CN204058604U - The device of ammonia and urea soln gas cleaning absorption liquid ammonium persulphate - Google Patents
The device of ammonia and urea soln gas cleaning absorption liquid ammonium persulphate Download PDFInfo
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- CN204058604U CN204058604U CN201420464750.XU CN201420464750U CN204058604U CN 204058604 U CN204058604 U CN 204058604U CN 201420464750 U CN201420464750 U CN 201420464750U CN 204058604 U CN204058604 U CN 204058604U
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- absorption liquid
- anolyte
- compartment
- ammonium persulphate
- ammonia
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Abstract
The utility model discloses the device of a kind of ammonia and urea soln gas cleaning absorption liquid ammonium persulphate.This device mainly comprises a cell body, a negative plate, a positive plate, barrier film, an anolyte container for storing liquid; An anolyte solution feed pump, an anode gas flow rate meter, a catholyte container for storing liquid, catholyte solution feed pump, a cathode system gauge and a DC voltage-stabilizing stable state power supply.Positive plate and negative plate are oppositely arranged, and are all connected to described power supply, to produce an electric field between negative plate and positive plate.The method is carried out desulphurization denitration absorption liquid and is prepared ammonium persulphate based on electrolyzer, and adopts plate barrier film to separate catholyte and anolyte; Improved by these, then control suitable response voltage, temperature and time.Effectively low value-added ammonium sulfate product can be converted into the ammonium persulphate product of high added value.Present method is simple to operate, can be applicable to process desulphurization denitration absorption liquid, has environmental protection, efficiently feature.
Description
Technical field
The utility model belongs to the field of smoke treatment desulphurization denitration absorption liquid in air environmental protection, relates to a kind of device utilizing ammonia and urea soln gas cleaning absorption liquid ammonium persulphate.
Background technology
At present, no matter domestic be ammonia type flue gas desulfurizing or the flue gas desulfurization of wet method lime-gypsum method, or wet flue gas simultaneous SO_2 and NO removal all exists the green process problem of secondary of the high added value of absorption liquid.In China's Practical Project, it is less that the wet process of FGD denitration absorbing liquor circulating resourcesization realized in complete meaning utilizes, which results in a large amount of wet process of FGD denitration absorbing liquor of current China in various degree create secondary pollution problem, especially in a wet process the secondary pollution of the absorption liquid of flue gas desulfurization is particularly outstanding, constrains greatly developing further of wet flue gas simultaneous SO_2 and NO removal.Therefore, the high added value recycling solving absorption liquid in wet flue gas simultaneous SO_2 and NO removal process is one of pendulum bottleneck problem in face of us.
Ammonia/urea soln flue gas and desulfurizing and denitrifying technique, it is a kind of novel, efficient, advanced flue gas and desulfurizing and denitrifying method, its working cost is relatively low, system water loss is little, byproduct is ammonium sulfate or ammonium bisulfite, byproduct is easy to recycle, and is a kind ofly have one of huge prospect, the simultaneous SO_2 and NO removal technology having researching value.But the recycling of its absorption liquid is at present still adopt conventional ammonium sulfate (or ammonium sulphite) crystallization process to carry out recycling, the power consumption of ammonium sulfate (or ammonium sulphite) crystallization process is high, and byproduct quality is not high, be worth also relatively limited, and there is the awkward situation of sales difficulty.Analyze discovery after deliberation, ammonium persulphate not only selling price is high, and has good existing market at home, and has huge potential market, and development prospect is very good.At chemical field, industrial production ammonium persulphate has two kinds of methods, i.e. electrolytic process and anthraquinone.The ammonium persulphate purity of anthraquinone production is low, and purifying technique is loaded down with trivial details, and production process is polluted large.Electrolytic process production process is simple, and pollute little, product separation is easy.And industrial electro solution produces (NH
4)
2s
2o
8technique comparative maturity, its mainly with ammonium sulfate or ammonium bisulfate solution for raw material, raw material is relatively simple.But find in the research to ammonia and urea soln flue gas and desulfurizing and denitrifying absorption liquid, account for main body with ammonium sulfate and ammonium sulphite in its absorption liquid, mass percentage concentration is about about 97%, and wherein ammonium sulfate mass percentage concentration reaches more than 82%; Ammonium nitrate mass percentage concentration accounts for about 2%, and ammonium nitrite mass percentage concentration concentration is less than 1%.Due to composition relative complex in ammonia/urea soln flue gas and desulfurizing and denitrifying absorption liquid, and there is a small amount of additive, its electrolytic process produces (NH
4)
2s
2o
8at home and abroad except bear source Research Team of Southeast China University has carried out certain theory and experimental study, there is no any other relevant research report.
The principle of ammonium sulfate electrolytic preparation ammonium persulphate is as follows:
Electrolytic process ionic reaction formula:
Anode: 2SO
4 2-→ S
2o
8 2-+ 2e (1)
Negative electrode: 2H
++ 2e →
2h ↑ (2)
The side reaction that this process occurs mainly contains following three:
Oxygen anodic evolution reacts:
2H
2O→4H
++O
2↑+4e (3)
Persulphate hydrolysis generates Lu and blocks acid, i.e. permonosulphuric acid:
S
2O
8 2-+H
2O→HSO
5 -+HSO
4 - (4)
Persulfate is reduced on negative electrode:
S
2O
8 2-+2e→2SO
4 2- (5)
Utility model content
Technical problem: the utility model provides a kind of efficient, it is low to consume energy, by-product value is high, and technique is simple and convenient, the device of the ammonia that technical process is short and urea soln gas cleaning absorption liquid ammonium persulphate.
Technical scheme: the device of ammonia of the present utility model and urea soln gas cleaning absorption liquid ammonium persulphate, for electrolyzer, comprise the electrolyzer anode chamber and cathode compartment that are separated into by the plate barrier film be arranged in cell body, anode compartment outlet and anolyte compartment's import is provided with in described anolyte compartment, inwall is provided with titanium platinum plated anode plate, cathode chamber outlet and cathode chamber inlet is provided with in described cathode compartment, inwall is provided with titanium negative plate, the import of described anolyte compartment is connected with anolyte solution feed pump and anode gas flow rate meter, described cathode chamber inlet is connected with catholyte solution feed pump and cathode system gauge, at anode compartment outlet, anolyte compartment's import, cathode chamber outlet and cathode chamber inlet place are respectively arranged with fluid temperature sensor.
In the preferred version of the utility model device, plate barrier film adopts ionic membrane.
The method of ammonia of the present utility model and urea soln gas cleaning absorption liquid ammonium persulphate, based on said apparatus, comprises the following steps:
1) after being mixed with oxygen inhibiting agent by the absorption liquid that ammonia and urea soln flue gas purifying technique obtain, pump into anolyte compartment, described oxygen inhibiting agent is ammonium thiocyanate or ammonium polyphosphate, pumps in cathode compartment by the sulphuric acid soln of mass percentage concentration 10%-40% simultaneously;
2) direct current applying 5-7V by DC voltage-stabilizing stable state power supply between titanium platinum plated anode plate and titanium negative plate carries out the electrolytic reaction of synthesizing ammonium persulphate;
3) after electrolysis 3-5 hour, when the ammonium persulphate mass concentration in anolyte reaches more than 200g/L, anolyte is discharged and carries out crystallization, obtain highly purified ammonium persulphate finished product.
In the preferred version of the utility model method, step 1) in, the mass percentage concentration that oxygen inhibiting agent accounts for the absorption liquid that ammonia and urea soln flue gas purifying technique obtain is 0.01%-0.1%.
The utility model utilizes the complicated absorption liquid produced in ammonia and urea soln flue gas purifying technique to prepare ammonium persulphate, technique is simple and convenient, technical process is short, and abandoned the crystallization process generally adopted at present and prepare the high energy consumption and low value-added problem that ammonium sulfate (or ammonium sulphite) technique brings, reduce operation energy consumption, improve byproduct quality and added value, thus effectively reduce the running cost of flue gas desulfurization and denitrification.
Beneficial effect: compared with prior art, the utility model has the following advantages:
1. the cathode material of electrolyzer mainly uses lead electrode at present.Lead electrode is easily produced lead sulfate by electrolytic corrosion and precipitates, and forms plumbous mud, causes certain pollution to environment.The utility model adopts the titanium panel material not yet seeing report as negative electrode, and its erosion resistance very well, stability is stronger, pollution-free, cost is low, is a kind of desirable cathode material.
2. domestic ammonium persulphate industry extensively adopts porous membrane that cathode compartment and anolyte compartment are separated, although it is easy for installation, bath voltage is higher.The utility model have employed that bath voltage is low, consume energy low and high to the separation efficiency of ion plate barrier film---ionic membrane.
3. domesticly at present all adopt conventional ammonium sulfate or ammonium sulphite crystallization process to carry out recycling for ammonia and urea soln simultaneous SO_2 and NO removal absorption liquid, but the low value-added flue gas desulfurization and denitration technique running cost that makes of the highly energy-consuming of crystallization process and byproduct remains high, and seriously constrains wideling popularize and application of this technique.But, by remaining liquid electrolytic synthesis ammonium persulphate technique is had reaction conditions gentleness, flow process simple, be easy to realize that automatic control, by product selectivity are high, non-secondary pollution, be one of critical path of green syt.Electrolysate---persulphate has the advantages such as applied range, the market requirement is large, price is high, is about about 10 times of ammonium sulfate price, can increases substantially the added value of by product, reduces the running cost of flue gas desulfurization and denitrification system.
5. pair ammonia and urea soln simultaneous SO_2 and NO removal absorption liquid are by electrolytic preparation ammonium persulphate, again by the purified ammonium sulfate of crystallization process, remaining liquid is recycled to the absorption liquid as desulphurization denitration in the absorption liquid recycle system of desulphurization denitration, thus form a closed desulphurization denitration absorption liquid circulation and treatment system, realize byproduct high value added utilization, and the target of non-secondary pollution discharge.
Accompanying drawing explanation
Fig. 1 is the device floor map of ammonia and urea soln gas cleaning absorption liquid ammonium persulphate.
Fig. 2 is the system and device figure of ammonia and urea soln gas cleaning absorption liquid high value added utilization and recirculation.
Have in figure: 1. anolyte compartment; 2, cathode compartment; 3, titanium platinum plated anode plate; 4, titanium negative plate; 5, plate barrier film; 6, anode export; 7, anode inlet; 8, cathode outlet; 9, cathode inlet; 10, fluid temperature sensor; 11, anolyte container for storing liquid; 12, catholyte container for storing liquid; 13, anolyte solution feed pump; 14, catholyte solution feed pump; 15, anode gas flow rate meter; 16, cathode system gauge; 17, DC voltage-stabilizing stable state power supply; 18, desulphurization denitration absorption tower; 19, absorption liquid reservoir; 20, electrolyzer; 21, crystallizer; 22, in desulphurization denitration circulation fluid and pump; 23, neutralization reactor; 24, neutralization reaction liquid overboard pump; 25, crystallizer solution feed pump; 26, remaining liquid reflux pump; 27, desulphurization denitration absorption liquid recycle pump.
Embodiment
Below in conjunction with Figure of description and embodiment, the utility model is elaborated.
Embodiment 1: the device of ammonia of the present utility model and urea soln gas cleaning absorption liquid ammonium persulphate, comprise by the plate barrier film 5 be arranged in the middle of cell body, anolyte compartment 1 and cathode compartment 2, anode compartment outlet 6 and anolyte compartment's import 7 is provided with in anolyte compartment 1, inwall is provided with titanium platinum plated anode plate 3, cathode chamber outlet 8 and cathode chamber inlet 9 is provided with in cathode compartment 2, inwall is provided with titanium negative plate 4, anolyte compartment's import 7 is connected with anolyte solution feed pump 16 and anode gas flow rate meter 18, anolyte compartment's inlet flow rate is controlled by anolyte solution feed pump 16 and anode gas flow rate meter 18, cathode chamber inlet 9 is connected with catholyte solution feed pump 17 and cathode system gauge 19, anolyte compartment's inlet flow rate is controlled by anolyte solution feed pump 17 and anode gas flow rate meter 19, anode export place fluid temperature sensor and cathode outlet place fluid temperature sensor 10 is respectively equipped with to detect the temperature of anolyte compartment and cathode chamber outlet liquid at anode compartment outlet 6 and cathode chamber outlet 8 place, fluid temperature sensor 10 is respectively arranged with to detect the temperature of anolyte compartment and cathode chamber inlet liquid in anolyte compartment's import 7 and cathode chamber inlet 9 place.
By the absorption liquid in the absorption liquid reservoir 19 of bottom, desulphurization denitration absorption tower 18 being pumped in neutralization reactor 23 with pump 22 in desulphurization denitration circulation fluid, by adding a certain amount of ammoniacal liquor by the pH regulator of circulation fluid between 4-6, by neutralization reaction liquid overboard pump 24, by the solution after neutralization, (the ammonium sulfate mass concentration in solution is 328g/L, ammonium sulphite mass concentration is 56g/L, ammonium nitrate mass concentration is 12g/L, ammonium nitrite mass concentration is 4.3g/L, urea quality concentration is 1.15g/L, the mass percentage concentration of diethanolamine and trolamine is 0.015%, the mass percentage concentration that anode presses down oxygen additive sulfur ammonium cyanate (or ammonium polyphosphate) is 0.1%) pump into anolyte container for storing liquid 11, then by anolyte solution feed pump 13, by anodic dissolution, the anolyte compartment 1 sent in electrolyzer 20 carries out cyclic electrolysis reaction.Meanwhile, the sulphuric acid soln in catholyte reservoir 12 pumps in the cathode compartment 2 of electrolyzer 20 and carries out cyclic electrolysis reaction by catholyte solution feed pump 14, and ensures that in catholyte container for storing liquid 12, sulfuric acid mass percentage concentration maintains 10% by supplementing sulphuric acid soln timely.The electric current be added between titanium negative plate 4 on electrolyzer 20 and titanium platinum plated anode plate 3 is direct current, and voltage is maintained between 5-7V.When the ammonium persulphate mass concentration in anolyte reaches more than 200g/L, anolyte to be sent in crystallizer 21 through centrifugation by crystallizer solution feed pump 25, obtains solid ammonium persulphate finished product.Remove after impurity through entering the absorption liquid reservoir 19 of bottom, desulphurization denitration absorption tower 18 again by remaining liquid reflux pump 26 from liquid more than crystallizer 21 flows out, after supplementing a certain amount of ammonia/urea mixing solutions timely, via desulphurization denitration absorption liquid recycle pump 27, desulphurization denitration absorption liquid is sent in the spraying layer on top, desulphurization denitration absorption tower 18, carry out simultaneous SO_2 and NO removal reaction.Thus form a closed absorption liquid circulation and treatment system, realize the target of non-secondary pollution discharge.
Embodiment 2: by the absorption liquid in the absorption liquid reservoir 19 of bottom, desulphurization denitration absorption tower 18 being pumped in neutralization reactor 23 with pump 22 in desulphurization denitration circulation fluid, by adding a certain amount of ammoniacal liquor by the pH regulator of circulation fluid between 4-6, by neutralization reaction liquid overboard pump 24, by the solution after neutralization, (ammonium sulfate concentrations in solution is 328g/L, ammonium sulphite mass concentration is 56g/L, ammonium nitrate mass concentration is 12g/L, ammonium nitrite mass concentration is 4.3g/L, urea quality concentration is 1.15g/L, the mass percentage concentration of diethanolamine and trolamine is 0.015%, it is 0.01% that anode presses down the mass percentage concentration that oxygen additive sulfur ammonium cyanate (or ammonium polyphosphate) accounts for the absorption liquid that ammonia and urea soln flue gas purifying technique obtain) pump into anolyte container for storing liquid 11, then by anolyte solution feed pump 13, by anodic dissolution, the anolyte compartment 1 sent in electrolyzer 20 carries out cyclic electrolysis reaction.Simultaneously, mass percentage concentration 25% sulphuric acid soln in catholyte reservoir 12 pumps in the cathode compartment 2 of electrolyzer 20 and carries out cyclic electrolysis reaction by catholyte solution feed pump 14, and ensures that in catholyte container for storing liquid 12, sulfuric acid mass percentage concentration maintains 10-40% by supplementing sulphuric acid soln timely.The electric current be added between titanium negative plate 4 on electrolyzer 20 and titanium platinum plated anode plate 3 is direct current, and voltage is maintained between 5-7V.When the ammonium persulphate mass concentration in anolyte reaches more than 200g/L, anolyte to be sent in crystallizer 21 through centrifugation by crystallizer solution feed pump 25, obtains solid ammonium persulphate finished product.Remove after impurity through entering the absorption liquid reservoir 19 of bottom, desulphurization denitration absorption tower 18 again by remaining liquid reflux pump 26 from liquid more than crystallizer 21 flows out, after supplementing a certain amount of ammonia/urea soln timely, via desulphurization denitration absorption liquid recycle pump 27, desulphurization denitration absorption liquid is sent in the spraying layer on top, desulphurization denitration absorption tower 18, carry out simultaneous SO_2 and NO removal reaction.Thus form a closed absorption liquid circulation and treatment system, realize the target of non-secondary pollution discharge.
In embodiment 3, the mass percentage concentration pumping into sulphuric acid soln in cathode compartment 2 is 40%, and the mass percentage concentration that the oxygen inhibiting agent pumping into anolyte compartment 1 accounts for the absorption liquid that ammonia and urea soln flue gas purifying technique obtain is
0.055%.basic procedure and all the other parameters are with embodiment 1.
In embodiment 4, the mass percentage concentration pumping into sulphuric acid soln in cathode compartment 2 is 30%, and the mass percentage concentration that the oxygen inhibiting agent pumping into anolyte compartment 1 accounts for the absorption liquid that ammonia and urea soln flue gas purifying technique obtain is
0.03%.basic procedure and all the other parameters are with embodiment 2.
In embodiment 5, the mass percentage concentration pumping into sulphuric acid soln in cathode compartment 2 is 15%, and the mass percentage concentration that the oxygen inhibiting agent pumping into anolyte compartment 1 accounts for the absorption liquid that ammonia and urea soln flue gas purifying technique obtain is
0.08%.basic procedure and all the other parameters are with embodiment 2.
Above-described embodiment is only preferred implementation of the present utility model; should be understood that; for those skilled in the art; under the prerequisite not departing from the utility model principle; some improvement and equivalent replacement can also be made; these improve the utility model claim and are equal to the technical scheme after replacing, and all fall into protection domain of the present utility model.
Claims (2)
1. the device of an ammonia and urea soln gas cleaning absorption liquid ammonium persulphate, it is characterized in that, this device is electrolyzer, comprise the electrolyzer anode chamber (1) and cathode compartment (2) that are separated into by the plate barrier film (5) be arranged in cell body, anode compartment outlet (6) and anolyte compartment's import (7) is provided with in described anolyte compartment (1), inwall is provided with titanium platinum plated anode plate (3), cathode chamber outlet (8) and cathode chamber inlet (9) is provided with in described cathode compartment (2), inwall is provided with titanium negative plate (4), described anolyte compartment import (7) is connected with anolyte solution feed pump (16) and anode gas flow rate meter (18), described cathode chamber inlet (9) is connected with catholyte solution feed pump (17) and cathode system gauge (19), in anode compartment outlet (6), anolyte compartment's import (7), cathode chamber outlet (8) and cathode chamber inlet (9) place are respectively arranged with fluid temperature sensor (10).
2. the device of ammonia according to claim 1 and urea soln gas cleaning absorption liquid ammonium persulphate, is characterized in that, described plate barrier film (5) adopts ionic membrane.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104152943A (en) * | 2014-08-15 | 2014-11-19 | 东南大学 | Device and method for preparing ammonium persulphate with ammonia and urea solution flue gas purified absorption solution |
| CN105107340A (en) * | 2015-08-17 | 2015-12-02 | 南京师范大学 | Desulfurization, denitrification and demercuration integration apparatus based on amino absorber and method therefor |
-
2014
- 2014-08-15 CN CN201420464750.XU patent/CN204058604U/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104152943A (en) * | 2014-08-15 | 2014-11-19 | 东南大学 | Device and method for preparing ammonium persulphate with ammonia and urea solution flue gas purified absorption solution |
| CN104152943B (en) * | 2014-08-15 | 2017-05-10 | 东南大学 | Device and method for preparing ammonium persulphate with ammonia and urea solution flue gas purified absorption solution |
| CN105107340A (en) * | 2015-08-17 | 2015-12-02 | 南京师范大学 | Desulfurization, denitrification and demercuration integration apparatus based on amino absorber and method therefor |
| CN105107340B (en) * | 2015-08-17 | 2017-05-17 | 南京师范大学 | Desulfurization, denitrification and demercuration integration apparatus based on amino absorber and method therefor |
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Granted publication date: 20141231 Termination date: 20190815 |
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