CN109354248A - A kind of processing method of wet desulphurization waste water - Google Patents

A kind of processing method of wet desulphurization waste water Download PDF

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CN109354248A
CN109354248A CN201811363267.1A CN201811363267A CN109354248A CN 109354248 A CN109354248 A CN 109354248A CN 201811363267 A CN201811363267 A CN 201811363267A CN 109354248 A CN109354248 A CN 109354248A
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waste water
hybrid reaction
processing method
clear liquid
sediment
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戴友芝
杨涵童
陈敏行
刘丹妮
彭亮平
翟亚丽
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Xiangtan University
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Xiangtan University
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00—Multistage treatment of water, waste water or sewage
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/722—Oxidation by peroxides
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/18—Nature of the water, waste water, sewage or sludge to be treated from the purification of gaseous effluents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00—Use of specific compounds during water treatment
    • C02F2305/02—Specific form of oxidant
    • C02F2305/026—Fenton's reagent

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  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Removal Of Specific Substances (AREA)
  • Treatment Of Water By Oxidation Or Reduction (AREA)

Abstract

The invention belongs to waste water treatment field more particularly to a kind of processing methods of wet desulphurization waste water.Method for treating desulfurized wastewater provided by the invention then with hydrogen peroxide and ferrous salt hybrid reaction, obtains oxidized waste water the following steps are included: the pH value of desulfurization wastewater a) is adjusted to 2.25~4.5；B) by the oxidized waste water and calper calcium peroxide hybrid reaction, sediment is removed, clear liquid is obtained；C) in Mg2+Under existence condition, by the clear liquid and hydrophosphate hybrid reaction, sediment is removed, processed waste water is obtained；The Mg2+Source be additional Mg2+And/or the Mg contained in the clear liquid2+.Present invention joint utilizes Fenton oxidation, calcium silicon composite precipitation and magnesium ammonium phosphate sediment technical treatment desulfurization wastewater, can efficiently remove the COD and ammonia nitrogen of wet desulphurization waste water.

Description

A kind of processing method of wet desulphurization waste water
This application claims in submission on November 12nd, 2018 Patent Office of the People's Republic of China, application No. is 201811338535.4, invention A kind of priority of the Chinese patent application of entitled " processing method of wet desulphurization waste water ", entire contents pass through reference knot It closes in this application.
Technical field
The invention belongs to waste water treatment field more particularly to a kind of processing methods of wet desulphurization waste water.
Background technique
Sintering flue gas desulfurization is the key that the non-electricities industry such as steel realizes energy-saving and emission-reduction.In sintering smoke wet method sulphur mistake Cheng Zhong, absorption tower and recycle slurry absorbing liquid system can enriched Cl-、SO4 2-And heavy metal ion, discharge/replacement section need to be passed through Useless circulating absorption solution is divided to reduce its harm to wet desulphurization operating system, to maintain stablizing for circulating absorption solution system to transport Row.The waste water that the circulating absorption solution being displaced dumps after cyclone is handled is desulfurization wastewater.Due in desulfurization wastewater Contain a large amount of heavy metal ion, suspended matter, high concentration dissolubility salt, reduction-state inorganic matter, ammonia nitrogen (NH3- N), halide and Silanes etc., it is therefore necessary to could outlet or reuse after certain processing.
Currently, wet desulphurization waste water treatment process generallys use chemical precipitation method and combinations thereof technique, such as three header works Skill.So-called three header is a kind of integrated wet desulphurization sewage treatment equipment, including neutralizes case (neutralization pond), settling tank (precipitating Pond) and flocculation tanks (flocculation basin), which has significantly the pollutants such as heavy metal, suspended matter in processing desulfurization wastewater Effect, but it is lower to the removal rate of the pollutants such as COD and ammonia nitrogen.
Summary of the invention
In view of this, the purpose of the present invention is to provide a kind of processing method of wet desulphurization waste water, it is provided by the invention Method is higher to the COD and ammonia nitrogen removal frank of wet desulphurization waste water.
The present invention provides a kind of processing methods of wet desulphurization waste water, comprising the following steps:
A) pH value of desulfurization wastewater is adjusted to 2.25~4.5, then with hydrogen peroxide and ferrous salt hybrid reaction, obtained Oxidized waste water；
B) by the oxidized waste water and calper calcium peroxide hybrid reaction, sediment is removed, clear liquid is obtained；
C) in Mg2+Under existence condition, by the clear liquid and hydrophosphate hybrid reaction, sediment is removed, after obtaining processing Waste water；
The Mg2+Source be additional Mg2+And/or the Mg contained in the clear liquid2+。
Preferably, the ferrous salt includes ferrous sulfate and/or frerrous chloride.
Preferably, the Fe in step a), in the hydrogen peroxide and ferrous salt2+Molar ratio be 1:(0.5~1.5).
Preferably, in step a), the amount ratio of the hydrogen peroxide and desulfurization wastewater is (0.5~5) mmol:1L.
Preferably, in step a), the time of the hybrid reaction is 10~20min.
Preferably, the molar ratio of hydrogen peroxide described in calper calcium peroxide described in step b) and step a) is (1~1.5): 1。
Preferably, in step b), the time of the hybrid reaction is 30~50min.
Preferably, in step c), the hydrophosphate includes Na2HPO4And/or NaH2PO4。
Preferably, the NH in acid ion and clear liquid in step c), in the hydrophosphate3The molar ratio of-N be (1~ 2):1。
Preferably, in step c), the time of the hybrid reaction is 20~40min.
Compared with prior art, the present invention provides a kind of processing methods of wet desulphurization waste water.It is provided by the invention de- Sulphur wastewater treatment method the following steps are included: the pH value of desulfurization wastewater a) is adjusted to 2.25~4.5, then with hydrogen peroxide and Ferrous salt hybrid reaction, obtains oxidized waste water；B) by the oxidized waste water and calper calcium peroxide hybrid reaction, sediment is removed, is obtained To clear liquid；C) in Mg2+Under existence condition, by the clear liquid and hydrophosphate hybrid reaction, sediment is removed, is given up after being handled Water；The Mg2+Source be additional Mg2+And/or the Mg contained in the clear liquid2+.The present invention joint using Fenton oxidation, Calcium silicon composite precipitation and magnesium ammonium phosphate sediment technical treatment desulfurization wastewater, the first step utilize Fe2+And H2O2Between chain reaction produce The raw OH with strong oxidizing property, can aoxidize a variety of toxic and difficult to degrade complex organic compound, to make to divide greatly in water Sub- oxidation operation is at low molecule organic matter or mineralising, such as the macromolecule organic silicon compound oxidation is organosiloxane, silanol Low molecule organic matter (being in dissolved state).Subsequent second step, by the way that calper calcium peroxide is added, on the one hand (in acid condition) is generated H2O2Fenton oxidation reaction, chemical equation are as follows: 2H can be strengthened++CaO2→Ca2++H2O2；On the other hand the Ca generated2+It can It polymerize various zwitterion (such as Fe in low molecule organosilicon material and water with these2+、Fe3+、Al3+、SO4 2-Deng) form calcium Silicon complex precipitate, so that organohalogen compounds and a variety of zwitterions in organo-silicon compound and waste water effectively be prevented to inhale The process of reaction enclosure formation solubilised state polymer.Simultaneously with the progress of reaction, solution system pH value is slowly improved, calper calcium peroxide It is reacted with water and generates calcium hydroxide and oxygen, chemical equation are as follows: 2CaO2+2H2O=2Ca (OH)2+O2↑, thus in water The acceleration of organic matter, inorganic matter composite precipitation provides suitable condition.By the above-mentioned first step and second step coupling reaction, make to give up The COD removal rate of water greatly improves.Moreover, Fe2+It is oxidized to Fe3+There is certain coagulating sedimentation afterwards, also has to ammonia nitrogen Certain place to go effect.Last third step makes Mg by adding magnesium salts and hydrophosphate into waste water2+、HPO4 2-(or H2PO4 -) With the NH in waste water3- N is chemically reacted, and generates double salt (MgNH4PO4·6H2O it) precipitates, thus by NH3N removal.Due to Calcium oxide oxidation process can more slowly improve the useless pH value of waste water in two steps, can provide one except ammonia nitrogen for magnesium ammonium phosphate sediment method A control environment, therefore efficient removal can be carried out to the ammonia nitrogen in waste water by third step.In addition, third step processing is obtained Sediment MgNH4PO4It is alternatively arranged as compound fertilizer, therefore for the waste water inherently containing magnesium ion, is mentioned using the present invention When the method for confession is handled, while removing COD and ammonia nitrogen, the resource utilization to magnesium ion in waste water can also be achieved.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this The embodiment of invention for those of ordinary skill in the art without creative efforts, can also basis The attached drawing of offer obtains other attached drawings.
Fig. 1 is the GC-MS map for the desulfurization wastewater that the embodiment of the present invention 1 provides；
Fig. 2 is the XRD spectrum that the embodiment of the present invention 1 provides.
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete Site preparation description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts every other Embodiment shall fall within the protection scope of the present invention.
The present invention provides a kind of processing methods of wet desulphurization waste water, comprising the following steps:
A) pH value of desulfurization wastewater is adjusted to 2.25~4.5, then with hydrogen peroxide and ferrous salt hybrid reaction, obtained Oxidized waste water；
B) by the oxidized waste water and calper calcium peroxide hybrid reaction, sediment is removed, clear liquid is obtained；
C) in Mg2+Under existence condition, by the clear liquid and hydrophosphate hybrid reaction, sediment is removed, after obtaining processing Waste water；
The Mg2+Source be additional Mg2+And/or the Mg contained in the clear liquid2+。
In the present invention, pH value adjusting being carried out to desulfurization wastewater first, desulfurization wastewater pH value after adjusting is 2.25~ 4.5, concretely 2.25,2.3,2.35,2.4,2.45,2.5,2.55,2.6,2.65,2.7,2.75,2.8,2.85,2.9, 2.95、3、3.05、3.1、3.15、3.2、3.25、3.3、3.35、3.4、3.45、3.5、3.55、3.6、3.65、3.7、3.75、 3.8,3.85,3.9,3.95,4,4.05,4.1,4.15,4.2,4.25,4.3,4.35,4.4,4.45 or 4.5.It is mentioned in the present invention In one embodiment of confession, the COD of the desulfurization wastewater is preferably 1000~2000mg/L, concretely 1000mg/L, 1100mg/L、1200mg/L、1280mg/L、1300mg/L、1400mg/L、1500mg/L、1600mg/L、1700mg/L、 1778mg/L, 1800mg/L, 1900mg/L or 2000mg/L；The ammonia-nitrogen content of the desulfurization wastewater is preferably 200~300mg/ L, concretely 210mg/L, 220mg/L, 226.7mg/L, 230mg/L, 240mg/L, 250mg/L, 260mg/L, 270mg/L, 280mg/L, 290mg/L or 300mg/L.In one embodiment provided by the invention, the magnesium ion in the desulfurization wastewater contains Amount preferably 2 × 104~4 × 104mg/L.Concretely 2 × 104mg/L、2.1×104mg/L、2.2×104mg/L、2.3× 104mg/L、2.4×104mg/L、2.5×104mg/L、2.6×104mg/L、2.7×104mg/L、2.8×104mg/L、2.9× 104mg/L、2.98×104mg/L、3×104mg/L、3.1×104mg/L、3.2×104mg/L、3.3×104mg/L、3.4× 104mg/L、3.5×104mg/L、3.6×104mg/L、3.7×104mg/L、3.8×104mg/L、3.9×104Mg/L or 4 × 104mg/L.In one embodiment provided by the invention, the zinc ion content in the desulfurization wastewater is preferably 0.5~1mg/ L, concretely 0.5mg/L, 0.55mg/L, 0.6mg/L, 0.65mg/L, 0.7mg/L, 0.75mg/L, 0.77mg/L, 0.8mg/ L, 0.82mg/L, 0.85mg/L, 0.9mg/L, 0.95mg/L or 1mg/L.It is described de- in one embodiment provided by the invention Lead ion content in sulphur waste water is preferably 3~8mg/L, concretely 3mg/L, 3.5mg/L, 4mg/L, 4.5mg/L, 4.6mg/ L, 4.8mg/L, 5mg/L, 5.5mg/L, 6mg/L, 6.5mg/L, 7mg/L, 7.5mg/L or 8mg/L.At one provided by the invention In embodiment, the cadmium ion content in the desulfurization wastewater is preferably 0.5~1mg/L, concretely 0.5mg/L, 0.55mg/L, 0.6mg/L、0.65mg/L、0.7mg/L、0.75mg/L、0.8mg/L、0.83mg/L、0.85mg/L、0.9mg/L、0.95mg/L Or 1mg/L.In one embodiment provided by the invention, the content of chromium ion in the desulfurization wastewater is preferably 0.3~ 0.8mg/L, concretely 0.3mg/L, 0.35mg/L, 0.4mg/L, 0.45mg/L, 0.5mg/L, 0.52mg/L, 0.55mg/L, 0.6mg/L, 0.65mg/L, 0.7mg/L, 0.75mg/L or 0.8mg/L.It is described de- in one embodiment provided by the invention Arsenic ion content in sulphur waste water is preferably 0.3~0.8mg/L, concretely 0.3mg/L, 0.35mg/L, 0.4mg/L, 0.45mg/L, 0.5mg/L, 0.55mg/L, 0.6mg/L, 0.65mg/L, 0.7mg/L, 0.75mg/L or 0.8mg/L.In the present invention In one embodiment of offer, the content of fluoride in the desulfurization wastewater is preferably 40~80mg/L, concretely 40mg/L, 42mg/L、44mg/L、45mg/L、46mg/L、48mg/L、50mg/L、52mg/L、54mg/L、55mg/L、56mg/L、58mg/L、 60mg/L、62mg/L、64mg/L、65mg/L、67mg/L、69mg/L、70mg/L、72mg/L、74mg/L、76mg/L、78mg/L Or 80mg/L.
The pH value of desulfurization wastewater is adjusted to after meeting the requirements, desulfurization wastewater is mixed instead with hydrogen peroxide and ferrous salt It answers.Wherein, the hydrogen peroxide mixes preferably in the form of hydrogen peroxide with the desulfurization wastewater, and the concentration of the hydrogen peroxide is preferred For 20~40wt%, concretely 20wt%, 25wt%, 30wt%, 35wt% or 40wt%；The ferrous salt includes but unlimited In ferrous sulfate and/or frerrous chloride；The amount ratio of the hydrogen peroxide and desulfurization wastewater is preferably (0.5~5) mmol:1L, Concretely 0.5mmol:1L, 1mmol:1L, 1.5mmol:1L, 2mmol:1L, 2.5mmol:1L, 3mmol:1L, 3.5mmol: 1L, 4mmol:1L, 4.5mmol:1L or 5mmol:1L；Fe in the hydrogen peroxide and ferrous salt2+Molar ratio be preferably 1:(0.5~1.5), concretely 1:0.5,1:0.6,1:0.7,1:0.8,1:0.9,1:1,1:1.1,1:1.2,1:1.3,1: 1.4 or 1:1.5；The temperature of the hybrid reaction is preferably 15~35 DEG C, concretely 15 DEG C, 20 DEG C, 25 DEG C (room temperature), 30 DEG C Or 35 DEG C；The hybrid reaction preferably carries out under agitation, and the revolving speed of the stirring is preferably 50~300r/min, specifically It can be 50r/min, 100r/min, 150r/min, 200r/min, 250r/min or 300r/min；The time of the hybrid reaction Preferably 10~20min, concretely 10min, 11min, 12min, 13min, 14min, 15min, 16min, 17min, 18min, 19min or 20min.After hybrid reaction, oxidized waste water is obtained.
After obtaining oxidized waste water, by the oxidized waste water and calper calcium peroxide hybrid reaction.Wherein, the calper calcium peroxide is with before The molar ratio of hydrogen peroxide described in one step be preferably (1~1.5): 1, concretely 1:1,1.05:1,1.1:1,1.15:1, 1.2:1,1.25:1,1.3:1,1.35:1,1.4:1,1.45:1 or 1.5:1；The temperature of the hybrid reaction is preferably 15~35 DEG C, concretely 15 DEG C, 20 DEG C, 25 DEG C (room temperature), 30 DEG C or 35 DEG C；The hybrid reaction preferably carries out under agitation, The revolving speed of the stirring is preferably 50~300r/min, concretely 50r/min, 100r/min, 150r/min, 200r/min, 250r/min or 300r/min；The time of the hybrid reaction preferably 30~50min, concretely 30min, 32min, 34min, 35min, 36min, 38min, 40min, 40min, 42min, 44min, 45min, 46min, 48min or 50min.Hybrid reaction knot Shu Hou removes the sediment in waste water, obtains clear liquid.Wherein, the pH value of the clear liquid is preferably 8.0~11.2, concretely 8.0、8.2、8.4、8.5、8.6、8.8、9.0、9.2、9.4、9.5、9.6、9.8、10.0、10.2、10.4、10.5、10.6、 10.8,11.0 or 11.2.
After obtaining clear liquid, by the clear liquid and hydrophosphate hybrid reaction.Wherein, if containing enough in the clear liquid Mg2+, then can be directly by clear liquid and hydrophosphate hybrid reaction；If being free of Mg in the clear liquid2+Or the too low Mg of content2+, then need Additional Mg2+.In one embodiment provided by the invention, as the Mg in clear liquid2+With the NH in clear liquid3When molar ratio >=1:1 of-N, It is preferred that not needing additional Mg then when >=1.2:12+, vice versa.In the present invention, the hydrophosphate includes but is not limited to Na2HPO4And/or NaH2PO4；The NH in acid ion and clear liquid in the hydrophosphate3The molar ratio of-N be preferably (1~ 2): 1, concretely 1.1:1,1.2:1,1.3:1,1.4:1,1.5:1,1.6:1,1.7:1,1.8:1,1.9:1 or 2:1；It is described The temperature of hybrid reaction is preferably 15~35 DEG C, and concretely 15 DEG C, 20 DEG C, 25 DEG C (room temperature), 30 DEG C or 35 DEG C；The mixing Reaction preferably carry out under agitation, the revolving speed of the stirring is preferably 50~300r/min, concretely 50r/min, 100r/min, 150r/min, 200r/min, 250r/min or 300r/min；The time of the hybrid reaction preferably 20~ 40min, concretely 20min, 25min, 30min, 35min or 40min.After hybrid reaction, the precipitating in waste water is removed Object obtains processed waste water.In the present invention, it is preferred to which waste water is first staticly settled one before the sediment in removal waste water The section time, the time staticly settled is preferably 5~30min, concretely 5min, 10min, 15min, 20min, 25min Or 30min.
Present invention joint utilizes Fenton oxidation, calcium silicon composite precipitation and magnesium ammonium phosphate sediment technical treatment desulfurization wastewater, The first step utilizes Fe2+And H2O2Between chain reaction generate have strong oxidizing property OH, a variety of toxic and difficult drop can be aoxidized The complex organic compound of solution, to make larger molecular organics in water be oxidized to low molecule organic matter or mineralising, as macromolecule has Organic silicon compound is oxidized to the low molecule organic matters such as organosiloxane, silanol (in dissolved state).Subsequent second step passes through addition Calper calcium peroxide, on the one hand (in acid condition) generates H2O2Fenton oxidation reaction, chemical equation are as follows: 2H can be strengthened++ CaO2→Ca2++H2O2；On the other hand the Ca generated2+Various yin-yang in low molecule organosilicon material and water can be polymerize with these Ion (such as Fe2+、Fe3+、Al3+、SO4 2-Deng) calcium silicon complex precipitate is formed, to effectively prevent organo-silicon compound and give up Organohalogen compounds and a variety of zwitterion adsorption reactions form the process of solubilised state polymer in water.Simultaneously with reaction It carries out, solution system pH value slowly improves, and calper calcium peroxide is reacted with water generates calcium hydroxide and oxygen, chemical equation are as follows: 2CaO2+2H2O=2Ca (OH)2+O2↑, so that the acceleration for Organic substance in water, inorganic matter composite precipitation provides suitable condition. By the above-mentioned first step and second step coupling reaction, greatly improve the COD removal rate of waste water.Moreover, Fe2+It is oxidized to Fe3+ There is certain coagulating sedimentation afterwards, also there is certain place to go effect to ammonia nitrogen.Last third step, by being added into waste water Magnesium salts and hydrophosphate, make Mg2+、HPO4 2-(or H2PO4 -) with waste water in NH3- N is chemically reacted, and generates double salt (MgNH4PO4·6H2O it) precipitates, thus by NH3N removal.Since calcium oxide oxidation process can be mentioned more slowly in second step High waste water gives up pH value, can provide a control environment except ammonia nitrogen for magnesium ammonium phosphate sediment method, therefore can be to waste water by third step In ammonia nitrogen carry out efficient removal.In addition, third step handles obtained sediment MgNH4PO4It is alternatively arranged as compound fertilizer, because This is for the waste water inherently containing magnesium ion, when being handled using method provided by the invention, in removing COD and ammonia While nitrogen, the resource utilization to magnesium ion in waste water can also be achieved.
For the sake of becoming apparent from, it is described in detail below by following embodiment.
It is de- that desulfurization wastewater used in the following embodiment and comparative examples of the present invention is all from Guangdong steel works sintering flue gas Sulphur workshop, the steel plant use the desulfurization of magnesium sulfite clear liquid, contain enough Mg in desulfurization wastewater2+, therefore do not need additional magnesium Source.
In the following embodiment and comparative examples of the present invention unless otherwise instructed, then reason step is in room temperature everywhere in being related to It is carried out under (25 DEG C).
Embodiment 1
(1) magnesium sulfite wet desulphurization waste water raw water is pre-processed, is later adjusted to the pH value of pretreated waste water 3.5。
GC-MS detection is carried out to the waste water that pH value is adjusted is completed, as a result as shown in Figure 1, Fig. 1 is that the embodiment of the present invention 1 mentions The GC-MS map of the desulfurization wastewater of confession.As seen in Figure 1, in pretreatment desulfurizing waste water containing octamethylcy-clotetrasiloxane, Decamethylcyclopentaandoxane, ten diformazan basic rings, six siloxanes, dodecyl siloxane, the pungent siloxanes of ring, cycloheptyl siloxanes.
Quantitative analysis is carried out to the pollutant component for completing to contain in the waste water that pH value is adjusted, as a result as shown in the table:
Index Numerical value
COD 1280mg/L
Ammonia nitrogen 226.7mg/L
Magnesium ion 2.98×104mg/L
Zinc ion 0.77mg/L
Lead ion 4.6mg/L
Cadmium ion 0.8mg/L
Chromium ion 0.45mg/L
Arsenic ion 0.5mg/L
Fluoride 60mg/L
(2) 1L is taken in beaker, to add FeSO thereto by the desulfurization wastewater of step (1) processing4·7H2O and concentration are Then the hydrogen peroxide of 30wt% is placed the beaker and is stirred on tetrad magnetic stirring apparatus, stirring rate is set as 150r/min, After stirring 15min, CaO is added into waste water2, continue to stir 30min, stop stirring, staticly settle 15min, obtaining pH value is 9.5~10.6 clear liquid (Mg in clear liquid2+Concentration be 2.17 × 104mg/L)。
In step (2), dosage of the hydrogen peroxide in waste water is 0.2ml/L (that is, H2O2Dosage be about 2mmol/L), The molar ratio of each reagent used is FeSO4:H2O2:CaO2=1:1:1.25.
XRD detection is carried out to the sediment that step (2) staticly settles, shown in result figure 2, Fig. 2 is implementation of the present invention The XRD spectrum that example 1 provides.Wherein, it is as shown in the table respectively to number corresponding substance title:
Number Substance title Number Substance title
A CaSO4·2H2O I Ca2Fe2O5
B Ca2Si2O5(OH)2·2H2O J CaAl2Si2O7(OH)2·H2O
C Ca2Al2SiO6(OH)2 K Al(OH)3
D Ca2Al2Si3O10(OH)2 L Ca5(SiO4)2SO4
E Ca2Si4·H2O M Ca3.2(H0.6Si2O7)OH
F Ca9(Si6O18H2)(OH)8·2H2O N Ca2Al2SiO6(OH)2
G Ca(Al,Si)2O4 O Ca4Al2Si6(OH)2
H Ca5Si6(O,OH,F)18·5H2O
Through the analysis result of above-mentioned XRD it is found that through the waste water of Fenton processing after calper calcium peroxide is added, calper calcium peroxide React the Ca generated2+It can to form calcium silicon compound heavy with polymerize low molecule organosilicon material and the various zwitterions in waste water Starch, so as to effectively prevent organohalogen compounds and a variety of zwitterion adsorption reaction shapes in organo-silicon compound and waste water At solubilised state polymer.
(3) according to the NH in clear liquid3HPO in-N and disodium hydrogen phosphate4 2-Molar ratio be 1:1.5, obtained to step (2) Disodium hydrogen phosphate is added in the clear liquid obtained, 30min is stirred under 150r/min revolving speed, stops stirring, staticly settles 15min, obtain To processing waste water.
COD and ammonia nitrogen detection are carried out to the waste water by step (3) processing, as a result as shown in the table:
Comparative example 1
(1) magnesium sulfite wet desulphurization waste water raw water is pre-processed, is later adjusted to the pH value of pretreated waste water 3.5。
Quantitative analysis is carried out to the pollutant component for completing to contain in the waste water that pH value is adjusted, as a result as shown in the table:
Index Numerical value
COD 1778mg/L
Ammonia nitrogen 240mg/L
Magnesium ion 3.02×104mg/L
Zinc ion 0.82mg/L
Lead ion 4.8mg/L
Cadmium ion 0.83mg/L
Chromium ion 0.52mg/L
Arsenic ion 0.55mg/L
Fluoride 67mg/L
(2) 1L is taken in beaker, to add FeSO thereto by the desulfurization wastewater of step (1) processing4·7H2O and concentration are Then the hydrogen peroxide of 30wt% is placed the beaker and is stirred on tetrad magnetic stirring apparatus, stirring rate is set as 150r/min, After stirring 15min, stops stirring, obtain processed waste water.
In step (2), dosage of the hydrogen peroxide in waste water is 0.5ml/L (that is, H2O2Dosage be about 5mmol/L), The molar ratio of each reagent used is FeSO4:H2O2=1:1.
COD and ammonia nitrogen detection are carried out to the waste water by step (2) processing, as a result as shown in the table:
Comparative example 2
1L is taken in beaker, to add CaO thereto by the desulfurization wastewater of 1 step of embodiment (1) processing2(dosage is 2mg/L), it then places the beaker and is stirred on tetrad magnetic stirring apparatus, stirring rate is set as 150r/min, stirring After 30min, stops stirring, the flocculant poly silicic acid iron chloride (PFSC) for accounting for wastewater quality 0.5wt% is added into waste water, it is quiet Precipitating 15min is set, processed waste water is obtained.
COD and ammonia nitrogen detection are carried out to treated waste water, as a result are as follows: the COD of processed waste water is 960mg/L, COD Removal rate is 25%；Ammonia-nitrogen content is 197.32mg/L, ammonia nitrogen removal frank 12.96%.
Comparative example 3
1L is taken in beaker, to add FeSO thereto by the desulfurization wastewater of 1 step of embodiment (1) processing4·7H2O and dense Degree is the hydrogen peroxide of 30wt%, then places the beaker and is stirred on tetrad magnetic stirring apparatus, stirring rate is set as 150r/ Min adds CaO into waste water after stirring 15min2, continue to stir 30min, stop stirring, staticly settle 15min, obtain pH The clear liquid that value is 9.5~10.6.
In above-mentioned processing step, dosage of the hydrogen peroxide in waste water is 0.2ml/L (that is, H2O2Dosage be about 2mmol/L), the molar ratio of each reagent used is FeSO4:H2O2:CaO2=1:1:1.25.
COD and ammonia nitrogen detection being carried out to treated waste water, as a result are as follows: the COD of processed waste water is 133.12mg/L, COD removal rate is 89.6%；Ammonia-nitrogen content is 121.71mg/L, ammonia nitrogen removal frank 46.31%.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered It is considered as protection scope of the present invention.

Claims (10)

1. a kind of processing method of wet desulphurization waste water, comprising the following steps:
A) pH value of desulfurization wastewater is adjusted to 2.25~4.5, then with hydrogen peroxide and ferrous salt hybrid reaction, is aoxidized Waste water；
B) by the oxidized waste water and calper calcium peroxide hybrid reaction, sediment is removed, clear liquid is obtained；
C) in Mg2+Under existence condition, by the clear liquid and hydrophosphate hybrid reaction, sediment is removed, processed waste water is obtained；
The Mg2+Source be additional Mg2+And/or the Mg contained in the clear liquid2+。
2. processing method according to claim 1, which is characterized in that the ferrous salt includes ferrous sulfate and/or chlorination It is ferrous.
3. processing method according to claim 1, which is characterized in that in step a), in the hydrogen peroxide and ferrous salt Fe2+Molar ratio be 1:(0.5~1.5).
4. processing method according to claim 3, which is characterized in that in step a), the hydrogen peroxide and desulfurization wastewater Amount ratio be (0.5~5) mmol:1L.
5. processing method according to claim 1, which is characterized in that in step a), the time of the hybrid reaction is 10 ~20min.
6. processing method according to claim 1, which is characterized in that institute in calper calcium peroxide described in step b) and step a) The molar ratio for stating hydrogen peroxide is (1~1.5): 1.
7. processing method according to claim 1, which is characterized in that in step b), the time of the hybrid reaction is 30 ~50min.
8. processing method according to claim 1, which is characterized in that in step c), the hydrophosphate includes Na2HPO4 And/or NaH2PO4。
9. processing method according to claim 1, which is characterized in that in step c), acid group in the hydrophosphate from Son and the NH in clear liquid3The molar ratio of-N is (1~2): 1.
10. processing method according to claim 1, which is characterized in that in step c), the time of the hybrid reaction is 20 ~40min.
CN201811363267.1A 2018-11-12 2018-11-15 A kind of processing method of wet desulphurization waste water Pending CN109354248A (en)

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Application publication date: 20190219