CN106938866A - A kind of desulfurization wastewater resource utilization system and method - Google Patents

A kind of desulfurization wastewater resource utilization system and method Download PDF

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Publication number
CN106938866A
CN106938866A CN201710303877.1A CN201710303877A CN106938866A CN 106938866 A CN106938866 A CN 106938866A CN 201710303877 A CN201710303877 A CN 201710303877A CN 106938866 A CN106938866 A CN 106938866A
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China
Prior art keywords
order reaction
reaction case
supernatant
depositing reservoir
level
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CN201710303877.1A
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Inventor
陈奎续
张晖栋
林福全
陈金亮
娄彤
黄友华
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Fujian Longking Co Ltd.
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Fujian Longking Co Ltd.
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Priority to CN201710303877.1A priority Critical patent/CN106938866A/en
Publication of CN106938866A publication Critical patent/CN106938866A/en
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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
    • C02F1/52Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • 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
    • C02F2001/007Processes including a sedimentation step
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/18Nature of the water, waste water, sewage or sludge to be treated from the purification of gaseous effluents
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2301/00General aspects of water treatment
    • C02F2301/08Multistage treatments, e.g. repetition of the same process step under different conditions
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00Use of specific compounds during water treatment
    • C02F2305/02Specific form of oxidant

Abstract

The invention belongs to water treatment field, more particularly to a kind of desulfurization wastewater resource utilization system and method.The system includes:Primary clarifier;The first order reaction case being connected with primary clarifier, is provided with milk of lime, alkali metal sulphide and flocculant charge door;The one-level depositing reservoir being connected with first order reaction case;The second order reaction case being connected with one-level depositing reservoir, is provided with alkali metal hydroxide charge door;Two grades of depositing reservoirs being connected with second order reaction case;The third-order reaction case being connected with two grades of depositing reservoirs, is provided with alkali metal meta-aluminate charge door;The three-level depositing reservoir being connected with third-order reaction case;The fourth-order reaction case being connected with three-level depositing reservoir, is provided with CO2Air inlet;The level Four depositing reservoir being connected with the outlet of fourth-order reaction case.Obtained waste water is handled using the system and meets the supplement water water quality requirement of desulfurizing tower, while the resource reclaim in waste water can be prepared to the chemicals such as magnesium hydroxide, calcium sulphoaluminate/calcium chloroaluminate and aluminium hydroxide.

Description

A kind of desulfurization wastewater resource utilization system and method
Technical field
The invention belongs to water treatment field, more particularly to a kind of desulfurization wastewater resource utilization system and method.
Background technology
" limestone/lime-gypsum method " is widely used in thermal power plant the features such as with system reliability height, efficiency high Flue gas desulfurization administer.But in order to maintain the material balance of flue gas desulphurization system, prevent that the chlorion of desulphurization system from exceeding rule Definite value and the quality for ensureing gypsum, it is necessary to certain waste water is discharged from system.This effluent part (desulfurization wastewater) water quality is complicated It is changeable, mainly contain solid suspension, supersaturated sulphite, sulfate, chloride, calcium ions and magnesium ions and micro heavy. Especially the chlorion of high concentration has the characteristics of corrosivity is big under conditions of slant acidity, causes the waste water after processing cannot be introduced into System reuse.
Water quality base after coal-fired plant flue gas wet desulphurization waste water is handled by traditional chemical precipitation method at present Originally thermal power plant's Limestone-gypsum Wet Flue Gas Desulfurization Process waste water quality Con trolling index (DL/T997-2006) can be met.The technique is general The process processing desulfurization wastewater such as neutralize, flocculate, settling using lime, by separation of solid and liquid, production water carries out dry ash and mixes wet or straight Run in and put.But this method has two shortcomings:One is that there is high sulfate radical, high chlorine root, high rigidity (the high magnesium of high calcium) to contain for water outlet Salt water quality characteristic, if directly discharging, certainly will cause salinization of soil, the influence biological growthing environment of soil;Two be that China is with coal Based on thermoelectricity big country, power plants water withdrawal accounts for the 30%~40% of industrial water, if water outlet is directly discharged, and will make Into the huge waste of the energy.Therefore, with the requirement more and more higher of environmental protection, it is necessary to carry out the characteristics of for power plant desulfurization waste water Reasonably technological design, to realize that desulfurization wastewater recycling, production water obtain reuse.
The content of the invention
In view of this, it is an object of the invention to provide a kind of desulfurization wastewater resource utilization system and method, using this Resource reclaim in waste water can be prepared chemicals by the system processing desulfurization wastewater that invention is provided, and be wanted while can obtain and meet reuse The water outlet asked.
The invention provides a kind of desulfurization wastewater resource utilization system, including:
Primary clarifier;
Be provided with the first order reaction case being connected with the delivery port of primary clarifier, first order reaction case milk of lime charge door, Alkali metal sulphide charge door and flocculant charge door;
The one-level depositing reservoir being connected with the outlet of first order reaction case;
Alkali metal hydroxide is provided with the second order reaction case being connected with the delivery port of one-level depositing reservoir, second order reaction case Charge door;
Two grades of depositing reservoirs being connected with the outlet of second order reaction case;
Alkali metal meta-aluminate is provided with the third-order reaction case being connected with the delivery port of two grades of depositing reservoirs, third-order reaction case Charge door;
The three-level depositing reservoir being connected with the outlet of third-order reaction case;
Carbon dioxide is provided with the fourth-order reaction case being connected with the delivery port of three-level depositing reservoir, fourth-order reaction case Mouthful;
The level Four depositing reservoir being connected with the outlet of fourth-order reaction case.
It is preferred that, it is provided with stirring in the first order reaction case, second order reaction case, third-order reaction case and fourth-order reaction case Device.
It is preferred that, it is provided with pH in the first order reaction case, second order reaction case, third-order reaction case and fourth-order reaction case Meter.
It is preferred that, the primary clarifier, one-level depositing reservoir, two grades of depositing reservoirs, two grades of depositing reservoirs and level Four depositing reservoir Sediment outlet is respectively connected with filter press.
The invention provides a kind of desulfurization wastewater resource utilization method, comprise the following steps:
A), desulfurization wastewater is clarified, and obtains the first supernatant;
B), first supernatant and milk of lime, alkali metal sulphide and flocculant hybrid reaction, clarification, obtain second Supernatant;
C), second supernatant and alkali metal hydroxide hybrid reaction, clarification, obtain the 3rd supernatant and hydroxide Magnesium precipitate;
D), the 3rd supernatant and alkali metal meta-aluminate hybrid reaction, clarification, obtain the 4th supernatant and glue Thing;The jelly is calcium sulphoaluminate and calcium chloroaluminate mixture.
E), the 4th supernatant and CO2Hybrid reaction, clarification, obtains processed waste water and aluminum hydroxide precipitation.
It is preferred that, in step b), the mode of mixing is addition milk of lime, alkali metal sulphide into the first supernatant successively And flocculant;
It is 9.0~9.5 that the mixed system pH value after milk of lime is added into the first supernatant;The addition of alkali metal sulphide Measure the heavy metal ion quality contained by the first supernatant 1.1~1.8 times;The addition of flocculant is the 0.05 of the first supernatant ~0.5wt%.
It is preferred that, in step c), second supernatant is with the mixed mixed system pH value of alkali metal hydroxide 11.5~12.5.
It is preferred that, in step d), the mode of mixing is that alkali metal meta-aluminate is added into the 3rd supernatant;
Stop addition alkali metal meta-aluminic acid during the hybrid reaction, when the pH value of system to be mixed will rise Salt.
It is preferred that, in step e), the mode of mixing is to be passed through CO into the 4th supernatant2
CO2During being passed through, the pH value of mixed system constantly declines, and stops being passed through when the pH of system to be mixed no longer declines CO2
It is preferred that, in step a), the pH value of first supernatant is 3~7, suspended solids content is 1000~ 80000mg/L, Ca2+Content is 500~6000mg/L, Mg2+Content is 200~9000mg/L, SO4 2- content be 1000~ 25000mg/L, C 1 content is 1000~15000mg/L, F-Content is 5~40mg/L, Pb2+Content is 2~15mg/L, Ni+Contain Measure as 0.1~5mg/L, full Fe contents are 0.1~5mg/L, Hg2+Content is 0.1~5mg/L, Cd2+Content is 1~10mg/L.
Compared with prior art, the invention provides a kind of desulfurization wastewater resource utilization system and method.The present invention is carried The desulfurization wastewater resource utilization system of confession includes:Primary clarifier;The first order reaction being connected with the delivery port of primary clarifier Milk of lime charge door, alkali metal sulphide charge door and flocculant charge door are provided with case, first order reaction case;With first order reaction The one-level depositing reservoir that the outlet of case is connected;Set on the second order reaction case being connected with the delivery port of one-level depositing reservoir, second order reaction case It is equipped with alkali metal hydroxide charge door;Two grades of depositing reservoirs being connected with the outlet of second order reaction case;With going out for two grades of depositing reservoirs Alkali metal meta-aluminate charge door is provided with the connected third-order reaction case in the mouth of a river, third-order reaction case;With going out for third-order reaction case The connected three-level depositing reservoir of mouth;Two are provided with the fourth-order reaction case being connected with the delivery port of three-level depositing reservoir, fourth-order reaction case Carbonoxide air inlet;The level Four depositing reservoir being connected with the outlet of fourth-order reaction case.The system operation that the present invention is provided is: 1), desulfurization wastewater is precipitated in primary clarifier, obtains primary clarifier supernatant;2), by the primary clarifier Clear liquid is delivered to first order reaction case, and to first order reaction case feeding lime breast, alkali metal sulphide and flocculant, obtains one-level anti- Answer case mixed liquor;3) the first order reaction case mixed liquor, is delivered to one-level depositing reservoir, first order reaction case mixed liquor is clear in one-level Precipitated in clear pond, obtained one-level depositing reservoir supernatant;4) one-level depositing reservoir supernatant, is delivered to second order reaction case, and Alkali metal hydroxide is added to second order reaction case, second order reaction case mixed liquor is obtained;5), by the second order reaction case mixed liquor Two grades of depositing reservoirs are delivered to, second order reaction case mixed liquor is precipitated in two grades of depositing reservoirs, obtain two grades of depositing reservoir supernatants And magnesium hydrate precipitate;6) two grades of depositing reservoir supernatants, are delivered to third-order reaction case, and alkali metal is added to third-order reaction case Meta-aluminate, obtains third-order reaction case mixed liquor;7) the third-order reaction case mixed liquor, is delivered to three-level depositing reservoir, three-level Reaction chamber mixed liquor is precipitated in three-level depositing reservoir, obtains three-level depositing reservoir supernatant and jelly, and the jelly is Calcium sulphoaluminate and calcium chloroaluminate mixture;8) three-level depositing reservoir supernatant, is delivered to fourth-order reaction case, and to fourth-order reaction case Logical CO2, obtain fourth-order reaction case mixed liquor;9) the fourth-order reaction case mixed liquor, is delivered to level Four depositing reservoir, fourth-order reaction Case mixed liquor is precipitated in level Four depositing reservoir, obtains level Four depositing reservoir supernatant and aluminum hydroxide precipitation.In the present invention, Desulfurization wastewater is obtained into the supernatant more clarified by primary clarifier, milk of lime is added, regulation pH makes heavy metal ion, fluorine Ion, arsenic ion and part of sulfuric acid radical ion etc. form sediment with calcium hydroxide and removed;Alkali metal hydroxide is added again Solution, adjusts pH again, removes the magnesium ion in solution, so as to prepare magnesium hydroxide products, magnesium hydroxide is widely used, Available for fire retardant, Green Water Treatment Reagents;Alkali metal meta-aluminate is added in above-mentioned clear liquid, with the calcium ion in solution, sulfuric acid Root, chlorion reaction prepare calcium sulphoaluminate/calcium chloroaluminate jelly, and calcium sulphoaluminate/calcium chloroaluminate is widely used, can be used for Water treatment agent, sealing agent, adsorbent;Excessive carbon dioxide is finally passed through to remove remaining alkali metal meta-aluminate and reduce molten The pH value of liquid, production water carries out reuse or advanced treating, while obtaining product aluminium hydroxide, aluminium hydroxide is widely used, can make Used for inorganic combustion inhibitor.The desulfurization wastewater resource utilization system that the present invention is provided uses alkali metal hydroxide demagging, alkali The deliming of metal meta-aluminate, sulfate radical, chlorion, carbon dioxide handle excessive alkali metal meta-aluminate, can effectively reduce Waste water hardness, while high chlorine root, high sulfate radical can also be removed, efficiently solves the equipment corrosion problem that high chlorine root is brought;And And the system that the present invention is provided does not have discharge of wastewater (zero-emission) during waste water is handled, production water can meet reuse requirement, Pollutant, which can obtain, fully recycles (recycling), realizes desulfurization wastewater from " zero-emission " to the transformation of " recycling ", reaches The purpose for arrived energy-saving and emission-reduction, turning waste into wealth;The system process route that the other present invention is carried is simple, and the equipment manufacturing cost used is low, It is easy to maintain, it is environmentally friendly, with good economic benefit and social benefit.Test result indicate that, using present invention offer The obtained waste water of system processing meet the supplement water water quality requirement of desulfurizing tower, while can be prepared by the resource reclaim in waste water into hydrogen The chemicals such as magnesia, calcium sulphoaluminate/calcium chloroaluminate and aluminium hydroxide.
Brief description of the drawings
In order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing The accompanying drawing to be used needed for having technology description is briefly described, it should be apparent that, drawings in the following description are only this The embodiment of invention, for those of ordinary skill in the art, on the premise of not paying creative work, can also basis The accompanying drawing of offer obtains other accompanying drawings.
Fig. 1 is desulfurization wastewater resource utilization system flow chart provided in an embodiment of the present invention.
Embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is carried out clear, complete Site preparation is described, it is clear that described embodiment is only a part of embodiment of the invention, rather than whole embodiments.It is based on Embodiment in the present invention, it is every other that those of ordinary skill in the art are obtained under the premise of creative work is not made Embodiment, belongs to the scope of protection of the invention.
The invention provides a kind of desulfurization wastewater resource utilization system, including:
Primary clarifier;
Be provided with the first order reaction case being connected with the delivery port of primary clarifier, first order reaction case milk of lime charge door, Alkali metal sulphide charge door and flocculant charge door;
The one-level depositing reservoir being connected with the outlet of first order reaction case;
Alkali metal hydroxide is provided with the second order reaction case being connected with the delivery port of one-level depositing reservoir, second order reaction case Charge door;
Two grades of depositing reservoirs being connected with the outlet of second order reaction case;
Alkali metal meta-aluminate is provided with the third-order reaction case being connected with the delivery port of two grades of depositing reservoirs, third-order reaction case Charge door;
The three-level depositing reservoir being connected with the outlet of third-order reaction case;
Carbon dioxide is provided with the fourth-order reaction case being connected with the delivery port of three-level depositing reservoir, fourth-order reaction case Mouthful;
The level Four depositing reservoir being connected with the outlet of fourth-order reaction case.
Referring to Fig. 1, Fig. 1 is desulfurization wastewater resource utilization system flow chart provided in an embodiment of the present invention.Wherein, 1 is Primary clarifier, 2 be first order reaction case, and 3 be one-level depositing reservoir, and 4 be second order reaction case, and 5 be two grades of depositing reservoirs, and 6 be that three-level is anti- Case is answered, 7 be three-level depositing reservoir, and 8 be fourth-order reaction case, and 9 be level Four depositing reservoir, and 1-1 is primary clarifier filter press, and 1-2 is first Level depositing reservoir sludge pump, 1-3 is primary clarifier filter press water outlet elevator pump, and 2-1 is first order reaction case pH meter, and 2-2 is one-level Box mixer is reacted, 3-1 is one-level depositing reservoir filter press.3-2 is one-level depositing reservoir sludge pump, and 3-3 is lifted for one-level depositing reservoir Pump, 4-1 is second order reaction case pH meter, and 4-2 is second order reaction box mixer, and 5-1 is two grades of depositing reservoir filter presses, and 5-2 is two grades Depositing reservoir sludge pump, 5-3 is two grades of depositing reservoir elevator pumps, and 6-1 is third-order reaction case pH meter, and 6-2 is third-order reaction box mixer, 7-1 is three-level depositing reservoir filter press, and 7-2 is three-level depositing reservoir sludge pump, and 7-3 is three-level depositing reservoir elevator pump, and 8-1 is that level Four is anti- Case pH meter is answered, 8-2 is fourth-order reaction box mixer, and 9-1 is level Four depositing reservoir filter press, and 9-2 is level Four depositing reservoir sludge pump, 9- 3 be level Four depositing reservoir elevator pump.
It is clear that the desulfurization wastewater resource utilization system that the present invention is provided includes primary clarifier 1, first order reaction case 2, one-level Clear pond 3, second order reaction case 4, two grades of depositing reservoirs 5, third-order reaction case 6, three-level depositing reservoir 7, fourth-order reaction case 8 and level Four depositing reservoir 9.Wherein, primary clarifier 1 be used for desulfurization wastewater carry out first time clarified separation, be provided with water inlet, delivery port and Sediment is exported.In one embodiment that the present invention is provided, the sediment outlet of primary clarifier 1 is connected with primary clarifier Filter press 1-1, the sediment for being discharged to primary clarifier carries out press filtration.In one embodiment that the present invention is provided, just Level depositing reservoir filter press 1-1 filtrate (liquid is connected with the water inlet of primary clarifier 1, primary clarifier filter press 1-1 filter Liquid to export and be provided with primary clarifier filter press water outlet elevator pump 1-3 on the connecting line with the water inlet of primary clarifier 1, is used for Press filtration filtrate is back to primary clarifier 1.In one embodiment that the present invention is provided, primary clarifier 1 is clarified with primary Primary clarifier sludge pump 1-2 is provided with pond filter press 1-1 connecting line, for the defeated of primary clarifier bottom of pond sediment Send.
In the present invention, first order reaction case 2 is used for waste water and milk of lime, alkali metal sulphide and flocculant hybrid reaction, So that heavy metal ion, fluorine ion, arsenic ion and part of sulfuric acid radical ion in waste water etc. forms sediment, it is provided with Milk of lime charge door, alkali metal sulphide charge door, flocculant charge door, waste water inlet and outlet, the waste water of first order reaction case 2 Import is connected with the delivery port of primary clarifier 1.In one embodiment that the present invention is provided, it is provided with first order reaction case 2 First order reaction case pH meter 2-1, for detecting the pH value in reaction chamber, so as to regulate and control reagent addition.One provided in the present invention In individual embodiment, first order reaction box mixer 2-2 is provided with first order reaction case 2.
In the present invention, one-level depositing reservoir 3 is used to carry out second of clarified separation to desulfurization wastewater, is provided with into water Mouth, delivery port and sediment outlet, the water inlet of one-level depositing reservoir 3 are connected with the outlet of first order reaction case 2.In present invention offer One embodiment in, the water inlet of one-level depositing reservoir 3 is clear with being provided with one-level on the connecting line of the outlet of first order reaction case 2 Clear pond elevator pump 3-3, for the mixed liquor in reaction chamber to be delivered into depositing reservoir.In one embodiment that the present invention is provided, The sediment outlet of one-level depositing reservoir 3 is connected with one-level depositing reservoir filter press 3-1, for the sediment discharged to one-level depositing reservoir Carry out press filtration.In one embodiment that the present invention is provided, one-level depositing reservoir filter press 3-1 filtrate (liquid and one-level depositing reservoir 3 are connected, for press filtration filtrate to be back into one-level depositing reservoir 3.In one embodiment that the present invention is provided, one-level depositing reservoir 3 With being provided with one-level depositing reservoir sludge pump 3-2 on one-level depositing reservoir filter press 3-1 connecting line, for one-level depositing reservoir bottom of pond The conveying of sediment.
In the present invention, second order reaction case 4 is used for waste water and alkali metal hydroxide hybrid reaction, so that in waste water Magnesium ion formation sediment, is provided with alkali metal hydroxide charge door, waste water inlet and outlet, second order reaction case 4 Waste water inlet is connected with the delivery port of one-level depositing reservoir 3.In one embodiment that the present invention is provided, set in second order reaction case 4 Second order reaction case pH meter 4-1 is equipped with, for detecting the pH value in reaction chamber, so as to regulate and control reagent addition.In present invention offer One embodiment in, second order reaction box mixer 4-2 is provided with second order reaction case 4.
In the present invention, two grades of depositing reservoirs 5 are used to carry out third time clarified separation to desulfurization wastewater, are provided with into water Mouth, delivery port and sediment outlet, the water inlet of two grades of depositing reservoirs 5 are connected with the outlet of second order reaction case 4.In present invention offer One embodiment in, the water inlet of two grades of depositing reservoirs 5 is clear with being provided with two grades on the connecting line of the outlet of second order reaction case 4 Clear pond elevator pump 5-3, for the mixed liquor in reaction chamber to be delivered into depositing reservoir.In one embodiment that the present invention is provided, The sediment outlet of two grades of depositing reservoirs 5 is connected with two grades of depositing reservoir filter press 5-1, for the sediment to two grades of depositing reservoir discharges Carry out press filtration.In one embodiment that the present invention is provided, two grades of depositing reservoir filter press 5-1 filtrate (liquid and two grades of depositing reservoirs 5 are connected, for press filtration filtrate to be back into two grades of depositing reservoirs 5.In one embodiment that the present invention is provided, two grades of depositing reservoirs 5 With being provided with two grades of depositing reservoir sludge pump 5-2 on two grades of depositing reservoir filter press 5-1 connecting line, for two grades of depositing reservoir bottom of pond The conveying of sediment.
In the present invention, third-order reaction case 6 is used for waste water and alkali metal meta-aluminate hybrid reaction, so that in waste water Calcium ion, sulfate radical, chlorion formation calcium sulphoaluminate and calcium chloroaluminate jelly, are provided with the charging of alkali metal meta-aluminate Mouth, waste water inlet and outlet, the waste water inlet of third-order reaction case 6 are connected with the delivery port of two grades of depositing reservoirs 5.In present invention offer One embodiment in, third-order reaction case pH meter 6-1 is provided with third-order reaction case 6, for detecting the pH value in reaction chamber, from And regulate and control reagent addition.In one embodiment that the present invention is provided, the stirring of third-order reaction case is provided with third-order reaction case 6 Device 6-2.
In the present invention, three-level depositing reservoir 7 is used to carry out desulfurization wastewater the separation of the 4th secondary clearing, is provided with into water Mouth, delivery port and sediment outlet, the water inlet of three-level depositing reservoir 7 are connected with the outlet of third-order reaction case 6.In present invention offer One embodiment in, the water inlet of three-level depositing reservoir 7 is clear with being provided with three-level on the connecting line of the outlet of third-order reaction case 6 Clear pond elevator pump 7-3, for the mixed liquor in reaction chamber to be delivered into depositing reservoir.In one embodiment that the present invention is provided, The sediment outlet of three-level depositing reservoir 7 is connected with three-level depositing reservoir filter press 7-1, for the sediment discharged to three-level depositing reservoir Carry out press filtration.In one embodiment that the present invention is provided, three-level depositing reservoir filter press 7-1 filtrate (liquid and three-level depositing reservoir 7 are connected, for press filtration filtrate to be back into three-level depositing reservoir 7.In one embodiment that the present invention is provided, three-level depositing reservoir 7 With being provided with three-level depositing reservoir sludge pump 7-2 on three-level depositing reservoir filter press 7-1 connecting line, for three-level depositing reservoir bottom of pond The conveying of sediment.
In the present invention, fourth-order reaction case 8 is used for waste water and CO2Hybrid reaction, so as to remove remaining inclined aluminium in waste water Hydrochlorate, is provided with carbon dioxide mouthful, waste water inlet and outlet, and waste water inlet and the three-level of fourth-order reaction case 8 are clarified The delivery port in pond 7 is connected.In one embodiment that the present invention is provided, fourth-order reaction case pH meter is provided with fourth-order reaction case 8 8-1, for detecting the pH value in reaction chamber, so as to regulate and control CO2Addition.In one embodiment that the present invention is provided, level Four Fourth-order reaction box mixer 8-2 is provided with reaction chamber 8.
In the present invention, level Four depositing reservoir 9 is used to carry out desulfurization wastewater the separation of the 5th secondary clearing, is provided with into water Mouth, delivery port and sediment outlet, the water inlet of level Four depositing reservoir 9 are connected with the outlet of fourth-order reaction case 8.In present invention offer One embodiment in, the water inlet of level Four depositing reservoir 9 is clear with being provided with level Four on the connecting line of the outlet of fourth-order reaction case 8 Clear pond elevator pump 9-3, for the mixed liquor in reaction chamber to be delivered into depositing reservoir.In one embodiment that the present invention is provided, The sediment outlet of level Four depositing reservoir 9 is connected with level Four depositing reservoir filter press 9-1, for the sediment discharged to level Four depositing reservoir Carry out press filtration.In one embodiment that the present invention is provided, level Four depositing reservoir filter press 9-1 filtrate (liquid and level Four depositing reservoir 9 are connected, for press filtration filtrate to be back into level Four depositing reservoir 9.In one embodiment that the present invention is provided, level Four depositing reservoir 9 With being provided with level Four depositing reservoir sludge pump 9-2 on level Four depositing reservoir filter press 9-1 connecting line, for level Four depositing reservoir bottom of pond The conveying of sediment.
The system operation that the present invention is provided is:1), desulfurization wastewater is precipitated in primary clarifier, obtains primary Depositing reservoir supernatant;2) the primary clarifier supernatant, is delivered to first order reaction case, and to first order reaction case feeding lime Breast, alkali metal sulphide and flocculant, obtain first order reaction case mixed liquor;3), the first order reaction case mixed liquor is delivered to One-level depositing reservoir, first order reaction case mixed liquor is precipitated in one-level depositing reservoir, obtains one-level depositing reservoir supernatant;4), will One-level depositing reservoir supernatant is delivered to second order reaction case, and adds alkali metal hydroxide to second order reaction case, obtains two grades instead Answer case mixed liquor;5) the second order reaction case mixed liquor, is delivered to two grades of depositing reservoirs, second order reaction case mixed liquor is clear at two grades Precipitated in clear pond, obtained two grades of depositing reservoir supernatants and magnesium hydrate precipitate;6), two grades of depositing reservoir supernatants are delivered to Third-order reaction case, and alkali metal meta-aluminate is added to third-order reaction case, obtain third-order reaction case mixed liquor;7), by described three Order reaction case mixed liquor is delivered to three-level depositing reservoir, and third-order reaction case mixed liquor is precipitated in three-level depositing reservoir, obtains three Level depositing reservoir supernatant and jelly, the jelly are calcium sulphoaluminate and calcium chloroaluminate mixture;8), by three-level depositing reservoir Clear liquid is delivered to fourth-order reaction case, and leads to CO to fourth-order reaction case2, obtain fourth-order reaction case mixed liquor;9) it is, that the level Four is anti- Case mixed liquor is answered to be delivered to level Four depositing reservoir, fourth-order reaction case mixed liquor is precipitated in level Four depositing reservoir, obtains level Four clear Clear pond supernatant and aluminum hydroxide precipitation.
In the present invention, desulfurization wastewater is obtained into the supernatant more clarified by primary clarifier, adds milk of lime, adjusted Section pH makes heavy metal ion, fluorine ion, arsenic ion and part of sulfuric acid radical ion etc. form sediment with calcium hydroxide and remove;Again Alkali hydroxide soln is added, pH is adjusted again, the magnesium ion in solution is removed, so as to prepare magnesium hydroxide production Product, magnesium hydroxide is widely used, available for fire retardant, Green Water Treatment Reagents;Alkali metal meta-aluminate is added in above-mentioned clear liquid, with Calcium ion, sulfate radical, chlorion reaction in solution prepare calcium sulphoaluminate/calcium chloroaluminate jelly, calcium sulphoaluminate/chlorine aluminium Sour calcium is widely used, available for water treatment agent, sealing agent, adsorbent;Finally it is passed through excessive carbon dioxide and removes remaining alkali The pH value of metal meta-aluminate and reduction solution, production water carries out reuse or advanced treating, while obtaining product aluminium hydroxide, hydrogen Aluminum oxide is widely used, can be used as inorganic combustion inhibitor.
The desulfurization wastewater resource utilization system that the present invention is provided uses alkali metal hydroxide demagging, alkali metal meta-aluminic acid Salt deliming, sulfate radical, chlorion, carbon dioxide handle excessive alkali metal meta-aluminate, can effectively reduce waste water hardness, together When can also remove high chlorine root, high sulfate radical, efficiently solve the equipment corrosion problem that high chlorine root is brought;And the present invention is provided System there is no a discharge of wastewater (zero-emission) during waste water is handled, production water can meet reuse requirement, and pollutant can obtain Fully recycle (recycling), realize transformation of the desulfurization wastewater from " zero-emission " to " recycling ", reached energy-saving and emission-reduction, The purpose turned waste into wealth;The system process route that the other present invention is carried is simple, and the equipment manufacturing cost used is low, it is easy to safeguard, to ring Border is friendly, with good economic benefit and social benefit.Test result indicate that, the system processing provided using the present invention is obtained Waste water meet the supplement water water quality requirement of desulfurizing tower, while the resource reclaim in waste water can be prepared to magnesium hydroxide, sulphur aluminic acid The chemicals such as calcium/calcium chloroaluminate and aluminium hydroxide.
The invention provides a kind of desulfurization wastewater resource utilization method, comprise the following steps:
A), desulfurization wastewater is clarified, and obtains the first supernatant;
B), first supernatant and milk of lime, alkali metal sulphide and flocculant hybrid reaction, clarification, obtain second Supernatant;
C), second supernatant and alkali metal hydroxide hybrid reaction, clarification, obtain the 3rd supernatant and hydroxide Magnesium precipitate;
D), the 3rd supernatant and alkali metal meta-aluminate hybrid reaction, clarification, obtain the 4th supernatant and glue Thing;The jelly is calcium sulphoaluminate and calcium chloroaluminate mixture.
E), the 4th supernatant and CO2Hybrid reaction, clarification, obtains processed waste water and aluminum hydroxide precipitation.
In the method that the present invention is provided, desulfurization wastewater is clarified first.In the present invention, desulfurization wastewater is preferably upper Clarified in the text primary clarifier, residence time of the desulfurization wastewater in the primary clarifier is preferably 1h~2h. After clarification, the first supernatant and sediment are obtained.Sediment preferably carries out press filtration, and the filtrate that press filtration is obtained is preferably returned to clarification work Arranged outside sequence, the sludge that press filtration is obtained.In one embodiment that the present invention is provided, the pH value of first supernatant is 3~7, Concretely 5.4 or 6.9;The suspended solids content of first supernatant is 1000~80000mg/L, concretely 9227mg/L or 12560mg/L;The Ca of first supernatant2+Content be 500~6000mg/L, concretely 1952mg/L or 5511mg/L;The Mg of first supernatant2+Content is 200~9000mg/L, concretely 922mg/L or 8655mg/L;Institute State the SO of the first supernatant4 2- content is 1000~25000mg/L, concretely 1468mg/L or 4231mg/L;On described first The C 1 content of clear liquid is 1000~15000mg/L, concretely 12025mg/L or 14386mg/L;First supernatant F- contents are 5~40mg/L, concretely 8mg/L or 9mg/L;The Pb of first supernatant2+Content is 2~15mg/L, tool Body can be 5mg/L or 6mg/L;The Ni of first supernatant+Content is 0.1~5mg/L, concretely 1mg/L or 2mg/L; Full Fe (the Fe of first supernatant2+And Fe3+) content is 0.1~20mg/L, concretely 1mg/L or 5mg/L;Described The Hg of one supernatant2+Content is 0.1~5mg/L, concretely 1mg/L or 5mg/L;The Cd of first supernatant2+Content is 1~10mg/L, concretely 2mg/L or 3mg/L.
Obtain after the first supernatant, first supernatant is mixed instead with milk of lime, alkali metal sulphide and flocculant Should.Wherein, the alkali metal sulphide is preferably potassium sulfide and/or vulcanized sodium;The flocculant is preferably polyacrylamide. In the present invention, the first supernatant and the mode that milk of lime, alkali metal sulphide and flocculant are mixed are preferably successively on first Milk of lime, alkali metal sulphide and flocculant are added in clear liquid.Wherein, the concentration of milk of lime is preferably 1~10wt%, more preferably For 5~6wt%, the addition of milk of lime is preferably controlled by mixed system pH value, is added into the first supernatant after milk of lime Mixed system pH value be preferably 9.0~9.5;The addition of alkali metal sulphide be preferably heavy metal contained by the first supernatant from 1.1~1.8 times of protonatomic mass;The addition of flocculant is preferably 0.05~0.5wt% of the first supernatant, concretely 0.1wt%.1h is stirred after alkali metal sulphide in the present invention, it is preferred to be added in the first supernatant, then is added into waste water Flocculant.In the present invention, first supernatant and milk of lime, alkali metal sulphide and flocculant are preferably described above one Hybrid reaction in order reaction case.During hybrid reaction, heavy metal ion, fluorine ion, arsenic ion and portion in the first supernatant Divide sulfate ion etc. after hybrid reaction terminates, the mixed liquor containing sediment can be obtained with milk of lime formation sediment.Mixed Close after liquid, the mixed liquor is clarified.In the present invention, mixed liquor preferably carries out clear in one-level depositing reservoir described above Clearly, residence time of the mixed liquor in the one-level depositing reservoir is preferably 1h~2h, concretely 1.5h.After clarification, is obtained Two supernatants and sediment.The sediment preferably carries out press filtration, and the filtrate that press filtration is obtained is preferably returned to clarification process, and press filtration is obtained Arranged outside the sludge arrived.
Obtain after the second supernatant, by second supernatant and alkali metal hydroxide hybrid reaction.Wherein, the alkali Metal hydroxides is preferably potassium hydroxide and/or NaOH;The consumption of alkali metal hydroxide preferably passes through mixed system PH value is controlled, and second supernatant and the mixed mixed system pH value of alkali metal hydroxide are preferably 11.5~12.5, Concretely 12;The alkali metal hydroxide is mixed preferably in the form of alkali metal hydroxide aqueous solution with the second supernatant Close, the concentration of the metal hydroxides aqueous solution is preferably 10~35wt%, more preferably 25~30wt%.In the present invention In, preferably stir 1h after the second supernatant is mixed with alkali metal hydroxide.In the present invention, second supernatant and alkali Metal hydroxides hybrid reaction preferably in second order reaction case described above.During hybrid reaction, in the second supernatant Magnesium ion after hybrid reaction terminates, can be obtained containing magnesium hydrate precipitate with alkali metal hydroxide formation magnesium hydrate precipitate thing The mixed liquor of thing.Obtain after mixed liquor, the mixed liquor is clarified.In the present invention, mixed liquor is preferably described above Clarified in two grades of depositing reservoirs, residence time of the mixed liquor in two grades of depositing reservoirs is preferably 1h~2h, concretely 1.5h.After clarification, the 3rd supernatant and magnesium hydrate precipitate are obtained.The magnesium hydrate precipitate preferably carries out press filtration, and press filtration is obtained To filtrate be preferably returned to clarification process, the filter cake that press filtration is obtained as magnesium hydroxide products.
Obtain after the 3rd supernatant, by the 3rd supernatant and alkali metal meta-aluminate hybrid reaction.Wherein, the alkali Metal meta-aluminate is preferably potassium metaaluminate and/or sodium metaaluminate.In the present invention, the 3rd supernatant and alkali metal meta-aluminate The mode of mixing is preferably that alkali metal meta-aluminate is added into the 3rd supernatant, and the addition of alkali metal meta-aluminate preferably leads to Stop addition alkali during crossing the control of mixed system pH value, hybrid reaction, when the pH value of system preferably to be mixed will rise Metal meta-aluminate.In the present invention, being slowly added to alkali metal meta-aluminate, the pH value of mixed system has one to fall before The variation tendency risen afterwards, it is all the process for consuming hydroxide ion (OH-) when reacting beginning that reason, which is, after reaction terminates, Add causes mixed system pH value to rise in the alkali metal meta-aluminate of alkalescence, therefore can immediately stop when pH value will rise Add alkali metal meta-aluminate.In the present invention, the alkali metal meta-aluminate is preferably with the alkali metal meta-aluminate aqueous solution Form is mixed with the 3rd supernatant, and the concentration of the alkali metal meta-aluminate aqueous solution is preferably 10~40wt%, more preferably 15~20wt%.In the present invention, it is preferred to stir 1h after the 3rd supernatant is mixed with alkali metal meta-aluminate.In the present invention In, the 3rd supernatant and alkali metal meta-aluminate hybrid reaction preferably in third-order reaction case described above.Hybrid reaction During, calcium ion, sulfate radical, chlorion in the 3rd supernatant etc. can with the formation of alkali metal meta-aluminate by calcium sulphoaluminate and The jelly that calcium chloroaluminate mixture is constituted, after hybrid reaction terminates, obtains the mixed liquor containing jelly.Obtain after mixed liquor, The mixed liquor is clarified.In the present invention, mixed liquor is preferably clarified in three-level depositing reservoir described above, mixing Residence time of the liquid in the three-level depositing reservoir is preferably 1h~2h, concretely 1.5h.After clarification, the 4th supernatant is obtained And jelly.The jelly preferably carries out press filtration, and the filtrate that press filtration is obtained is preferably returned to clarification process, the filter cake that press filtration is obtained As calcium sulphoaluminate/calcium chloroaluminate product.
Obtain after the 4th supernatant, by the 4th supernatant and CO2Hybrid reaction.In the present invention, on the described 4th Clear liquid and CO2The mode of mixing is preferably to be passed through CO into the 4th supernatant2。CO2During being passed through, the pH of mixed system Value constantly declines, and stops being passed through CO preferably when the pH of mixed system no longer declines2.In the present invention, the 4th supernatant With CO2Mixed mixed system pH value is preferably 7~8, and concretely 7.53.In the present invention, it is preferred in the 4th supernatant With CO21h is stirred after mixing.In the present invention, the 4th supernatant and CO2It is preferred that being mixed in fourth-order reaction case described above Reaction.During hybrid reaction, remaining meta-aluminate can be with CO in the 4th supernatant2Form aluminum hydroxide precipitate, mixing After reaction terminates, the mixed liquor of aluminium hydroxide sediment is obtained.Obtain after mixed liquor, the mixed liquor is clarified. In the present invention, mixed liquor is preferably clarified in level Four depositing reservoir described above, and mixed liquor is in the level Four depositing reservoir Residence time is preferably 1h~2h, concretely 1.5h.After clarification, the 4th supernatant and aluminum hydroxide precipitation are obtained.Wherein, Four supernatants are the processed waste water that the inventive method is obtained, the processed waste water can as desulfurizing tower supplement Water circulation, Or further advanced treating.The aluminum hydroxide precipitation preferably carries out press filtration, and the filtrate that press filtration is obtained is preferably returned to clarification process, The filter cake that press filtration is obtained as aluminum hydroxide product.
In the present invention, desulfurization wastewater is obtained into the supernatant more clarified by primary clarifier, adds milk of lime, adjusted Section pH makes heavy metal ion, fluorine ion, arsenic ion and part of sulfuric acid radical ion etc. form sediment with calcium hydroxide and remove;Again Alkali hydroxide soln is added, pH is adjusted again, the magnesium ion in solution is removed, so as to prepare magnesium hydroxide production Product, magnesium hydroxide is widely used, available for fire retardant, Green Water Treatment Reagents;Alkali metal meta-aluminate is added in above-mentioned clear liquid, with Calcium ion, sulfate radical, chlorion reaction in solution prepare calcium sulphoaluminate/calcium chloroaluminate jelly, calcium sulphoaluminate/chlorine aluminium Sour calcium is widely used, available for water treatment agent, sealing agent, adsorbent;Finally it is passed through excessive carbon dioxide and removes remaining alkali The pH value of metal meta-aluminate and reduction solution, production water carries out reuse or advanced treating, while obtaining product aluminium hydroxide, hydrogen Aluminum oxide is widely used, can be used as inorganic combustion inhibitor.The desulfurization wastewater resource utilization system that the present invention is provided uses alkali Metal hydroxides demagging, the deliming of alkali metal meta-aluminate, sulfate radical, chlorion, carbon dioxide handles excessive alkali metal Meta-aluminate, can effectively reduce waste water hardness, while high chlorine root, high sulfate radical can also be removed, efficiently solve high chlorine root band The equipment corrosion problem come;And the system that the present invention is provided does not have discharge of wastewater (zero-emission) during waste water is handled, Production water can meet reuse requirement, and pollutant, which can obtain, fully recycles (recycling), realizes desulfurization wastewater by " zero-emission " To the transformation of " recycling ", the purpose for reached energy-saving and emission-reduction, turning waste into wealth;The system process route letter that the other present invention is carried Single, the equipment manufacturing cost used is low, it is easy to safeguard, environmentally friendly, with good economic benefit and social benefit.Experimental result Show, the waste water that the method processing provided using the present invention is obtained meets the supplement water water quality requirement of desulfurizing tower, while will can give up Resource reclaim in water prepares the chemicals such as magnesium hydroxide, calcium sulphoaluminate/calcium chloroaluminate and aluminium hydroxide.
For the sake of becoming apparent from, it is described in detail below by following examples.
Embodiment 1
A) desulfurization wastewater resource utilization system
The system that the present embodiment is provided mainly includes primary clarifier, first order reaction case, one-level depositing reservoir, second order reaction Case, two grades of depositing reservoirs, third-order reaction case, three-level depositing reservoir, fourth-order reaction pond and level Four depositing reservoir composition.Wherein, primary clarification Pond, one-level depositing reservoir, two grades of depositing reservoirs, three-level depositing reservoirs and level Four depositing reservoir are exported with delivery port and sediment, primary Depositing reservoir delivery port is connected with first order reaction case, and the outlet of first order reaction case is connected with one-level depositing reservoir entrance, one-level clarification Pond delivery port is connected with second order reaction case, and the outlet of second order reaction case is connected with two grades of depositing reservoirs, after two grades of depositing reservoir water outlets It is connected with third-order reaction case, the outlet of third-order reaction case is connected with three-level depositing reservoir entrance, three-level depositing reservoir delivery port and four Order reaction case is connected, and the outlet of fourth-order reaction case is connected with level Four depositing reservoir.The first order reaction case, second order reaction case, three Order reaction case, fourth-order reaction case are equipped with agitator and pH meter.The primary clarifier, one-level depositing reservoir, two grades of depositing reservoirs, three Level depositing reservoir, level Four depositing reservoir sediment entrance are equipped with corresponding elevator pump.The primary clarifier, one-level depositing reservoir, two Level depositing reservoir, three-level depositing reservoir, the outlet of level Four depositing reservoir sediment are all provided with sludge pump and corresponding filter press, the filtrate of filter press Outlet is connected with the water inlet of corresponding depositing reservoir.
B) desulfurization wastewater resource utilization method
Certain coal-fired plant flue gas wet desulphurization waste water is taken, desulfurization wastewater recycling is carried out using said system, specifically Process includes:
1) desulfurization wastewater first passes around primary clarifier and carries out clarified separation 1.5h, and the clarified pond sludge pump of sediment enters Depositing reservoir filter press is dehydrated, and filtrate is back to primary clarifier, and filter cake carries out outward transport processing.And depositing reservoir waste water is carried out Sampling, and Water quality detected is done, its main component is as follows:
2) primary clarifier supernatant is input to first order reaction case, and pH meter, agitator in starting box after water quality detection, The milk of lime regulation pH value for adding 5wt% simultaneously is stopping addition milk of lime after 9.5, then adds vulcanized sodium, the throwing of vulcanized sodium Dosage is 20mg/L, polyacrylamide is added after stirring 1h, the dosage of polyacrylamide is 0.1wt%.Above-mentioned solid-liquid mixing Thing enters one-level depositing reservoir clarified separation 1.5h by depositing reservoir elevator pump, and the clarified pond sludge pump of sediment enters depositing reservoir pressure Filter is dehydrated, and filtrate is back to one-level depositing reservoir, and filter cake carries out outward transport processing.Through the water quality detection after this step process point Analysis is as follows:
a)pH:9.5 b)Ca2+:7587mg/L c)Mg2+:896mg/L
d)SO4 2-:1489mg/L e)Cl-:11789mg/L f)F-:Trace
H) other heavy metal ion:Trace
3) one-level depositing reservoir supernatant is input to second order reaction case, and pH meter, agitator in starting box, adds simultaneously 30wt% NaOH regulation pH value is 12.0, then stirs 1h.The solidliquid mixture of acquisition enters by depositing reservoir elevator pump Enter two grades of depositing reservoir clarified separation 1.5h, the clarified pond sludge pump of sediment is dehydrated into depositing reservoir filter press, and filtrate is returned Two grades of depositing reservoirs are back to, filter cake is magnesium hydroxide products.It is as follows through the Water quality detected after this step process:
a)pH:12.0 b)Ca2+:7620mg/L c)SO4 2-:1423mg/L
d)Cl-:11800mg/L
4) two grades of depositing reservoir supernatants are input to third-order reaction case, and pH meter, agitator in starting box, add simultaneously 20wt% sodium aluminate solution, pH value is gradually decreased down 10.6 by 12.0 and kept for a period of time, and pH value is stopped immediately when rising Sodium aluminate solution is only added, 1h is then stirred.The solidliquid mixture of acquisition enters three-level depositing reservoir by depositing reservoir elevator pump Clarified separation 1.5h, the clarified pond sludge pump of sediment is dehydrated into depositing reservoir filter press, and filtrate is back to three-level clarification Pond, filter cake is calcium sulphoaluminate/calcium chloroaluminate product.It is as follows through the Water quality detected after this step process:
a)pH:10.6 b)Ca2+:156mg/L c)SO4 2-:245mg/L
d)Cl-:5423mg/L e)Al:2455mg/L
5) three-level depositing reservoir supernatant is input to fourth-order reaction case, and pH meter, agitator in starting box, while being passed through dioxy Change carbon, the pH value of mixed system constantly declines during carbon dioxide is passed through, when pH value no longer declines, stopping is passed through titanium dioxide Carbon, then stirs 1h.The solidliquid mixture of acquisition enters level Four depositing reservoir clarified separation 1.5h, precipitation by depositing reservoir elevator pump The clarified pond sludge pump of thing is dehydrated into depositing reservoir filter press, and filtrate is back to level Four depositing reservoir, and filter cake is hydroxide Aluminium product.It is as follows through the change of water quality after this step process:
a)pH:7.5 b)Ca2+:167mg/L c)SO4 2-:261mg/L
d)Cl-:5356mg/L
Desulfurization wastewater after being handled through the inventive method meets the supplement water water quality requirement of desulfurizing tower, can be used as desulfurizing tower Supplement water is able to reuse.
Embodiment 2:
Certain another coal-fired plant flue gas wet desulphurization waste water is taken, desulfurization wastewater recycling is carried out using the system of embodiment 1 Utilize, detailed process includes:
1) desulfurization wastewater first passes around primary clarifier and carries out clarified separation 2h, and the clarified pond sludge pump of sediment enters clear Clear pond filter press is dehydrated, and filtrate is back to primary clarifier through primary clarifier filter press water outlet elevator pump, and filter cake is carried out Outward transport is handled.And depositing reservoir waste water is sampled, and Water quality detected is done, its main component is as follows:
2) primary clarifier supernatant is input to first order reaction case, and pH meter, agitator in starting box after water quality detection, The milk of lime regulation pH value for adding 5wt% simultaneously is stopping addition milk of lime after 9.5, then adds vulcanized sodium, the throwing of vulcanized sodium Dosage is 25mg/L, polyacrylamide is added after stirring 1h, the dosage of polyacrylamide is 0.1wt%.Above-mentioned solid-liquid mixing Thing enters one-level depositing reservoir clarified separation 2h by depositing reservoir elevator pump, and the clarified pond sludge pump of sediment enters depositing reservoir press filtration Machine is dehydrated, and filtrate is back to one-level depositing reservoir, and filter cake carries out outward transport processing.Through the Water quality detected after this step process It is as follows:
a)pH:9.5 b)Ca2+:4686mg/L c)Mg2+:8432mg/L
d)SO4 2-:4134mg/L e)Cl-:14350mg/L f)F-:Trace
H) other heavy metal ion:Trace
3) one-level depositing reservoir supernatant is input to second order reaction case, and pH meter, agitator in starting box, while adding 30% NaOH regulation pH value be 12.0, then stir 1h.The solidliquid mixture of acquisition enters two grades by depositing reservoir elevator pump Depositing reservoir clarified separation 2h, the clarified pond sludge pump of sediment is dehydrated into depositing reservoir filter press, and filtrate is back to two grades Depositing reservoir, filter cake is magnesium hydroxide products.It is as follows through the Water quality detected after this step process:
a)pH:12.0 b)Ca2+:4536mg/L c)SO4 2-:3956mg/L
d)Cl-:14349mg/L
4) two grades of depositing reservoir supernatants are input to third-order reaction case, and pH meter, agitator in starting box, add simultaneously 20wt% sodium aluminate solution, pH value is gradually decreased down 10.5 by 12.0 and kept for a period of time, and pH value is stopped immediately when rising Sodium aluminate solution is only added, 1h is then stirred.The solidliquid mixture of acquisition enters three-level depositing reservoir by depositing reservoir elevator pump Clarified separation 2h, the clarified pond sludge pump of sediment is dehydrated into depositing reservoir filter press, and filtrate is back to three-level depositing reservoir, Filter cake is calcium sulphoaluminate/calcium chloroaluminate product.It is as follows through the Water quality detected after this step process:
a)pH:10.5 b)Ca2+:231mg/L c)SO4 2-:321mg/L
d)Cl-:6523mg/L e)Al:3556mg/L
5) three-level depositing reservoir supernatant is input to fourth-order reaction case, and pH meter, agitator in starting box, while being passed through dioxy Change carbon, the pH value of mixed system constantly declines during carbon dioxide is passed through, when pH value no longer declines, stopping is passed through titanium dioxide Carbon, then stirs 1h.The solidliquid mixture of acquisition enters level Four depositing reservoir clarified separation 2h, sediment by depositing reservoir elevator pump Clarified pond sludge pump is dehydrated into depositing reservoir filter press, and filtrate is back to level Four depositing reservoir, and filter cake is aluminium hydroxide Product.It is as follows through the change of water quality after this step process:
a)pH:7.3 b)Ca2+:232mg/L c)SO4 2-:326mg/L
d)Cl-:6521mg/L
Desulfurization wastewater after being handled through the inventive method can be able to reuse as the supplement water of desulfurizing tower.
The above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should It is considered as protection scope of the present invention.

Claims (10)

1. a kind of desulfurization wastewater resource utilization system, including:
Primary clarifier;
Milk of lime charge door, alkali gold are provided with the first order reaction case being connected with the delivery port of primary clarifier, first order reaction case Belong to sulfide charge door and flocculant charge door;
The one-level depositing reservoir being connected with the outlet of first order reaction case;
Alkali metal hydroxide charging is provided with the second order reaction case being connected with the delivery port of one-level depositing reservoir, second order reaction case Mouthful;
Two grades of depositing reservoirs being connected with the outlet of second order reaction case;
The charging of alkali metal meta-aluminate is provided with the third-order reaction case being connected with the delivery port of two grades of depositing reservoirs, third-order reaction case Mouthful;
The three-level depositing reservoir being connected with the outlet of third-order reaction case;
Carbon dioxide mouthful is provided with the fourth-order reaction case being connected with the delivery port of three-level depositing reservoir, fourth-order reaction case;
The level Four depositing reservoir being connected with the outlet of fourth-order reaction case.
2. system according to claim 1, it is characterised in that the first order reaction case, second order reaction case, third-order reaction case Agitator is provided with fourth-order reaction case.
3. system according to claim 1, it is characterised in that the first order reaction case, second order reaction case, third-order reaction case PH meter is provided with fourth-order reaction case.
4. system according to claim 1, it is characterised in that the primary clarifier, one-level depositing reservoir, two grades of clarifications The sediment outlet in pond, two grades of depositing reservoirs and level Four depositing reservoir is respectively connected with filter press.
5. a kind of desulfurization wastewater resource utilization method, comprises the following steps:
A), desulfurization wastewater is clarified, and obtains the first supernatant;
B), first supernatant and milk of lime, alkali metal sulphide and flocculant hybrid reaction, clarification, obtain the second supernatant Liquid;
C), second supernatant and alkali metal hydroxide hybrid reaction, clarification, obtains the 3rd supernatant and magnesium hydroxide is heavy Form sediment;
D), the 3rd supernatant and alkali metal meta-aluminate hybrid reaction, clarification, obtain the 4th supernatant and jelly;Institute Jelly is stated for calcium sulphoaluminate and calcium chloroaluminate mixture;
E), the 4th supernatant and CO2Hybrid reaction, clarification, obtains processed waste water and aluminum hydroxide precipitation.
6. method according to claim 5, it is characterised in that in step b), the mode of mixing is successively to the first supernatant Milk of lime, alkali metal sulphide and flocculant are added in liquid;
It is 9.0~9.5 that the mixed system pH value after milk of lime is added into the first supernatant;The addition of alkali metal sulphide is 1.1~1.8 times of heavy metal ion quality contained by first supernatant;The addition of flocculant for the first supernatant 0.05~ 0.5wt%.
7. method according to claim 5, it is characterised in that in step c), second supernatant and alkali metal hydrogen-oxygen The mixed mixed system pH value of compound is 11.5~12.5.
8. method according to claim 5, it is characterised in that in step d), the mode of mixing is into the 3rd supernatant Add alkali metal meta-aluminate;
Stop addition alkali metal meta-aluminate during the hybrid reaction, when the pH value of system to be mixed will rise.
9. method according to claim 5, it is characterised in that in step e), the mode of mixing is into the 4th supernatant It is passed through CO2
CO2During being passed through, the pH value of mixed system constantly declines, and stops being passed through CO when the pH of system to be mixed no longer declines2
10. the method according to any one of claim 5~9, it is characterised in that in step a), first supernatant PH value is 3~7, and suspended solids content is 1000~80000mg/L, Ca2+Content is 500~6000mg/L, Mg2+Content is 200 ~9000mg/L, SO4 2-Content is 1000~25000mg/L, Cl-Content is 1000~15000mg/L, F-Content is 5~40mg/ L, Pb2+Content is 2~15mg/L, Ni+Content is 0.1~5mg/L, and full Fe contents are 0.1~5mg/L, Hg2+Content be 0.1~ 5mg/L, Cd2+Content is 1~10mg/L.
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Cited By (2)

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Publication number Priority date Publication date Assignee Title
CN107325823A (en) * 2017-08-16 2017-11-07 宁夏大学 The soil conditioner and soil improvement method in a kind of salt-soda soil
CN109173956A (en) * 2018-03-01 2019-01-11 中国石油大学(北京) The system for handling chlorine aluminium acidic ionic liquids dead catalyst and alkaline waste water

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107325823A (en) * 2017-08-16 2017-11-07 宁夏大学 The soil conditioner and soil improvement method in a kind of salt-soda soil
CN109173956A (en) * 2018-03-01 2019-01-11 中国石油大学(北京) The system for handling chlorine aluminium acidic ionic liquids dead catalyst and alkaline waste water

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