handled, and the partial mother liquid is handled through chemical precipitation processing system, and it is dense to reduce scale-forming ion in mother liquor After degree and corrosive ions concentration, it is again introduced into multi-effect evaporating device and is evaporated.
The present invention in the waste water after being handled through chemical precipitation method by adding Na2CO3Solution carries out second order reaction processing, With CO3 2-Precipitate Ca therein2+、Mg2+Ion, reduce the Ca in water2+、Mg2+Ion concentration, the fouling for reducing desulfurization wastewater are inclined To;Desulfurization wastewater is changed into solute as the solution system based on NaCl simultaneously.Desulfurization wastewater after second order reaction is handled, it is right It carries out multiple-effect vacuum evaporating, concentrating and crystallizing, moisture in desulfurization wastewater is separated with salinity, and moisture recycles, and produces main Composition is NaCl two level industrial goods salt byproduct, realizes the processing system of desulfurization wastewater zero-emission.The processing system is main The clear water for producing high-purity recycles, while produces the two level industrial goods salt byproduct that main component is NaCl, creates additional Value.The concentration of scale-forming ion in multi-effect evaporating device in mother liquor reaches before fouling concentration or corrosive ions concentration reaches corrosion The partial mother liquid in multi-effect evaporating device is introduced into one-level chemical precipitation processing system 1 before heat exchanger tube concentration, so as to reduce multiple-effect The ion concentration of mother liquor in evaporating, concentrating and crystallizing device, avoids the generation of fouling or corrosion.
Further, in addition to by separation of solid and liquid the mother liquor obtained is introduced to the step of multi-effect evaporating device is evaporated.
Further, the scale-forming ion concentration for being additionally included in the mother liquor that separation of solid and liquid obtains reaches before fouling concentration or corroded Before ion concentration reaches corrosion heat exchanger tube concentration, the mother liquor is introduced into the step of one-level chemical precipitation processing system 1 is handled.Avoid The mother liquor with high concentration scale-forming ion and corrosive ions enters multiple-effect evaporation concentration and crystallization device, and then avoids high concentration Scale-forming ion can on the heat exchanger tube of vaporization chamber 8 fouling and influence heat transfer, the corrosive ions of high concentration can be to steaming after enrichment method The generation for phenomena such as hair heat exchanger tube of room 8 causes corrosion.
Further, in addition to by condensed water caused by multi-effect evaporating device to the desulfurization before entering multi-effect evaporating device give up The step of water is preheated.So as to which desulfurization wastewater is gone before multi-effect evaporating device is entered to scale-forming ion and corrosive ions Remove.
Preferably, the exhaust steam that multi-effect evaporating device is sent using power station is used as heating steam, using exhaust steam of electric power plant to desulfurization Waste water carries out multiple-effect vacuum evaporating, concentrating and crystallizing, moisture in desulfurization wastewater is separated with salinity.It is weary so as to take full advantage of power plant The heat energy of vapour, saves resource, avoids the waste of heat energy.
Further, the step of described desulfurization wastewater is evaporated into multi-effect evaporating device be:
Desulfurization wastewater advection enters multiple evaporating, concentrating and crystallizing devices of multi-effect evaporating device, head effect evaporating, concentrating and crystallizing dresses The heating steam put is provided by external steam source, and indirect steam caused by previous effect enters next effect evaporating, concentrating and crystallizing device, Dense salt slurry is using material mode is turned, and the mother liquor that salinity is improved through previous effect enters next effect evaporating, concentrating and crystallizing device, and end effect is steamed The mother liquor of hair concentration and crystallization device enters equipment for separating liquid from solid.
Further, in each effect evaporating, concentrating and crystallizing device, the condensed water that heating steam is formed flows into level of condensation weighing apparatus Bucket 9, condensed water balance caused flash-off steam in bucket 9 and return to heating chamber 7, condensed caused by previous effect evaporating, concentrating and crystallizing device Water conservancy delivers to latter effect condensed water balance bucket 9 after being collected with condensed water balance bucket 9, condensed water caused by heating chamber 7 is imitated with latter Next effect condensed water balance bucket 9 is delivered to after mixing shwoot some vapor.
Preferably, the condensed water in the condensed water balance bucket 9 of end effect evaporating, concentrating and crystallizing device introduces preheater 5 to entering Desulfurization wastewater before multi-effect evaporating device is preheated.
Further, the steam of the vaporization chamber 8 of last effect evaporating, concentrating and crystallizing device enters vapour condensation device.
Further, the step of described desulfurization wastewater is handled through one-level chemical precipitation processing system 1 uses existing routine Technology, generally comprise the steps:Desulfurization wastewater is introduced and neutralizes case, aqua calcis regulation pH is added in case to neutralizing Value, while make Mg2+、Pb2+、Cr3+、Cd2+Plasma is precipitated out with hydroxide form, the F in waste water-Ion is with CaF2Shape Formula is settled, and neutralizes the waste water for completing to react in case and enters flow tank, and organic sulfur is added into flow tank, makes remnants' Pb2+、Cr3+、Cd2+It is precipitated out etc. heavy metal ion with sulphided form, the waste water that reaction is completed in flow tank enters flocculation Case, flocculant chloro sulphuric acid iron and/or flocculation aid PAM are added into flocculation tanks makes sediment combine sedimentation, is discharged through flocculation tanks The clarification of waste water clarified device after, complete one-level chemical precipitation processing system 1 and handle.
Using the concentration of two ways control system internal corrosive ion and fouling tendency type ion in treatment method In limits:1 sets multi-effect evaporating device mother liquor reflux pipe to front end chemical precipitation processing system;2 equipment for separating liquid from solid Caused mother liquor reflux is to chemical precipitation processing system.
Using a kind of system of zero emission treatment of desulfured waste water, including what is set gradually be used to remove desulfurization and give up Heavy metal ion and F in water-The one-level chemical precipitation processing system 1 of ion, by adding Na2CO3Solution is to remove desulfurization wastewater In Ca2+、Mg2+Ion and secondary chemical precipitation process system, multi-effect evaporating device and the equipment for separating liquid from solid for generating NaCl, Also include the pipeline that the mother liquor in multi-effect evaporating device is introduced to one-level chemical precipitation processing system 1.
The present invention in the waste water after being handled through chemical precipitation method by adding Na2CO3Solution carries out second order reaction processing, With CO3 2-Precipitate Ca therein2+、Mg2+Ion, reduce the Ca in water2+、Mg2+Ion concentration, the fouling for reducing desulfurization wastewater are inclined To;Desulfurization wastewater is changed into solute as the solution system based on NaCl simultaneously.Desulfurization wastewater after second order reaction is handled, it is right It carries out multiple-effect vacuum evaporating, concentrating and crystallizing, moisture in desulfurization wastewater is separated with salinity, and moisture recycles, and produces main Composition is NaCl two level industrial goods salt byproduct, realizes the processing system of desulfurization wastewater zero-emission.The processing system is main The clear water for producing high-purity recycles, while produces the two level industrial goods salt byproduct that main component is NaCl, creates additional Value.
And the concentration of the scale-forming ion in multi-effect evaporating device in mother liquor reaches before fouling concentration or corrosive ions concentration Reach and the partial mother liquid in multi-effect evaporating device is introduced into one-level chemical precipitation processing system 1 before corrosion heat exchanger tube concentration, so as to The scale-forming ion of mother liquor and the concentration of corrosive ions in multiple-effect evaporation concentration and crystallization device are reduced, avoids the hair of fouling or corrosion It is raw.
One-level chemical precipitation processing system 1 is that the device of desulfurization wastewater processing is carried out using the traditional chemical precipitation method, to pass System equipment, it generally comprises neutralization case, flow tank, flocculation tanks and the primary-clarifiers set gradually, and desulfurization wastewater, which enters, to be neutralized After case, aqua calcis regulation pH value is added in case to neutralizing, while make Mg2+、Pb2+、Cr3+、Cd2+Plasma is with hydroxide Thing form is precipitated out, the F in waste water-Ion is with CaF2Form settles, and neutralizes the waste water for completing to react in case and enters sedimentation Case, and organic sulfur is added into flow tank, make remnants Pb2+、Cr3+、Cd2+It is settled out etc. heavy metal ion with sulphided form Come, the waste water that reaction is completed in flow tank enters flocculation tanks, and flocculant chloro sulphuric acid iron, flocculation aid PAM are added into flocculation tanks Sediment is set to combine sedimentation, through the waste water of flocculation tanks discharge after primary-clarifiers are clarified, into secondary chemical precipitation process system System.
Described secondary chemical precipitation process system includes the second order reaction case 2, Secondary clarifier 3 and filtering set gradually Device 4.Na is added into second order reaction case 22CO3Solution is with CO3 2-Precipitate Ca therein2+、Mg2+Ion, reduce the Ca in water2+、 Mg2+Ion concentration, reduces the fouling tendency of desulfurization wastewater, while desulfurization wastewater is changed into solute for the solution body based on NaCl System, enter multi-effect evaporating device after Secondary clarifier 3 and filter 4 remove precipitation.
Described multi-effect evaporating device includes multiple evaporating, concentrating and crystallizing devices, and each evaporating, concentrating and crystallizing device is respectively provided with There is the pipeline that its internal mother liquor is introduced to one-level chemical precipitation processing system 1.The steam of input is utilized repeatedly, and steam is sharp Number is referred to as " effect number ", and the heating steam of head effects is provided by external steam feeding mechanism, it is preferred that the heating steam of head effects There is provided by exhaust steam of electric power plant, indirect steam caused by previous effect evaporation enters next effect evaporating, concentrating and crystallizing device, as next effect The heating steam of evaporating, concentrating and crystallizing device, by that analogy, steam is repeatedly utilized, and the evaporation of end effect evaporated crystallization device produces Indirect steam deliver to end effect vapour condensation device and be cooled with circulating water to form vacuum, improve heat transfer temperature difference.Dense salt slurry uses Turn material mode by effect, i.e., first effect concentrate is transferred to two effects and concentrated again, and two effect concentrates are transferred to next effect, by that analogy. The salt slurries of end effect evaporating, concentrating and crystallizing device enter equipment for separating liquid from solid.During the effect evaporating, concentrating and crystallizing device quantitative design of centre Increased and decreased according to system processing power.
Described evaporating, concentrating and crystallizing device includes heating chamber 7, circulating pump 6 and vaporization chamber 8, and the drainpipe of vaporization chamber 8 connects Connect the water inlet of circulating pump 6, the water inlet pipe of the discharge outlet connection heater of circulating pump 6, the drainpipe connection vaporization chamber 8 of heater Water inlet pipe, the liquid in vaporization chamber 8 and heater circulates in the presence of circulating pump 6, and row's steam pipe of vaporization chamber 8 connects The steam input pipe of the heating chamber 7 of next effect evaporating, concentrating and crystallizing device is connect, the heating chamber 7 of head effect evaporating, concentrating and crystallizing devices Steam input pipe connects SS, is provided between adjacent two-effect evaporation concentration and crystallization device by previous effect evaporating, concentrating and crystallizing The mother liquor of device introduces the pipeline of next effect evaporating, concentrating and crystallizing device, and the mother liquor discharge pipe of end effect evaporating, concentrating and crystallizing device connects Equipment for separating liquid from solid is connect, the wastewater drainage pipe of secondary chemical precipitation process system is connected with each effect evaporating, concentrating and crystallizing device, given up The pipeline of the drainpipe and the water inlet of circulating pump 6 of the connection vaporization chamber 8 of each effect evaporating, concentrating and crystallizing device of water drainpipe connection. The often effect for making the desulfurization wastewater advection after second order reaction processing enter in multiple-effect evaporation concentration and crystallization device, i.e., often imitate vaporization chamber 8 In enter fresh desulfurization wastewater.
Heating chamber 7 is heat exchanger structure, after the steam input pipe of heating steam heated room 7 enters heating chamber 7, with heating Liquid in the pipeline of room 7 is exchanged heat, and Heat Room is discharged after being condensed into condensate liquid.Wastewater mother liquor under the driving of circulating pump 6 Circulated in heating chamber 7 and vaporization chamber 8.
The desulfurization wastewater forced circulation under the effect of forced circulation pump 6, secondary chemical precipitation in evaporating, concentrating and crystallizing device Desulfurization wastewater advection after processing system processing is sent into each effect evaporating, concentrating and crystallizing device circulation pipe, is improved through forced circulation pump 6 Enter heating chamber 7 after flow velocity and carry out gas-liquid separation with entering vaporization chamber 8 after steam heat-exchanging heating.
Described evaporating, concentrating and crystallizing device improves rate of circulating flow using forced circulation, improves heat transfer coefficient, reduces equipment Investment, while reduce heat exchanger tube fouling tendency.
Preferably, the steam that described multi-effect evaporating device uses is exhaust steam caused by power station, i.e. multi-effect evaporating device The exhaust steam discharge pipe in the steam input pipe connection power station of the heating chamber 7 of head effect evaporating, concentrating and crystallizing devices, the exhaust steam that power station is sent Deliver to first effect heating chamber 7 to heat desulfurization wastewater, indirect steam is as next effect heating chamber 7 caused by head effect vaporization chambers 8 Thermal source, the like.Multiple-effect vacuum evaporation and concentration is carried out to the desulfurization wastewater after second order reaction is handled using exhaust steam of electric power plant Crystallization, makes moisture in desulfurization wastewater be separated with salinity.So as to take full advantage of the heat energy of exhaust steam of electric power plant, resource is saved, is avoided The waste of heat energy.
Described evaporating, concentrating and crystallizing device also includes condensed water balance bucket 9, and the condensed water discharge pipe connection of heating chamber 7 is cold Condensate balances bucket 9, and the condensed water that heating steam is formed flows into level of condensation weighing apparatus bucket 9, and condensed water balance bucket 9 is provided with flash-off steam Discharge pipe, flash-off steam discharge pipe connect the steam input pipe of heating chamber 7.
Further, the latter effect evaporation of drainpipe connection of the condensed water balance bucket 9 of previous effect evaporating, concentrating and crystallizing device The condensed water balance bucket 9 of concentration and crystallization device, so as to utilization of condensed water condensed water caused by previous effect evaporating, concentrating and crystallizing device Balance bucket 9 delivers to latter effect condensed water balance bucket 9 after collecting, condensed water mixing shwoot part caused by heating chamber 7 is imitated with latter Next effect condensed water balance bucket 9, so circulation are delivered to after steam.
Preferably, described system also includes a preheater 5, and the discharging tube connection of secondary chemical precipitation process system should It is connected again with evaporating, concentrating and crystallizing device after preheater 5, the drainpipe of the condensed water balance bucket 9 of end effect evaporating, concentrating and crystallizing device Condensed water bucket 14 is reconnected after connecting the preheater 5 by pipeline, so as to be arranged by condensed water secondary chemical precipitation process system The desulfurization wastewater gone out is preheated, and the condensed water after heat exchange flow to condensed water bucket 14 and reclaimed again, cold so as to take full advantage of The heat energy of condensate, that is, take full advantage of the heat energy of heating steam.The condensed water that condensed water bucket 14 is collected can send power plant's recovery profit back to With.
Described equipment for separating liquid from solid includes the thickener 10 and centrifuge 11 set gradually, thickener 10 and centrifuge 11 Liquid discharge tube connection mother vat 12, mother vat 12 discharging tube connection multiple-effect evaporation concentration and crystallization device.Multiple-effect evaporation is dense The salt slurries of output deliver to suspension separation again in thickener 10 in contracting crystallization apparatus, and the salt slurry after thickening recycles centrifuge 11 Separation of solid and liquid is carried out, solid salt is isolated and is taken out as Nacl, the saline solution isolated, which is returned in vaporization chamber 8, to be evaporated.
Preferably, the discharging tube of mother vat 12 also connects one-level chemical precipitation processing system 1 by pipeline, in mother vat 12 Before scale-forming ion concentration in interior mother liquor reaches before fouling concentration or corrosive ions concentration reaches corrosion heat exchanger tube concentration, by mother The inside decomposition mother solution of liquid bucket 12 introduces one-level chemical precipitation processing system 1, so as to reduce mother liquor in multiple-effect evaporation concentration and crystallization device Ion concentration, avoid the generation of fouling or corrosion.
Described system also includes end effect vapour condensation device, the end effect evaporating, concentrating and crystallizing device of multi-effect evaporating device Row's steam pipe of vaporization chamber 8 connects the end effect vapour condensation device, and the condensed water discharging tube connection of end effect vapour condensation device is cold Condensate bucket 14.Described end effect vapour condensation device is surface condenser 13, it is preferred that surface condenser 13 be connected with one it is right Its vavuum pump 15 vacuumized, for fixed gas to be emptied.
Using the present invention, for the desulfurization wastewater of different disposal amount, required heat exchange area only need to be calculated, with reference to investment etc. Effect quantity can be achieved among selection is suitable.
Multiple-effect vacuum evaporating, concentrating and crystallizing technology in the multiple-effect evaporation condensing crystallizing system is using two ways control system The concentration of system internal corrosive ion and fouling tendency type ion is in limits:1 sets multi-effect evaporating device mother liquor reflux Pipe is to front end one-level chemical precipitation processing system 1;Mother liquor reflux caused by 2 equipment for separating liquid from solid to one-level chemical precipitation is handled System 1.
As described above, it can preferably realize the present invention.

Claims (8)

1. a kind of zero emission treatment of desulfured waste water, it is characterised in that comprise the following steps:Desulfurization wastewater is heavy through one-level chemistry After shallow lake processing system (1) processing, into desulfurization wastewater adding sodium carbonate is reacted, after then desulfurization wastewater is precipitated, filter It is sent into multi-effect evaporating device to be evaporated, the steam for evaporating output obtains condensed water after heat exchange, and the salt slurry for evaporating output enters Equipment for separating liquid from solid carries out separation of solid and liquid, obtains solid salt, the concentration of the scale-forming ion of mother liquor reaches in multi-effect evaporating device Before fouling concentration or corrosive ions concentration reach corrosion heat exchanger tube concentration before, by multi-effect evaporating device partial mother liquid introduce one Level chemical precipitation processing system (1) processing, the partial mother liquid are handled through chemical precipitation processing system, reduce scale-forming ion in mother liquor After concentration and corrosive ions concentration, it is again introduced into multi-effect evaporating device and is evaporated;
The step of described desulfurization wastewater is evaporated into multi-effect evaporating device be:Desulfurization wastewater advection fills into multiple-effect evaporation The multiple evaporating, concentrating and crystallizing devices put, the heating steam of head effect evaporating, concentrating and crystallizing devices is provided by external steam source, previous Indirect steam caused by effect enters next effect evaporating, concentrating and crystallizing device, and dense salt slurry is improved using material mode is turned through previous effect The mother liquor of salinity enters next effect evaporating, concentrating and crystallizing device, and the mother liquor of end effect evaporating, concentrating and crystallizing device fills into separation of solid and liquid Put;
In each effect evaporating, concentrating and crystallizing device, the condensed water that heating steam is formed flows into level of condensation weighing apparatus bucket (9), level of condensation Caused flash-off steam returns to heating chamber (7) in weighing apparatus bucket (9), and utilization of condensed water caused by previous effect evaporating, concentrating and crystallizing device is cold Condensate balance bucket (9) delivers to latter effect condensed water balance bucket (9) after collecting, with latter effect heating chamber (7) caused by condensed water mix Next effect condensed water balance bucket (9) is delivered to after closing shwoot some vapor.
2. a kind of zero emission treatment of desulfured waste water according to claim 1, it is characterised in that also include solid-liquid point The step of multi-effect evaporating device is evaporated is introduced to from obtained mother liquor.
3. a kind of zero emission treatment of desulfured waste water according to claim 1 or 2, it is characterised in that be additionally included in solid The scale-forming ion concentration of the isolated mother liquor of liquid reaches before fouling concentration or corrosive ions concentration reaches corrosion heat exchanger tube concentration Before, the mother liquor is introduced into the step of one-level chemical precipitation processing system (1) is handled.
4. a kind of zero emission treatment of desulfured waste water according to claim 1, it is characterised in that also include steaming multiple-effect The step of condensed water caused by transmitting apparatus preheats to the desulfurization wastewater before entering multi-effect evaporating device.
A kind of 5. zero emission treatment of desulfured waste water according to claim 1, it is characterised in that described multiple-effect evaporation Device is using the exhaust steam that power station is sent as heating steam.
6. a kind of zero emission treatment of desulfured waste water according to claim 1, it is characterised in that end effect is concentrated by evaporation knot Condensed water in the condensed water balance bucket (9) of brilliant device introduces preheater (5) to the desulfurization wastewater before entering multi-effect evaporating device Preheated.
7. a kind of zero emission treatment of desulfured waste water according to claim 1, it is characterised in that last effect evaporation is dense The steam of the vaporization chamber (8) of contracting crystallization apparatus enters vapour condensation device.
A kind of 8. zero emission treatment of desulfured waste water according to claim 1, it is characterised in that described desulfurization wastewater The step of being handled through one-level chemical precipitation processing system (1) is to introduce desulfurization wastewater to neutralize case, and hydrogen-oxygen is added to neutralizing in case Change calcium solution, neutralize the waste water for completing to react in case and enter flow tank, and organic sulfur is added into flow tank, completed in flow tank The waste water of reaction enters flocculation tanks, and flocculant or flocculation aid are added into flocculation tanks makes sediment combine sedimentation, is arranged through flocculation tanks After the clarified device clarification of waste water gone out, one-level chemical precipitation processing system (1) processing is completed.
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