CN107413180A - A kind of flue gas integration desulfurization denitration system and method - Google Patents
A kind of flue gas integration desulfurization denitration system and method Download PDFInfo
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- CN107413180A CN107413180A CN201610348919.9A CN201610348919A CN107413180A CN 107413180 A CN107413180 A CN 107413180A CN 201610348919 A CN201610348919 A CN 201610348919A CN 107413180 A CN107413180 A CN 107413180A
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- denitration
- flue gas
- desulfurization
- desulfuration
- desulphurization
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
- B01D53/50—Sulfur oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/54—Nitrogen compounds
- B01D53/56—Nitrogen oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/75—Multi-step processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/40—Alkaline earth metal or magnesium compounds
- B01D2251/402—Alkaline earth metal or magnesium compounds of magnesium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
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- Chemical & Material Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
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- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Treating Waste Gases (AREA)
Abstract
The present invention relates to a kind of flue gas integration desulfurization denitration system and method, wherein system includes pre- system for desulfuration and denitration, rear system for desulfuration and denitration and recycling system, and the rear system for desulfuration and denitration is connected with the pre- system for desulfuration and denitration and recycling system respectively；The pre- system for desulfuration and denitration includes serum producing system, ozone loading system and pre- denitration desulfurization cooler, and the pre- denitration desulfurization cooler is connected with the serum producing system and ozone loading system respectively；System for desulfuration and denitration is provided with spraying layer and spiral board after described, the spraying layer is connected with the spiral board, the present invention is combine sodalime double alkali method the advantages of on the basis of original magnesium processes desulfurization, solves the shortcomings that magnesium processes desulfurization product is difficult to handle, regeneration treatment is carried out to desulfurization waste liquor using the second alkali, desulfurizing agent is replaced, the product of the inventive method is (NH4)2SO4, Fertilizer application can be used as.
Description
Technical field
The present invention relates to exhaust-gas treatment field, more particularly to a kind of flue gas integration desulfurization denitration system
System and method.
Background technology
Desulfurization for flue gas mainly uses Wet Flue Gas Desulfurization Technique.Conventional Wet Flue Gas Desulfurization Technique master
Have：
1. wet desulfurization of flue gas by limestone-gypsum method；
2. sodium alkali flue gas desulfurization；
3. flue gas desulfurization by sodium-calcium dual-alkali scrubbing method；
4. magnesium method flue gas desulphurization；
5. ammonia type flue gas desulfurizing.
The advantage and disadvantage of each method：
Limestone-gypsum method is due to desulfurization product CaSO3* 1/2H2O easily ties when pH value is higher
Crystalline substance, so pipeline can be blocked；
Sodalime double alkali method in soda regenerator section due in the process of running, adding CaO as again
Agent is given birth to, Ca (OH) occurs in regenerative process2Excessive situation, Ca (OH) 2 enter with doctor solution
After desulfurizing tower with SO2Reaction can also generate CaSO3* 1/2H2O, equally can in desulfurization crystallization inside tower,
Block pipeline；
The desulfurization product of magnesium method flue gas desulphurization is MySO4Solution.Desulfurization product post processing is difficult, row
It is put into natural environment and pollution is produced to environment；
The product of the ammonia process of desulfurization easily generates aerosol in neat stress and discharged with chimney, in cigarette
Chimney is formed about a large amount of white hazes.
The content of the invention
In view of technology above shortcomings, the present invention provide a kind of flue gas integrated desulfurization at present
Denitrating system and method, the present invention sodalime double alkali method is combined on the basis of original magnesium processes desulfurization the advantages of,
Solve the shortcomings that magnesium processes desulfurization product is difficult to handle, desulfurization waste liquor is carried out at regeneration using the second alkali
Reason, desulfurizing agent is replaced, the product of the inventive method is (NH4)2SO4, Fertilizer application can be used as.
The present invention's adopts the following technical scheme that：
A kind of flue gas integration desulfurization denitration system, including pre- system for desulfuration and denitration, rear desulphurization denitration
System and recycling system, it is described after system for desulfuration and denitration respectively with the pre- system for desulfuration and denitration and
Recycling system is connected；The pre- system for desulfuration and denitration includes serum producing system, ozone filling system
System and pre- denitration desulfurization cooler, the pre- denitration desulfurization cooler respectively with the serum producing system and
Ozone loading system is connected；System for desulfuration and denitration is provided with spraying layer and spiral board, the spraying layer after described
It is connected with the spiral board.
As the preferred technical solution of the present invention, the rear system for desulfuration and denitration is additionally provided with demister,
Demisting plate cleaning spray is provided between the demister and the spraying layer and import is strengthened in hydrogen peroxide denitration.
As the preferred technical solution of the present invention, scrubbing tower is provided with above the rear system for desulfuration and denitration,
The scrubbing tower is connected with chimney.
As the preferred technical solution of the present invention, the recycling system be provided with separator,
Evaporator and residual filter, the particle separator are connected with the evaporator.
A kind of method of flue gas integration desulfurization denitration, comprises the following steps：
Flue gas is cooled and carries out pre- desulphurization denitration processing；
Desulphurization denitration is handled and in flue gas after being carried out to the flue gas for carrying out pre- desulphurization denitration processing
Element sulphur and nitre element are recycled.
It is described that flue gas is cooled and carries out pre- desulfurization as the preferred technical solution of the present invention
The step of denitration process, includes：
Cooling processing is carried out to flue gas；
The flue gas for the processing that cools is mixed with ozone.
As the preferred technical solution of the present invention, the described pair of flue gas for carrying out pre- desulphurization denitration processing
The step that desulphurization denitration is handled and recycled to the element sulphur in flue gas and nitre element after progress
Suddenly include：
Desulphurization denitration is carried out to flue gas by magnesium hydroxide and oxidation additive and carries flue gas secretly
Droplet traps；
By magnesia slurry preparation system, it is sent into after being made into slurries in desulfurizing tower, with heat
Flue gas fully contacts and the nitrogen oxides of sulfur dioxide and high-valence state is absorbed；
After magnesium hydroxide solution sulfur dioxide absorption and nitrogen oxides, magnesium sulfite is converted into
It is converted into magnesium sulfate and magnesium nitrate.
The present invention relates to a kind of flue gas integration desulfurization denitration system to have advantages below：1st, it is our
Method advantage desulfuration efficiency is high, desulphurization plant small volume；2nd, without fouling, clogging；3rd, smokeless
Band ammonia and other secondary pollution problems.
Brief description of the drawings
Technical scheme in order to illustrate the embodiments of the present invention more clearly, below will be to embodiment
In the required accompanying drawing used be briefly described, it should be apparent that, drawings in the following description
Only some embodiments of the present invention, for those of ordinary skill in the art, do not paying
On the premise of going out creative work, other accompanying drawings can also be obtained according to these accompanying drawings.
Fig. 1 is the structural representation of the present invention.
Embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, to the technical side in the embodiment of the present invention
Case is clearly and completely described, it is clear that described embodiment is only the present invention one
Divide embodiment, rather than whole embodiments.It is general based on the embodiment in the present invention, this area
The every other embodiment that logical technical staff is obtained under the premise of creative work is not made,
Belong to the scope of protection of the invention.
As shown in figure 1, the present invention provides a kind of flue gas integration desulfurization denitration system, including it is pre- de-
Sulphur denitrating system, rear system for desulfuration and denitration and recycling system, rear system for desulfuration and denitration respectively with advance
System for desulfuration and denitration is connected with recycling system；Pre- system for desulfuration and denitration include serum producing system 1,
Ozone loading system 2 and pre- denitration desulfurization cooler 3, pre- denitration desulfurization cooler 3 respectively with slurries system
Standby system 1 is connected with ozone loading system 2；System for desulfuration and denitration is provided with spraying layer 4 and spiral board 5 afterwards,
Spraying layer 4 is connected with spiral board 5.Wherein serum producing system 1 is used to prepare magnesia, is made into
It is sent into desulfurizing tower, is fully contacted with heat smoke and to sulfur dioxide and the nitrogen oxides of high-valence state after slurries
Absorbed, reach desulfurization purpose；Caused by ozone loading system 2 ozone injection flue gas and quickly with
Flue gas mixes, and the NO in flue gas will form the NO that can be absorbed by downstream doctor solution rapidly and ozone reaction2
Contour oxides；Pre- denitration desulfurization cooler 3 carries out cooling processing to flue gas, while by flue gas
Most of sulfur dioxide and NO2Removing；Spraying layer 4 and spiral board 5, to sulfur dioxide, nitrogen oxides
But while continuing to absorb, having can be concentrated by evaporation by heat smoke, the sulfuric acid in final doctor solution
Ammonium, ammonium nitrate reach higher concentration, are advantageous to its follow-up circular regeneration recovery.
In the present invention, rear system for desulfuration and denitration is additionally provided with demister 6, demister 6 and spraying layer
Demisting plate cleaning spray 7 is provided between 4 and import 8 is strengthened in hydrogen peroxide denitration.
In the present invention, scrubbing tower 9 is provided with above rear system for desulfuration and denitration, scrubbing tower 9 is connected with cigarette
Chimney 10.
In the present invention, recycling system is provided with particle separator 11, evaporator 12 and residual
Slag filter 13, particle separator 11 are connected with evaporator 12, and wherein evaporator 12 is preferably sulphur
Ammonium evaporator.
The another side of the present invention, a kind of method of flue gas integration desulfurization denitration, comprises the following steps：
Step S1：Flue gas is cooled and carries out pre- desulphurization denitration processing, wherein specifically including step
S1a：Cooling processing, step S1b are carried out to flue gas：The flue gas for the processing that cools is mixed with ozone.Tool
Body is；The flue gas come out from coking furnace, after waste heat boiler cools, proceed by oxidation and denitration processing.
Using appropriate mixing arrangement, ozone caused by ozone generator is directly injected into flue gas and quickly and cigarette
Gas mixes, and the NO in flue gas will form the NO that can be absorbed by downstream doctor solution rapidly and ozone reaction2
Contour oxides.The pre- desulfurization section that flue gas enters before desulfurizing tower afterwards, is carried out at cooling to flue gas
Reason, while by the most of sulfur dioxide and NO in flue gas2Removing.At the same time, heat smoke is also to de-
Sulphur liquid has preferable concentrate to act on.
Step S2：Desulphurization denitration is handled and to flue gas after being carried out to the flue gas for carrying out pre- desulphurization denitration processing
In element sulphur and nitre element recycled, including step S2a：Pass through magnesium hydroxide and oxygen
Change the droplet that additive carries out desulphurization denitration to flue gas and carries flue gas secretly to trap；Step S2b：It is logical
Peromag serum producing system, it is sent into desulfurizing tower after being made into slurries, is fully contacted with heat smoke
And the nitrogen oxides of sulfur dioxide and high-valence state is absorbed；Step S2c：Pass through magnesium hydroxide solution
After sulfur dioxide absorption and nitrogen oxides, it is converted into magnesium sulfite and is converted into magnesium sulfate and magnesium nitrate, specifically
To enter main body desulphurization denitration tower after the flue gas of pre- desulphurization denitration, in magnesium hydroxide and small amounts
The effect of additive (hydrogen peroxide), continue desulphurization denitration, while the droplet of flue gas entrainment is trapped
Get off.A small amount of desulphurization denitration accessory substance is also oxidized simultaneously, is converted into ammonium sulfate and ammonium nitrate.Afterwards
Discharge standard can be fully achieved in flue gas, and has chimney to be discharged.
In the present invention, desulfurization passes through oxidation by the use of magnesia (magnesium hydroxide) as the first desulfurizing agent
Magnesium serum producing system, it is sent into desulfurizing tower after being made into slurries, is fully contacted and to two with heat smoke
Sulfur oxide and the nitrogen oxides of high-valence state are absorbed, and reach desulfurization purpose.Magnesium hydroxide solution absorbs two
After after sulfur oxide and nitrogen oxides, magnesium sulfite is converted into, and (in absorb the bottom of the tower after air oxidation
Carry out) magnesium sulfate and magnesium nitrate are converted into, after doctor solution circulates certain time in main desulfurizing tower, it will make
For the spray liquid of pre- desulfurizing tower, while continuing to absorb to sulfur dioxide, nitrogen oxides, there is energy
It is concentrated by evaporation by heat smoke, but the ammonium sulfate, ammonium nitrate in final doctor solution reach higher concentration,
Be advantageous to its follow-up circular regeneration recovery.
In the present invention, it is anti-to be progressively sent to regeneration for resulting 10-20% magnesium sulfate/magnesium nitrate solution
Answer tower.Liquefied ammonia (or ammoniacal liquor) with one other Adlerika outside tower then by premixing outside regenerator
(have not enough time to react) after conjunction, be sent into the regenerator with agitator.Ammonia in regenerator with magnesium sulfate
Solution is sufficiently mixed, and is reacted.When magnesium sulfate fully reacts in regenerator, resulting hydroxide
After the concentration of slurry of magnesium (or basic magnesium carbonate) reaches certain level, the blowing of regenerator bottom can be opened
Valve, the mixed liquor containing ammonium sulfate and magnesium hydrate precipitate enter separation of solid and liquid tank.Magnesium hydrate precipitate is again
It is secondary to be utilized as desulfurizing agent.Ammonium sulfate carries out subsequent concentration processing and is used as Fertilizer application.
In the present invention, specific course of reaction is：
(1) desulphurization reaction:
MgO+SO2+xH2O→MgSO3↓
Mg(OH)2+SO2→MgSO3↓+H2O
MgSO3+SO2+H2O→Mg(HSO3)2
(2) oxidation reaction：
Mg(HSO3)2+O2→MgSO4+H2SO4
MgSO3+1/2O2→MgSO4
(3) regenerative response
MgSO4+2NH3·H2O→Mg(OH)2↓+(NH4)2SO4
MgSO4+2NH4·HCO3→MgCO3↓+(NH4)2SO4+CO2+H2O
The invention has the advantages that：
(1) this method advantage desulfuration efficiency height, desulphurization plant small volume, relative to lime/lime stone
For doctor treatment, magnesium hydroxide slurry and SO2 affinity are strong, and desulphurization reaction speed (is mainly bullied soon
Membrane mass transfer controls), thus less liquid-gas ratio is can use, required desulphurization plant volume is also smaller, takes off
Sulphur efficiency operates steadily up to more than 95%.This technology combines work using high efficiency spray with multi-functional column plate
Skill, equipment volume and liquid-gas ratio is set further to reduce.
(2) without fouling, clogging, in sweetening process, the desulfurizing byproduct formed is (such as Asia
Magnesium sulfate or magnesium bisulfite) solubility it is higher, it is less scaling.Even if caused by misoperation temporarily
Scale formation, it can also be eliminated by the method for the pH value for reducing doctor solution.In addition, magnesium hydroxide
And its chemical property of desulfurization product is gentleer, any excitant or corrosivity will not be produced.
(3) smokeless band ammonia and other secondary pollution problems, in direct ammonia desulfurizing process, in order to
Ensureing certain desulfurization degree, the ammonia density in solution needs to maintain higher level, but now in heat smoke
Under effect, the ammonia in solution is easy to be volatized into flue gas, not only causes the loss of raw material, and causes
New pollution, easily cause downstream flue and inner wall of stack scab, discharge flue gas and contain aerosol and thorn
Swash property ammonia taste etc..Precooling is carried out even if to flue gas and except tower flue gas washing is also difficult to thoroughly solve above-mentioned ask
Topic.
(4) exhaust gas temperature can be controlled in higher level, and exhaust gas temperature is too low can be to the anti-corrosion of downstream flue
It is required that, the high altitude discharge feature of the life-span of air-introduced machine and flue gas can make a big impact.Due to magnesium hydroxide
Non-volatility component in slurries, and still have preferable absorbability to sulfur dioxide at relatively high temperatures, because
This flue gas is before desulfurizing tower is entered without cooling in advance.It is smaller plus the liquid-gas ratio needed for sweetening process, so
Heat loss of the flue gas in absorption tower is relatively low, therefore flue gas can still be protected by the flue gas after desulfurizing tower
Hold higher temperature；And the ammonia process of desulfurization then contrast, cause a series of problems to downstream smoke evacuation.
(5) recycling of desulfurization product is convenient, technical matters has flexibility, with common lime/
Limestone desulfurization method or traditional hydroxide magnesium processes are compared, and the final desulfurization product ammonium sulfate obtained by this technology can
As Fertilizer application, there is preferable economic benefit.The adaptability of this technology technique is preferable, in magnesium hydroxide
Cyclic process in, the magnesium hydroxide conduct of high added value according to market needs, can be also extracted from technique
Functional material (is used as fire-retardant for plastic).
(6) by being added in gas approach, ozone machine hydrogen peroxide can be realized while desulfurization takes off while flue gas
Nitre.
The foregoing is only a specific embodiment of the invention, but protection scope of the present invention is simultaneously
This is not limited to, any those skilled in the art is in technology model disclosed by the invention
In enclosing, the change or replacement that can be readily occurred in, it should all be included within the scope of the present invention.
Therefore, protection scope of the present invention should be based on the protection scope of the described claims.
Claims (7)
- A kind of 1. flue gas integration desulfurization denitration system, it is characterised in that including pre- system for desulfuration and denitration, System for desulfuration and denitration and recycling system afterwards, it is described after system for desulfuration and denitration respectively with the pre- desulfurization Denitrating system is connected with recycling system；The pre- system for desulfuration and denitration include serum producing system, Ozone loading system and pre- denitration desulfurization cooler, the pre- denitration desulfurization cooler respectively with the slurries Preparation system is connected with ozone loading system；System for desulfuration and denitration is provided with spraying layer and spiral board after described, The spraying layer is connected with the spiral board.
- A kind of 2. flue gas integration desulfurization denitration system according to claim 1, it is characterised in that System for desulfuration and denitration is additionally provided with demister after described, and demisting is provided between the demister and the spraying layer Import is strengthened in plate cleaning spray and hydrogen peroxide denitration.
- A kind of 3. flue gas integration desulfurization denitration system according to claim 1, it is characterised in that Scrubbing tower is provided with above system for desulfuration and denitration after described, the scrubbing tower is connected with chimney.
- 4. according to a kind of any described flue gas integration desulfurization denitration systems of claim 1-3, its feature It is, the recycling system is provided with separator, evaporator and residual filter, the separation Device is connected with the evaporator.
- A kind of 5. method of flue gas integration desulfurization denitration, it is characterised in that comprise the following steps：Flue gas is cooled and carries out pre- desulphurization denitration processing；Desulphurization denitration is handled and to the element sulphur in flue gas after being carried out to the flue gas for carrying out pre- desulphurization denitration processing Recycled with nitre element.
- A kind of 6. flue gas integration desulfurization denitration method according to claim 5, it is characterised in that It is described that flue gas is cooled and included the step of carrying out pre- desulphurization denitration processing：Cooling processing is carried out to flue gas；The flue gas for the processing that cools is mixed with ozone.
- A kind of 7. flue gas integration desulfurization denitration method according to claim 5, it is characterised in that Desulphurization denitration is handled and to the element sulphur in flue gas after the described pair of flue gas for carrying out pre- desulphurization denitration processing is carried out The step of being recycled with nitrogen includes：The droplet for carrying out desulphurization denitration by magnesium hydroxide and oxidation additive to flue gas and carrying flue gas secretly is caught Collection gets off；By magnesia slurry preparation system, it is sent into desulfurizing tower after being made into slurries, is filled with heat smoke Tap is touched and the nitrogen oxides of sulfur dioxide and high-valence state is absorbed；After magnesium hydroxide solution sulfur dioxide absorption and nitrogen oxides, it is oxidized to be converted into magnesium sulfite It is converted into magnesium sulfate and magnesium nitrate.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108261905A (en) * | 2018-04-08 | 2018-07-10 | 北京美斯顿科技开发有限公司 | A kind of denitration integrated device and method |
| CN109179485A (en) * | 2018-11-13 | 2019-01-11 | 常宁市华兴冶化实业有限责任公司 | A method of it emulsifying zinc oxide desulfurization and prepares zinc sulfate |
| CN109621662A (en) * | 2018-12-18 | 2019-04-16 | 河南科技大学 | A kind of equipment for denitrifying flue gas for coal-burning boiler |
| CN110090550A (en) * | 2019-04-17 | 2019-08-06 | 昆明理工大学 | A kind of coke oven flue gas sulfur method thermally decomposed in advance based on magnesium salts |
-
2016
- 2016-05-24 CN CN201610348919.9A patent/CN107413180A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108261905A (en) * | 2018-04-08 | 2018-07-10 | 北京美斯顿科技开发有限公司 | A kind of denitration integrated device and method |
| CN109179485A (en) * | 2018-11-13 | 2019-01-11 | 常宁市华兴冶化实业有限责任公司 | A method of it emulsifying zinc oxide desulfurization and prepares zinc sulfate |
| CN109621662A (en) * | 2018-12-18 | 2019-04-16 | 河南科技大学 | A kind of equipment for denitrifying flue gas for coal-burning boiler |
| CN110090550A (en) * | 2019-04-17 | 2019-08-06 | 昆明理工大学 | A kind of coke oven flue gas sulfur method thermally decomposed in advance based on magnesium salts |
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| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20171201 |