CN107285489A - A kind of device and method of desulfurization wastewater pretreatment - Google Patents

A kind of device and method of desulfurization wastewater pretreatment Download PDF

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Publication number
CN107285489A
CN107285489A CN201710623483.4A CN201710623483A CN107285489A CN 107285489 A CN107285489 A CN 107285489A CN 201710623483 A CN201710623483 A CN 201710623483A CN 107285489 A CN107285489 A CN 107285489A
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CN
China
Prior art keywords
desulfurization wastewater
waste water
reactor
pretreatment
added
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Pending
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CN201710623483.4A
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Chinese (zh)
Inventor
刘海洋
杨春平
陈海杰
谷小兵
江澄宇
李叶红
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Datang Environment Industry Group Co Ltd
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Datang Environment Industry Group Co Ltd
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Priority to CN201710623483.4A priority Critical patent/CN107285489A/en
Publication of CN107285489A publication Critical patent/CN107285489A/en
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    • 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
    • C02F2101/00Nature of the contaminant
    • C02F2101/10Inorganic compounds
    • C02F2101/101Sulfur compounds
    • 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
    • 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

Abstract

The present invention provides a kind of device of desulfurization wastewater pretreatment.Including flowing to what is set along desulfurization wastewater:First-stage reactor, adds unit and an organic sulfur provided with a barium hydroxide or sulfide adds unit;Second reactor, unit is added provided with barium salt.By optimizing the softening pretreatment process method that desulfurization wastewater is evaporated before crystallization, the cost that desulfurization wastewater is handled using evaporative crystallization method can be effectively reduced.A kind of device is separately provided, organic sulfur or sulfide are added into unit and barium salt adds the position exchange of unit.The method that the desulfurization wastewater pretreatment implemented based on above two device is provided simultaneously.

Description

A kind of device and method of desulfurization wastewater pretreatment
Technical field
The invention belongs to environmental protection technical field, and in particular to a kind of device and method of desulfurization wastewater pretreatment.
Background technology
Coal fired power generation occupies critical role in China's energy resource supply.For environment protection, China is most in recent years Number power plant employs Limestone-gypsum Wet Flue Gas Desulfurization Process technology, to remove the sulfur dioxide in flue gas.Coal-burning power plant's wet desulphurization Waste component is complicated, contains high concentration suspended matter, oversaturated sulphite, chlorion, sulfate and various heavy.Mesh Preceding desulfurization wastewater is mainly handled using chemical precipitation method, part index number difficulty up to standard, even if after processing up to standard, due to big in waste water The presence of the sulfate and chloride of amount, water outlet salt content is still up to 2%~4%, it is difficult to reuse, can also cause after outer row Surface water and soil ecology are broken, cause secondary pollution.Therefore, the exploitation of desulfurization wastewater zero discharge treatment technology is increasingly by weight Depending on.
In a variety of developing ways of desulfurization wastewater Zero-discharge treating process, evaporative crystallization method is current research staff in the industry The main process of concern.Although can largely reduce the water outlet after desulfurization wastewater processing on evaporative crystallization law theory Salt content, even up to near-zero release standard brick, but in industrial practice, existed using evaporative crystallization method and unavoidably existed Shortcoming.
Shortcoming is mainly reflected in following two aspects:
First is that evaporative crystallization cost is high, needs to consume the substantial amounts of energy, therefore, operating cost using evaporative crystallization technique It is high;Second, minimizing processing is carried out to waste water using membrane separation techniques such as counter-infiltrations first, the concentrated water that UF membrane is produced is entered again Row evaporative crystallization, can effectively reduce evaporation process load and save processing cost.But needed when using the membrane treatment process such as RO Strict pretreatment is carried out to waste water, because calcium and magnesium concentration is high in waste water, calcium sulfate is in hypersaturated state, causes softening pre- Processing cost is high, general up to 15~30 yuan/ton, and substantial amounts of precipitating sludge can be also produced in preprocessing process, additionally Increase the processing cost of precipitating sludge.
In order to reduce desulfurization wastewater zero discharge treatment cost, evaporative crystallization method processing desulfurization wastewater technique is promoted, in view of existing The shortcoming and defect of desulfurization wastewater technique of zero discharge is deposited, the desulfurization wastewater preprocess method of developing low-cost is most important.
The content of the invention
In view of the above-mentioned problems, it is an object of the invention to provide a kind of device and method of desulfurization wastewater pretreatment.By excellent Change the softening pretreatment process method that desulfurization wastewater is evaporated before crystallization, can effectively reduce de- using the processing of evaporative crystallization method The cost of sulphur waste water.
For up to above-mentioned purpose, the present invention is adopted the technical scheme that:
A kind of device of desulfurization wastewater pretreatment, including flow to what is set along desulfurization wastewater:
First-stage reactor, adds unit and an organic sulfur provided with a barium hydroxide or sulfide adds unit;
Second reactor, unit is added provided with barium salt.
Further, in addition to the preliminary sedimentation tank that is arranged between first-stage reactor and second reactor;It is arranged at two grades instead Answer the second pond in device downstream.
Further, in addition to it is arranged at the pretreatment system of first-stage reactor upstream.
Further, the pretreatment system includes COD processing units and/or suspension processing unit.
Further, the first-stage reactor and second reactor are equipped with agitating unit.Agitating unit can be machinery Formula agitating unit, it would however also be possible to employ aeration agitation unit.
Further, the first-stage reactor includes the first reaction member and the second reaction member, and barium hydroxide adds list Member is located at the first reaction member, and organic sulfur or sulfide add unit located at the second reaction member.
Further, between the first-stage reactor and preliminary sedimentation tank, it is equipped with flocculation between second reactor and second pond Reaction member.
Further, the bottom of the preliminary sedimentation tank and second pond is respectively provided with mud discharging mouthful.
A kind of device of desulfurization wastewater pretreatment, including flow to what is set along desulfurization wastewater:
First-stage reactor, adds unit provided with a barium hydroxide and a barium salt adds unit;
Second reactor, unit is added provided with an organic sulfur or sulfide.
A kind of method of desulfurization wastewater pretreatment, comprises the following steps:
Barium hydroxide is added into desulfurization wastewater, pH value of waste water is adjusted to 8.5-10;Then organic sulfur or sulfide are added, Carry out except reacting and removing part of sulfuric acid root again, obtain except weight waste water;
Barium salt is added in except weight waste water, is removed except remaining sulfate ion in weight waste water.
A kind of method of desulfurization wastewater pretreatment, comprises the following steps:
Barium hydroxide is added into desulfurization wastewater, pH value of waste water is adjusted to 8.5-10;Then barium salt is added, is carried out except weight is anti- Part of sulfuric acid root and should be removed, is obtained except weight waste water;
Organic sulfur or sulfide are added in except weight waste water, is removed except remaining sulfate ion in weight waste water.
By taking the route of demagging simultaneously and deliming in above-mentioned technical proposal, abandoning tradition sofening treatment of the present invention, adopt Combine the method removed weight and remove sulfate radical with barium hydroxide and barium chloride, while heavy metal in waste water is removed, effectively keep away Exempt from the calcium sulfate scaling problem in follow-up Waste water concentrating processing, with technique is simple, added amount of chemical is few, operating cost is low, dirt Mud yield is few and is easy to the advantage that is combined with other techniques.Especially adapt to the processing for high-chlorine and high-calcium desulfurization wastewater.And And due to dosing can be reduced, the cost of desulfurization wastewater softening pretreatment can be greatly reduced, is conducive to evaporative crystallization method The technique for handling desulfurization wastewater is promoted.
Brief description of the drawings
Fig. 1 is the schematic device of desulfurization wastewater pretreatment in one embodiment of the invention.
Fig. 2 is its arrangement schematic diagram of first order reaction in another embodiment of the present invention.
Description of reference numerals:1- first-stage reactors, 2- preliminary sedimentation tanks, 3- mud dischargings mouth, 4- second reactors, 5- bis- sink Pond, 6- mud dischargings mouthful.
Embodiment
The present invention will be further described with embodiment with reference to the accompanying drawings and detailed description.
As shown in figure 1, in one embodiment there is provided desulfurization wastewater processing device, it flows to cloth according to desulfurization wastewater Put as follows:Including first-stage reactor 1, preliminary sedimentation tank 2, second reactor 4, second pond 5, the bottom difference of preliminary sedimentation tank 2 and second pond 6 Mud discharging mouthful 3 and mud discharging mouthful 6 are set.By setting preliminary sedimentation tank and second pond that heavy metal sewage sludge can be separated to independent place Reason, advantageously reduces Treatment of Sludge cost.
In not shown embodiment, desulfurization wastewater can enter back into reactor 1 after appropriate pretreatment.Pretreatment system System can be pre-processed using one or more of processing methods such as COD processing, suspension processing are included to desulfurization wastewater, pre- place The process requirements and desulfurization wastewater composition that the processing method that the choice of reason and specific pretreatment are used can combine reality adjust, It will not be repeated here, can be considered the common processing mode of desulfurization wastewater, unnecessarily associated with the application core purport.
As schemed, first-stage reactor 1 is provided with stirring system, can use mechanical agitation, it would however also be possible to employ aeration agitation, be used for Ensure that water quality is uniform in reactor.
First-stage reactor 1 is provided with adding of agent system, and medicament A and B are respectively barium hydroxide and organic sulfur, useless for removing Heavy metal and part of sulfuric acid root in water.Organic sulfur is mainly the removal of mercury, it would however also be possible to employ vulcanized sodium sulfides, but organic sulfur Application effect is good, it is easy to operate, and other heavy metals are mainly removed by barium hydroxide, and order of adding is necessary for after A elder generations B, because Organic sulfur also can remove other heavy metals, but organic sulfur price is very expensive.
In a further embodiment, first-stage reactor may be arranged as double-reactor as shown in Figure 2, and medicine is added successively Agent A and medicament B, is respectively used to carry out barium hydroxide except reaction and organic sulfur again are except reacting again.
In addition, flocculation reaction system can be arranged as required between first-stage reactor 1 and preliminary sedimentation tank 2, to improve sludge Sedimentation effect.Flocculation reaction medicament is similarly known, will not be repeated here.
The sludge of the discharge of mud discharging mouthful 3 is after dehydrating, further disposal;The sludge of the discharge of mud discharging mouthful 6 Deliver to Desulfurization tower slurry or drain into gypsum dehydration machine.
Stirring system and medicament addition device are again provided with second reactor 4.
Stirring system can use mechanical agitation, it would however also be possible to employ aeration agitation, for ensureing that water quality is uniform in reactor;
And medicament C is barium salt, preferably barium chloride, the sulfate radical for removing waste water residual.
Flocculation reaction system can be arranged as required between second reactor 4 and second pond 5, to improve sludge settling effect Rate.
The method that desulfurization wastewater pretreatment is carried out using said apparatus, can specifically be achieved by the steps of:
Desulfurization wastewater initially enters first-stage reactor 1, barium hydroxide and organic sulfur medicament is added into reactor, by waste water PH is adjusted to 9.5 or so, heavy metal in waste water is generated Precipitation, while part sulfate radical is combined to form with barium ions in waste water Barium sulfate precipitate.Above-mentioned pH adjusted values are preferred value under certain condition, indeed, it is possible to as needed by the adjustment of pH value Scope is arranged on 8.5 to 10.
The water outlet of first-stage reactor 1 enters in preliminary sedimentation tank 2, under gravity, realizes mud-water separation, and the sludge of generation leads to The discharge of mud discharging mouthful 3 is crossed after dehydrating, further disposal, supernatant enters in second reactor 4.
In order to improve sludge settling performance, flocculated before preliminary sedimentation tank 2 can be entered from first-stage reactor 1 with desulfurization wastewater Reaction.
Add barium salt into second reactor 4, preferably barium chloride, make sulfate radical in waste water reaction generation barium sulfate, will Sulfate radical is reduced to required level, it is ensured that will not substantially fouling in the processing of waste water subsequent concentration.
The water outlet of second reactor 4 enters in second pond 5, and after mud-water separation, supernatant is further disposed, second pond The sludge produced in 5 goes to Desulfurization tower slurry by the discharge of mud discharging mouthful 6 or drains into gypsum dehydration machine.
Likewise it is possible to set flocculation reaction system between second reactor 4 and second pond 5.
The above method can be adjusted, and device also does accommodation:Scheme is as follows:
Desulfurization wastewater initially enters first-stage reactor, and barium hydroxide and barium chloride medicament are added into reactor, is rationally set The dosage of two kinds of medicaments is put, wastewater pH is adjusted to 9.5 or so, heavy metal in waste water is generated Precipitation, while by waste water Middle part sulfate radical reaction generation barium sulfate precipitate, makes sulfate radical in waste water be reduced to target level.Barium chloride dosage according to Subsequent concentration technique needs, and flexibly determines, mainly controls sulfate concentration remaining in waste water.
Equally can according to actual needs, desulfurization wastewater can enter back into first-stage reactor after appropriate pretreatment.
The water outlet of first-stage reactor can be directly entered in second reactor.
Organic sulfur is added into second reactor, the heavy metals such as Mercury in Wastewater are further removed.
The water outlet of second reactor enters in second pond, and after mud-water separation, supernatant is further disposed, in second pond The sludge that the sludge of generation is produced by mud discharging mouthful carries out subsequent treatment.
Below by actual experimentation, the feasibility and superiority of the device and method of the application are verified.Tested Journey is as follows:
Certain power plant's practical sulphur removal waste water is taken, raw water pH is concentration of suspension about 20000mg/L in 6.8, waste water, is passed through first Simple filtration removes the suspension in waste water, and the calcium ion content in waste water is about 2600mg/L, and magnesium ion is 600mg/L, Sulfate concentration is 1000mg/L.It should be noted that heavy metal processing is conventional meanses in desulfurization wastewater processing, it is not this Apply for the emphasis of concern, the application focuses on entirely pre-processing cost, therefore does not provide content of beary metal herein.Next respectively Carry out following two groups of experiments:
Experiment one, using conventional pretreatment technique, i.e. milk of lime+organic sulfur+soda ash tenderizer, first to 1000mL waste water Wastewater pH is modulated 11.5 by the middle milk of lime (mass concentration is 5% suspension) that adds, while being stirred to waste water, it is ensured that anti- Should be fully and uniform, after reaction 15min, organic sulfur and sodium carbonate (mass concentration is 10% solution) are then added into waste water, Magnesium ion in waste water produces magnesium hydrate precipitate and entered in sludge, and waste water passes through calcium ion in flocculation sediment processed waste water Concentration is reduced to 20mg/L, and then heavy metal in waste water qualified discharge adds hydrochloric acid and wastewater pH is pulled back into 9.5, as a result show Added amount of chemical is milk of lime 4.0g/L, organic sulfur 50mg/L, soda ash 10.40g/L, and salt acid consumption is 3g/L.According to market Price, hydrochloric acid (30%), lime, organic sulfur (100%) and soda ash are respectively 300,500,120000 and 1500 yuan/ton, required Medicament totle drilling cost is about 24.1 yuan/ton.After measured, (sedimentation time is 20 minutes), precipitating sludge cumulative volume after two-stage precipitation About 230mL.Waste water after processing can meet film concentration water inlet hardness requirement.
Experiment two:Using the technique in the present invention, waste water is after preliminary filtering removes most suspended substances, to 1000mL Barium hydroxide solution (mass concentration 2%) is added in waste water, wastewater pH is adjusted to 9.5, organic sulfur solution, reaction is then added After 10min, added into waste water after flocculant and flocculation aid reaction 5min, determine sludge volume after static 15 minutes, then will Added after waste water filtering into filtrate after barium chloride, reaction 10min, flocculant and flocculation aid reaction 5min are added into waste water Afterwards, then static 15 minutes, supernatant sulfate radical and heavy metal concentration and precipitating sludge volume are determined.
As a result show, the sulfate radical in waste water is down to 20mg/L, during heavy metal qualified discharge, now barium hydroxide is added Measure as 0.05g/L, barium chloride dosage is 3.05g/L, and organic sulfur dosage is 50mg/L, according to the barium chloride market price 2600 yuan/ton, the barium hydroxide market price is 4500 yuan/ton, and the organic sulfur market price is 120000 yuan/ton, then ton water process About 14 yuan of reagent cost.After measured, after precipitation 15min, one-level precipitating sludge volume is 50mL, and two-stage precipitation sludge volume is about 20mL。
Experiment three:Using present invention process, waste water is after preliminary filtering removes most suspended substances, to 1000mL waste water Middle addition barium hydroxide solution (mass concentration 2%), 9.5 are adjusted to by wastewater pH, then add barium chloride (mass concentration 10%) After solution, reaction 10min, added into waste water after organic sulfur, reaction 10min, add flocculant into waste water and flocculation aid is anti- Answer after 5min, then after precipitation clarification 15min, determine supernatant sulfate radical and heavy metal concentration and precipitating sludge volume.
Found through overtesting, the sulfate radical in waste water is down to 20mg/L, during heavy metal qualified discharge, now barium hydroxide Dosage is 0.05g/L, and barium chloride dosage is 3.15g/L, and organic sulfur dosage is 50mg/L, according to barium chloride market 2600 yuan/ton of price, the barium hydroxide market price is 4500 yuan/ton, and the organic sulfur market price is 120000 yuan/ton, then ton water About 14.2 yuan for the treatment of agent cost.After measured, sludge cumulative volume about 65mL after being precipitated in 15min sedimentation basins.It is useless after raw processing Water can meet film concentration inflow requirement.
As can be seen from the above-described embodiment, using the PROCESS FOR TREATMENT desulfurization wastewater of the present invention, medicament expense is only 14 yuan/ Ton, 24.1 yuan/ton than traditional handicraft are greatly reduced, and the sludge quantity produced is also greatly reduced, and advantageously reduces follow-up sludge Handle load and processing cost.
Obviously, described embodiment is only a part of embodiment of the invention, rather than whole embodiments.Based on this hair Embodiment in bright, the every other implementation that those of ordinary skill in the art are obtained under the premise of creative work is not made Example, belongs to the scope of protection of the invention.

Claims (11)

1. a kind of device of desulfurization wastewater pretreatment, it is characterised in that including flowing to what is set along desulfurization wastewater:
First-stage reactor, adds unit and an organic sulfur provided with a barium hydroxide or sulfide adds unit;
Second reactor, unit is added provided with barium salt.
2. the device of desulfurization wastewater pretreatment as claimed in claim 1, it is characterised in that also including being arranged at first-stage reactor Preliminary sedimentation tank between second reactor;It is arranged at the second pond in second reactor downstream.
3. the device of desulfurization wastewater pretreatment as claimed in claim 2, it is characterised in that the first-stage reactor and preliminary sedimentation tank Between, between second reactor and second pond be equipped with flocculation reaction unit.
4. the device of desulfurization wastewater pretreatment as claimed in claim 2, it is characterised in that the bottom of the preliminary sedimentation tank and second pond Portion is respectively provided with mud discharging mouthful.
5. the device of desulfurization wastewater pretreatment as claimed in claim 1, it is characterised in that also including being arranged at first-stage reactor The pretreatment system of upstream.
6. the device of desulfurization wastewater pretreatment as claimed in claim 5, it is characterised in that the pretreatment system includes COD Processing unit and/or suspension processing unit.
7. the device of desulfurization wastewater as claimed in claim 1 pretreatment, it is characterised in that the first-stage reactor and two grades it is anti- Device is answered to be equipped with agitating unit.
8. the device of desulfurization wastewater pretreatment as claimed in claim 1, it is characterised in that the first-stage reactor includes first Reaction member and the second reaction member, barium hydroxide add unit located at the first reaction member, and organic sulfur or sulfide add list Member is located at the second reaction member.
9. a kind of method of desulfurization wastewater pretreatment, comprises the following steps:
Barium hydroxide is added into desulfurization wastewater, pH value of waste water is adjusted to 8.5-10;Then organic sulfur or sulfide are added, is carried out Except reacting and removing part of sulfuric acid root again, obtain except weight waste water;
Barium salt is added in except weight waste water, is removed except remaining sulfate ion in weight waste water.
10. a kind of device of desulfurization wastewater pretreatment, it is characterised in that including flowing to what is set along desulfurization wastewater:
First-stage reactor, adds unit provided with a barium hydroxide and a barium salt adds unit;
Second reactor, unit is added provided with an organic sulfur or sulfide.
11. a kind of method of desulfurization wastewater pretreatment, comprises the following steps:
Barium hydroxide is added into desulfurization wastewater, pH value of waste water is adjusted to 8.5-10;Then barium salt is added, remove and reacts again simultaneously Part of sulfuric acid root is removed, is obtained except weight waste water;
Organic sulfur or sulfide are added in except weight waste water, is removed except remaining sulfate ion in weight waste water.
CN201710623483.4A 2017-07-27 2017-07-27 A kind of device and method of desulfurization wastewater pretreatment Pending CN107285489A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108298755A (en) * 2018-03-05 2018-07-20 中化工程集团环保有限公司 Sulfate radical method of comprehensive utilization in coal chemical industrial waste water
CN109678279A (en) * 2019-02-27 2019-04-26 杭州航航环保科技有限公司 Sewage desulfurization process device
CN113060870A (en) * 2021-04-02 2021-07-02 大唐环境产业集团股份有限公司 Triple-box type desulfurization wastewater treatment method

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108298755A (en) * 2018-03-05 2018-07-20 中化工程集团环保有限公司 Sulfate radical method of comprehensive utilization in coal chemical industrial waste water
CN109678279A (en) * 2019-02-27 2019-04-26 杭州航航环保科技有限公司 Sewage desulfurization process device
CN113060870A (en) * 2021-04-02 2021-07-02 大唐环境产业集团股份有限公司 Triple-box type desulfurization wastewater treatment method

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