CN105217852A - A kind of wet desulfurization system of non-wastewater discharge and technique - Google Patents
A kind of wet desulfurization system of non-wastewater discharge and technique Download PDFInfo
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- CN105217852A CN105217852A CN201510752077.9A CN201510752077A CN105217852A CN 105217852 A CN105217852 A CN 105217852A CN 201510752077 A CN201510752077 A CN 201510752077A CN 105217852 A CN105217852 A CN 105217852A
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- electrodialysis
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Abstract
The invention provides a kind of wet desulfurization system and technique of non-wastewater discharge.This system utilizes the mode of electrolysis-electrodialysis associating, to be rich in desulphurization system chlorion plaster serum rotational flow device overflowing liquid and process from the gypsum filtrate water of water extracter, chlorion is wherein discharged desulfurization slurry system with the form of chlorine, the low chlorine produced, the mixed solution of high ph-values, send into sprinkling system and again utilize.This system obviates the discharge of desulfurization wastewater, can desulfurization synergistic be realized, and obtain excellent byproduct hydrogen gas and chlorine, there is good economic implications and environment protection significance.
Description
Technical field
The invention belongs to flue gas desulfurization technique field, be specifically related to a kind of wet desulfurization system and technique of non-wastewater discharge.
Background technology
China is coal production maximum in the world and country of consumption, the coal amount of China's production and consumption in 2013 accounts for 47.4% and 50.3% of world's total amount respectively, the ratio of coal in the primary energy structure of China is up to more than 70% for a long time, causes the SO that China discharges thus
2about 90% is had to come from fire coal.Coal fire discharged a large amount of SO
2cause significant damage to farm crop, forest, building and human health, China is every year because of SO
2the financial loss that causes of discharge reach hundreds billion of unit.
Limestone-gypsum method flue gas desulfurization technology (WFGD) because of its coal wide accommodation, the advantage such as desulfuration efficiency is high, sorbent utilization is high, technical maturity and serviceability are high, become application flue gas desulfurization technique the most widely in present stage world wide.In this technological process, chlorine element in chlorine element in flue gas, the chlorine element in process water and sweetening agent (Wingdale) constantly enters desulfurization slurry and enrichment gradually, the chlorion of slurries middle and high concentration has reduction desulfuration efficiency, acceleration equipment corrosion and affects numerous harm such as gypsum qualitt, therefore in conventional WFGD process operation process, in order to maintain system stability safe operation and keep higher desulfuration efficiency, a certain amount of waste water must be discharged.
Desulfurization wastewater contains chlorion and other pollutents of high density, can not recycle and can not directly discharge, and therefore wet desulfurization system still needs the system setting up complexity to carry out wastewater treatment.Current thermal power plant adopts maximum method for treating desulfurized wastewaters to be traditional chemical precipitation method, and the method processes waste water through the process such as neutralization, sedimentation, flocculation and clarification, and this technics comparing is complicated, investment is large and need consumption various medicaments.
Chinese patent literature CN101486517A, CN103086550A, CN104150569A, CN101844819A, CN101417827A, CN101851041A, CN102020369A, CN103787541A, CN103896420A, CN104649498A, CN101486517A, CN101803504A etc. disclose some desulfuration waste water treatment process, these techniques simplify traditional chemical precipitator method technique all to a certain extent, but above-mentioned all technique is all the waste water discharged for desulphurization system to be processed, and is not fundamentally avoid desulphurization system waste discharge.
Summary of the invention
In order to overcome above-mentioned the deficiencies in the prior art, the present invention proposes a kind of wet desulfurization system and technique of non-wastewater discharge, this system have structure simple, take up an area less, the not advantage such as chemical agent consumption, the recycling of desulphurization system chlorion can be realized, and recyclable high-purity hydrogen, saving sweetening agent, and desulphurization system can be avoided to produce waste water.
For achieving the above object, the technical solution used in the present invention is:
A wet desulfurizing process for non-wastewater discharge, comprises the following steps:
(1) from the gypsum slurries of desulfurizer after gypsum swirler is separated, overflowing liquid enters overflowing liquid case and collects, and concentrated solution obtains desulfurization filtrate and enters filtrate box and collect after delivering to water extracter;
(2) the desulfurization filtrate in step (1) after filtrate box collects enters the electrodialysis chamber of electrolysis-electrodialysis composite slot, under galvanic effect, realizes electrodialytic desalting, obtains de-salted water;
(3) de-salted water in step (2) together enters the cathode compartment of electrolysis-electrodialysis composite slot with the swirler overflowing liquid from overflowing liquid case, and reacting at negative plate generates Ca (OH)
2, be rich in Ca (OH)
2catholyte enter in desulfurizer and carry out desulfurization; Dilute hydrochloric acid is full of, from the Cl that electrodialysis chamber's migration comes in anolyte compartment
-constantly generate chlorine in positive plate electric discharge.
In step (2), under galvanic effect, the Ca in desulfurization filtrate
2+cathode compartment is migrated to through cationic exchange membrane, Cl under electrical forces effect
-under electrical forces effect, migrate to anolyte compartment through anion-exchange membrane, achieve electrodialytic desalting.
In step (3), when the de-salted water in step (2) together enters the cathode compartment of electrolysis-electrodialysis composite slot with the swirler overflowing liquid from overflowing liquid case, there is following evolving hydrogen reaction at negative plate:
2H
2O+2e
-→H
2↑+2OH
-
The OH that catholyte generates
-the Ca come is moved with electrodialysis chamber
2+form Ca (OH)
2, be rich in Ca (OH)
2catholyte deliver in desulfurizer and carry out desulfurization, principal reaction is:
Ca(OH)
2+SO
2→CaSO
3+H
2O
Dilute hydrochloric acid is full of, from the Cl that electrodialysis chamber's migration comes in anolyte compartment
-constantly generate chlorine in positive plate electric discharge, electrolytic reaction is as follows:
2Cl
--2e
-→Cl
2↑
Because chlorine, in water, following hydrolysis reaction can occur:
Cl
2+H
2O→HClO+HCl
And the anolyte compartment of electrolysis-electrodialysis composite slot is filled with dilute hydrochloric acid, therefore can suppress the generation that said hydrolyzed is reacted, thus the chlorine that anode electrolysis produces constantly can be separated out.In addition, the dilute hydrochloric acid in operational process Anodic electricity room does not consume, and is only ensure the electroconductibility of electrolysis-electrodialysis device and the environment providing chlorine to separate out.
The hydrogen that step (3) obtains delivers to hydrogen-holder, and for selling outward or hydrogen cooled generator benefit hydrogen, the chlorine of acquisition delivers to recirculating cooling water system, for disinfection, algae removal.
In step (3), described in be rich in Ca (OH)
2the pH value of catholyte be 9 ~ 12.The mixed solution of high ph-values, the sprinkling system sending into desulfurizer utilizes again.
In order to better implement the wet desulfurizing process of non-wastewater discharge of the present invention, the present invention also provides a kind of wet desulfurization system.
A wet desulfurization system for non-wastewater discharge, comprise desulfurizer and electrolysis-electrodialysis composite slot, described electrolysis-electrodialysis composite slot is at least divided into three parts, is followed successively by cathode compartment, electrodialysis chamber and anolyte compartment;
The outlet end of described desulfurizer is connected with gypsum swirler;
The underflow opening of described gypsum swirler is connected with filtrate box by water extracter, and described filtrate box is connected with the liquid feeding end of described cathode compartment by the electrodialysis chamber of electrolysis-electrodialysis composite slot;
The effluent head of described gypsum swirler is connected with the cathode compartment of electrolysis-electrodialysis composite slot by overflowing liquid case; The outlet end of described cathode compartment is connected with the liquid feeding end structure of desulfurizer.
Wherein, described electrolysis-electrodialysis composite slot is provided with cationic exchange membrane and anion-exchange membrane, electrolysis-electrodialysis composite slot is divided into three parts by described cationic exchange membrane and anion-exchange membrane, be followed successively by cathode compartment, electrodialysis chamber and anolyte compartment, described cathode compartment is provided with negative plate, and described anolyte compartment is provided with positive plate.
In described electrolysis-electrodialysis composite slot, cationic exchange membrane, anion-exchange membrane, negative plate and positive plate adopt mode arranged in parallel to arrange.
Preferably, the cathode compartment of described electrolysis-electrodialysis composite slot is also connected with hydrogen-holder.The hydrogen that native system obtains is delivered to hydrogen-holder, for selling or hydrogen cooled generator benefit hydrogen outward.
Preferably, the anolyte compartment of described electrolysis-electrodialysis composite slot is connected with recirculating cooling water system.The chlorine that native system obtains is delivered to recirculating cooling water system, for disinfection, algae removal.
Preferably, described electrolysis-electrodialysis composite slot is connected with the liquid feeding end of desulfurizer by slush pump.
Preferably, the cathode compartment of described electrolysis-electrodialysis composite slot is connected with the top layer spraying layer of desulfurizer, or the cathode compartment of described electrolysis-electrodialysis composite slot is connected with the inlet duct before the top layer spraying layer slurry circulating pump in desulfurizer.The catholyte flowed out from cathode compartment delivers to thionizer top layer spraying layer for desulfurization synergistic after nozzle atomization through slush pump, or the inlet duct before the slurry circulating pump delivering to top layer spraying layer.
Preferably, described desulfurizer is thionizer.Industrial gaseous waste is carried out to the desulfurizer of desulfurization process, in the majority with tower equipment, its sweetening effectiveness is excellent.
Preferably, described water extracter is vacuum belt machine.Adopt vacuum belt machine to dewater to concentrated solution, can obtain desulfurization filtrate, the main component in desulfurization filtrate is CaCl
2.
The invention has the beneficial effects as follows:
(1) this system utilizes the mode of electrolysis-electrodialysis associating, to be rich in desulphurization system chlorion plaster serum rotational flow device overflowing liquid and process from the gypsum filtrate water of water extracter, chlorion is wherein discharged desulfurization slurry system with the form of chlorine, the low chlorine produced, the mixed solution of high ph-values, the sprinkling system sent in desulfurizer utilizes again.This system obviates the discharge of desulfurization wastewater, can desulfurization synergistic be realized, and obtain excellent byproduct hydrogen gas and chlorine, there is good economic implications and environment protection significance.
(2) system is simple, takes up an area few, non-wastewater discharge, eliminates complicated Waste Water Treatment.
(3) the harmful ion chlorion in desulphurization system is turned waste into wealth change chlorine into, for recirculated cooling water sterilization and disinfection, greatly save the preparing chlorine by electrolysis energy consumption of recirculating cooling water system.
(4) can desulfurization synergistic be realized, save sweetening agent, excellent byproduct hydrogen can be obtained simultaneously, improve economic benefit.
Accompanying drawing explanation
Fig. 1 is the wet desulfurization system figure of non-wastewater discharge of the present invention.
Fig. 2 is the structure iron for electrolysis of the present invention-electrodialysis composite slot.
Wherein:
1-thionizer, 2-gypsum swirler; 3-vacuum belt machine, 4-filtrate box, 5-hydrogen-holder, 6-overflowing liquid case, 7-slush pump, 8-electrolysis-electrodialysis composite slot, 9-recirculating cooling water system.
8-1-cathode compartment, 8-2-electrodialysis chamber, 8-3-anolyte compartment, 8-4-negative plate, 8-5-positive plate, 8-6-cationic exchange membrane, 8-7-anion-exchange membrane.
Embodiment
Below in conjunction with drawings and Examples, the present invention is further described.
Embodiment 1
As illustrated in fig. 1 and 2, a kind of wet desulfurization system of non-wastewater discharge, comprise thionizer 1 and electrolysis-electrodialysis composite slot 8, described electrolysis-electrodialysis composite slot 8 is provided with cationic exchange membrane 8-6 and anion-exchange membrane 8-7, electrolysis-electrodialysis composite slot is divided into three parts by described cationic exchange membrane 8-6 and anion-exchange membrane 8-7, be followed successively by cathode compartment 8-1, electrodialysis chamber 8-2 and anolyte compartment 8-3, negative plate 8-4 is provided with in described cathode compartment 8-1, positive plate 8-5 is provided with in described anolyte compartment 8-3, cationic exchange membrane 8-6 in wherein said electrolysis-electrodialysis composite slot 8, anion-exchange membrane 8-7, negative plate 8-4 and positive plate 8-5 adopts mode arranged in parallel to arrange.
Outlet end bottom described thionizer 1 is connected with gypsum swirler 2, the underflow opening of described gypsum swirler 2 is connected with filtrate box 4 by vacuum belt machine 3, described filtrate box 4 is connected with the electrodialysis chamber 8-2 of electrolysis-electrodialysis composite slot 8, the outlet end of described electrodialysis chamber 8-2 is connected with the liquid feeding end of cathode compartment 8-1, and the outlet side of described cathode compartment 8-1 is connected with hydrogen-holder 5.
The effluent head of described gypsum swirler 2 is connected by the cathode compartment 8-1 of overflowing liquid case 6 with electrolysis-electrodialysis composite slot 8, and the outlet end of the cathode compartment 8-1 of electrolysis-electrodialysis composite slot 8 to be connected with thionizer 1 top layer shower by slush pump 7 and to be connected; The anolyte compartment 8-3 of described electrolysis-electrodialysis composite slot 8 is connected with recirculating cooling water system 9.
Embodiment 2
A kind of wet desulfurizing process utilizing the non-wastewater discharge of system in embodiment 1, comprise the following steps: deliver to after gypsum swirler 2 is separated from the gypsum slurries of thionizer 1, gained swirler overflowing liquid delivers to overflowing liquid case 6, concentrated solution is delivered to vacuum belt machine 3 and is carried out processed, overflowing liquid (main component CaCl
2) the cathode compartment 8-1 of electrolysis-electrodialysis composite slot 8 is sent into after the pooling at overflowing liquid case 6.
(main component is CaCl to the filtrate that concentrated solution obtains after vacuum belt machine 3 dewaters
2) deliver to filtrate box 4, deliver to the electrodialysis chamber 8-2 of electrolysis-electrodialysis composite slot 8 after the pooling, Ca wherein
2+cathode compartment 8-1 is entered through cationic exchange membrane 8-6, Cl under electrical forces effect
-under electrical forces effect, enter anolyte compartment 8-3 through anion-exchange membrane 8-7, realize desalting.Filtrate water (de-salted water that saltiness is lower) after electrodialysis process delivers to the cathode compartment 8-1 of electrolysis-electrodialysis composite slot 8, together process in the cathode compartment 8-1 of electrolysis-electrodialysis composite slot 8 with the overflowing liquid from overflowing liquid case 6, negative plate 8-5 sends out the raw OH of evolving hydrogen reaction not stopping pregnancy
-, move with electrodialysis chamber 8-2 the Ca come
2+form Ca (OH)
2, gained is rich in Ca (OH)
2catholyte (pH value is 9 ~ 12) delivered to the top layer shower of thionizer 1 by slush pump 7, for desulfurization after nozzle atomization.The gas that the negative electrode of electrolysis-electrodialysis composite slot 8 produces delivers to hydrogen-holder 5, as hydrogen cooled generator group supplemental hydrogen source or sell outward, is full of dilute hydrochloric acid, moves from electrodialysis chamber 8-2 the Cl of coming in the anolyte compartment 8-3 of electrolysis-electrodialysis cell 8
-constantly discharge at positive plate 8-5 and generate chlorine, the chlorine herein produced directly is delivered to and is followed air ring water system 9 and to carry out disinfection sterilization.
The present invention reclaims the chlorion in desulphurization system by electrolysis-electrodialysis mode, avoid the discharge of waste water, eliminates complicated desulfurization wastewater treatment system simultaneously, also can save sweetening agent in addition, and obtain excellent byproduct hydrogen gas.This system has good economic implications and environment protection significance.
By reference to the accompanying drawings the specific embodiment of the present invention is described although above-mentioned; but not limiting the scope of the invention; one of ordinary skill in the art should be understood that; on the basis of technical scheme of the present invention, those skilled in the art do not need to pay various amendment or distortion that creative work can make still within protection scope of the present invention.
Claims (10)
1. a wet desulfurizing process for non-wastewater discharge, is characterized in that, comprises the following steps:
(1) from the gypsum slurries of desulfurizer after gypsum swirler is separated, overflowing liquid enters overflowing liquid case and collects, and concentrated solution obtains desulfurization filtrate and enters filtrate box and collect after delivering to water extracter;
(2) the desulfurization filtrate in step (1) after filtrate box collects enters the electrodialysis chamber of electrolysis-electrodialysis composite slot, under galvanic effect, realizes electrodialytic desalting, obtains de-salted water;
(3) de-salted water in step (2) together enters the cathode compartment of electrolysis-electrodialysis composite slot with the swirler overflowing liquid from overflowing liquid case, and reacting at negative plate generates Ca (OH)
2, be rich in Ca (OH)
2catholyte enter in desulfurizer and carry out desulfurization; Dilute hydrochloric acid is full of, from the Cl that electrodialysis chamber's migration comes in anolyte compartment
-constantly generate chlorine in positive plate electric discharge.
2. technique as claimed in claim 1, is characterized in that: in step (2), under galvanic effect, the Ca in desulfurization filtrate
2+cathode compartment is migrated to through cationic exchange membrane, Cl under electrical forces effect
-under electrical forces effect, migrate to anolyte compartment through anion-exchange membrane, realize electrodialytic desalting.
3. technique as claimed in claim 1, it is characterized in that: in step (3), when the de-salted water in step (2) together enters the cathode compartment of electrolysis-electrodialysis composite slot with the swirler overflowing liquid from overflowing liquid case, there is following evolving hydrogen reaction at negative plate: 2H
2o+2e
-→ H
2↑+2OH
-, the OH that catholyte generates
-the Ca come is moved with electrodialysis chamber
2+form Ca (OH)
2, be rich in Ca (OH)
2catholyte deliver in desulfurizer and carry out desulfurization.
4. technique as claimed in claim 3, is characterized in that: the hydrogen that step (3) obtains delivers to hydrogen-holder, and for selling outward or hydrogen cooled generator benefit hydrogen, the chlorine of acquisition delivers to recirculating cooling water system, for disinfection, algae removal.
5. for realizing the system of the wet desulfurizing process of non-wastewater discharge any one of Claims 1 to 4, comprising desulfurizer, it is characterized in that:
Also comprise electrolysis-electrodialysis composite slot, described electrolysis-electrodialysis composite slot is at least divided into three parts, is followed successively by cathode compartment, electrodialysis chamber and anolyte compartment;
The outlet end of described desulfurizer is connected with gypsum swirler;
The underflow opening of described gypsum swirler is connected with filtrate box by water extracter, and described filtrate box is connected with the liquid feeding end of described cathode compartment by the electrodialysis chamber of electrolysis-electrodialysis composite slot;
The effluent head of described gypsum swirler is connected with the cathode compartment of electrolysis-electrodialysis composite slot by overflowing liquid case; The outlet end of described cathode compartment is connected with the liquid feeding end structure of desulfurizer.
6. system as claimed in claim 5, is characterized in that: the cathode compartment of described electrolysis-electrodialysis composite slot is also connected with hydrogen-holder.
7. system as claimed in claim 5, is characterized in that: the anolyte compartment of described electrolysis-electrodialysis composite slot is connected with recirculating cooling water system.
8. system as claimed in claim 5, it is characterized in that: described electrolysis-electrodialysis composite slot is provided with cationic exchange membrane and anion-exchange membrane, electrolysis-electrodialysis composite slot is divided into three parts by described cationic exchange membrane and anion-exchange membrane, be followed successively by cathode compartment, electrodialysis chamber and anolyte compartment, described cathode compartment is provided with negative plate, and described anolyte compartment is provided with positive plate.
9. system as claimed in claim 5, is characterized in that: in described electrolysis-electrodialysis composite slot, cationic exchange membrane, anion-exchange membrane, negative plate and positive plate adopt mode arranged in parallel to arrange.
10. system as claimed in claim 5, is characterized in that: described electrolysis-electrodialysis composite slot is connected with the liquid feeding end of desulfurizer by slush pump.
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|---|---|---|---|
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110316883A (en) * | 2019-06-28 | 2019-10-11 | 武汉大学 | Desulfurization wastewater recycling electrodialytic technique |
| CN112194318A (en) * | 2020-09-28 | 2021-01-08 | 国家电投集团远达环保工程有限公司重庆科技分公司 | Flue gas waste heat concentration method and device for desulfurization wastewater |
| CN113433258A (en) * | 2021-06-16 | 2021-09-24 | 青岛盛瀚色谱技术有限公司 | Ion chromatograph with multiple working modes |
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Cited By (4)
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|---|---|---|---|---|
| CN110316883A (en) * | 2019-06-28 | 2019-10-11 | 武汉大学 | Desulfurization wastewater recycling electrodialytic technique |
| CN112194318A (en) * | 2020-09-28 | 2021-01-08 | 国家电投集团远达环保工程有限公司重庆科技分公司 | Flue gas waste heat concentration method and device for desulfurization wastewater |
| CN113433258A (en) * | 2021-06-16 | 2021-09-24 | 青岛盛瀚色谱技术有限公司 | Ion chromatograph with multiple working modes |
| CN113433258B (en) * | 2021-06-16 | 2024-06-07 | 青岛盛瀚色谱技术有限公司 | Ion chromatograph with multiple working modes |
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