CN107335331A - A kind of sulfur method of coke oven tail gas - Google Patents
A kind of sulfur method of coke oven tail gas Download PDFInfo
- Publication number
- CN107335331A CN107335331A CN201710780801.8A CN201710780801A CN107335331A CN 107335331 A CN107335331 A CN 107335331A CN 201710780801 A CN201710780801 A CN 201710780801A CN 107335331 A CN107335331 A CN 107335331A
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- Prior art keywords
- tail gas
- desulfurizing tower
- coke oven
- oven tail
- ammonium
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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
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/77—Liquid phase processes
- B01D53/79—Injecting reactants
-
- 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
- B01D53/501—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound
- B01D53/502—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound characterised by a specific solution or suspension
-
- 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
- B01D53/501—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound
- B01D53/504—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound characterised by a specific device
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/24—Sulfates of ammonium
- C01C1/245—Preparation from compounds containing nitrogen and sulfur
- C01C1/246—Preparation from compounds containing nitrogen and sulfur from sulfur-containing ammonium compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/20—Reductants
- B01D2251/206—Ammonium compounds
Abstract
The invention belongs to tail gas desulfurization technical field, is related to a kind of sulfur method of coke oven tail gas.The sulfur method of described coke oven tail gas comprises the following steps：From being passed through described coke oven tail gas positioned at the bottom of desulfurizing tower bottom spraying layer 3, and spray into ammonium sulfite solution from the top uniform atomizing positioned at described spraying layer 3, so that coke oven tail gas reacts with ammonium sulfite solution counter current contacting, desulfurizing tower bottom of towe efflux returns the pH value that desulfurizing tower circulated and passed through the ammoniacal liquor added from desulfurizing tower bottom of towe and adjust whole circulating system through circulating pump.With the present invention method desulfurization is carried out to coke oven tail gas, can more existing coke oven tail gas sulfur method significantly improve desulfuration efficiency.
Description
Technical field
The invention belongs to tail gas desulfurization technical field, is related to a kind of sulfur method of coke oven tail gas.
Background technology
Contain sulfur dioxide, sulfur trioxide and various dust-like materials in coke oven tail gas, being directly discharged into air can be to air
Environment causes seriously to pollute.Therefore, coke oven tail gas can just be discharged into air after having to pass through processing, especially desulfurization process.Ammonia process
Desulfurization is a kind of important method of coke oven tail gas desulfurization, and its principle is in desulfurizing tower, utilizes the reaction of ammoniacal liquor and sulfur dioxide
Or the reaction of ammoniacal liquor and ammonium sulfite removes the sulfur dioxide in coke oven tail gas.The ammonium bisulfite of said process generation may be used also
Further being passed through AMMONIA TREATMENT makes it be converted into ammonium sulfite, and oxidation processes also can be further carried out to ammonium sulfite with by its turn
Turn to ammonium sulfate.The chemical reaction that each process is related to above is as follows：
SO2+2NH3+H2O=(NH4)2SO3
SO2+(NH4)2SO3+H2O=2NH4HSO3
NH3+NH4HSO3=(NH4)2SO3
SO3+H2O=H2SO4
H2SO4+2NH3·H2O=(NH4)2SO4+2H2O
2(NH4)2SO3+O2=2 (NH4)2SO4
It is using subject matter existing for the existing ammonia-process desulfurization technique of as above principle：Due in desulfurizing tower ammoniacal liquor it is logical
Enter and be distributed not do to optimize, so causing desulfuration efficiency not high；And either still exist in desulfurizing tower internal oxidition ammonium sulfite
Desulfurizing tower external oxidation ammonium sulfite, the efficiency that ammonium sulfite is converted into ammonium sulfate are all not high enough.
The content of the invention
It is an object of the invention to provide a kind of sulfur method of coke oven tail gas, the more existing coke oven tail gas desulfurization side of this method
Method can significantly improve desulfuration efficiency.
In order to achieve this, in the embodiment on basis, the present invention provides a kind of sulfur method of coke oven tail gas, and it is wrapped
Include following steps：
(1) from being passed through described coke oven tail gas positioned at the bottom of desulfurizing tower bottom spraying layer, and from positioned at described spray
The top uniform atomizing of layer sprays into ammonium sulfite solution, so that coke oven tail gas occurs instead with ammonium sulfite solution counter current contacting
Should, desulfurizing tower bottom of towe efflux through circulating pump return desulfurizing tower circulated and pass through from desulfurizing tower bottom of towe add ammoniacal liquor adjust it is whole
The pH value of individual circulating system.
In a preferred embodiment, the present invention provides a kind of sulfur method of coke oven tail gas, wherein described is de-
Sulphur tower is spray column, by the way of hollow-spraying-tower.
In a preferred embodiment, the present invention provides a kind of sulfur method of coke oven tail gas, wherein being passed through described
The mass percent concentration of ammonium sulfite solution of desulfurizing tower be 15-25%.
In a preferred embodiment, the present invention provides a kind of sulfur method of coke oven tail gas, wherein being passed through described
The mass percent concentration of ammoniacal liquor of desulfurizing tower be 5-20%.
In a preferred embodiment, the present invention provides a kind of sulfur method of coke oven tail gas, wherein described spray
The height of drenching layer is 500-800mm.
A kind of in a preferred embodiment, sulfur method of coke oven tail gas of present invention offer, wherein coke oven tail gas,
The volume flow ratio of ammonium sulfite solution is 1:400.
In a preferred embodiment, the present invention provides a kind of sulfur method of coke oven tail gas, wherein described is de-
Sulphur tower is additionally provided with cleaning layer on the top of spraying layer, to remove a small amount of micron order ammonium bisulfite in tail gas, ammonium sulfate, small
Solid particle and free ammonia, effectively solve the problems, such as aerosol, the escaping of ammonia and tail gas trailing whites.
In a preferred embodiment, the present invention provides a kind of sulfur method of coke oven tail gas, wherein described is de-
Sulphur tower is additionally provided with demisting layer on the top of spraying layer, and described demisting layer is removed in tail gas by the demister being disposed therein
The droplet of entrainment.
In a preferred embodiment, the present invention provides a kind of sulfur method of coke oven tail gas, wherein described removes
Mist layer is further provided with technique water washing device above demister, and the demister for cleaning described prevents from blocking, and
The ammonia carried secretly in tail gas is absorbed again, ammonia content in tail gas is discharged to reduce.
In a preferred embodiment, the present invention provides a kind of sulfur method of coke oven tail gas, wherein described is de-
Sulphur tower is disposed with cleaning layer and demisting layer, the described demisting layer processing of described tail gas warp on the top of described spraying layer
Arranged afterwards from the top of described desulfurizing tower to air.
In a preferred embodiment, the present invention provides a kind of sulfur method of coke oven tail gas, wherein described side
Described coke oven tail gas is first passed to pre- desulfurizing tower by method before step (1), the described coke oven tail gas in described pre- desulfurizing tower
Ammonium sulfite solution with spraying into described pre- desulfurizing tower reacts to remove the sulfur dioxide in partial tail gas.
In a preferred embodiment, the present invention provides a kind of sulfur method of coke oven tail gas, wherein being passed through described
The mass percent concentration of ammonium sulfite solution of pre- desulfurizing tower be 3-5%.
In a preferred embodiment, the present invention provides a kind of sulfur method of coke oven tail gas, wherein described is pre-
Coke oven tail gas, the volume flow ratio of ammonium sulfite solution are 1 in desulfurizing tower:400.
In a preferred embodiment, the present invention provides a kind of sulfur method of coke oven tail gas, wherein described side
Method further comprises the steps after step (1)：
(2) the desulfurizing tower bottom of towe efflux described in returns desulfurizing tower through circulating pump, and when warp, repeatedly circulation makes described desulfurization
When the gross mass percent concentration of ammonium sulfite and ammonium bisulfite in tower bottom of towe efflux reaches 20%, by described desulfurization
Tower bottom of towe efflux is pumped to static mixer through circulation, is adjusted in static mixer by controlling the addition of ammoniacal liquor mixed
The pH value of solution is closed, so as to which the ammonium bisulfite in desulfurizing tower bottom of towe efflux is converted into ammonium sulfite.
In a preferred embodiment, the present invention provides a kind of sulfur method of coke oven tail gas, wherein in step (2)
The mass percent concentration for being passed through ammoniacal liquor is 5-20%.
In a preferred embodiment, the present invention provides a kind of sulfur method of coke oven tail gas, wherein in step (2)
The mixing ratio of bottom of towe efflux and ammoniacal liquor is 0.5-1% in described static mixer:1.
In a preferred embodiment, the present invention provides a kind of sulfur method of coke oven tail gas, wherein described side
Method further comprises the steps after step (2)：.
(3) solution after step (2) is converted is sent into oxidation trough and aoxidized, so as to be sulfuric acid by sulfite oxidation
Ammonium.
In a preferred embodiment, the present invention provides a kind of sulfur method of coke oven tail gas, wherein in step (3)
The concentration of volume percent of oxygen is 15-21%.
In a preferred embodiment, the present invention provides a kind of sulfur method of coke oven tail gas, wherein in step (3)
The mixing mol ratio of solution ammonium sulfite and oxygen after described conversion is 2-5.
In a preferred embodiment, the present invention provides a kind of sulfur method of coke oven tail gas, wherein described oxygen
Change groove and share two-stage, so that described ammonium sulfite point two-stage is aoxidized.
The technical effects of the invention are that the sulfur method of the coke oven tail gas using the present invention, can more existing coke oven tail
Desulfurization method significantly improves desulfuration efficiency, and the ammonium sulfite that desulfurization is generated more completely is converted into ammonium sulfate；And de-
Also the escaping of ammonia caused by circulating pumping action lower part Ammonia valatilization can be effectively prevented in sulphur tower sweetening process, and prevents desulfurization from generating
Bisulfite ammonia aerosols with flue gas from tower top discharge, cause flue gas trailing whites.
Brief description of the drawings
Fig. 1 is a kind of installation drawing of the sulfur method of coke oven tail gas of the present invention.
Embodiment
The embodiment of the present invention is further illustrated below in conjunction with accompanying drawing.
Embodiment 1：The desulfurizing tower processing of coke oven tail gas
Desulfurizing tower 2 in Fig. 1 is divided into spraying layer 3, cleaning layer 4,5 three layers of demisting layer, three layers of height point from bottom to top
Wei not 14m, 0.5m, 6m.
Coke oven tail gas (tail gas caused by coke oven combustion, wherein titanium dioxide are passed through in the bottom of the bottom spraying layer 3 of desulfurizing tower 2
Sulfur content 500mg/Nm3), the top uniform atomizing of spraying layer 3 sprays into ammonium sulfite solution, so that coke oven tail gas and sulfurous acid
Ammonium salt solution counter current contacting reacts.SO in coke oven tail gas2Deng sour gas and ammonium sulfite solution reaction generation sulfurous acid
Hydrogen ammonium enters bottom of towe efflux, and the dust and ammonia carried secretly in coke oven tail gas are also washed down.The bottom of towe efflux of desulfurizing tower 2 is through following
Ring pump is returned desulfurizing tower 2 and circulated and through the pH value of the whole circulating system of ammoniacal liquor regulation from the addition of the bottom of towe of desulfurizing tower 2.Circulation
Desulphurization reaction is carried out until the gross mass percent concentration of the ammonium sulfite and ammonium bisulfite in the bottom of towe efflux of desulfurizing tower 2 reaches
It is measured to sampling when more than 20%.
Coke oven tail gas in spraying layer 3 after desulfurization, by flue enter desulfurizing tower rapid ball cleaning layer 4 (built-in many-sided ball,
By increasing the dust in gas liquid interfacial area removal flue gas), to remove a small amount of micron order ammonium bisulfite, ammonium sulfate in tail gas
With minute solid particles and free ammonia, effectively solve the problems, such as aerosol, the escaping of ammonia and tail gas trailing whites.
Tail gas is upwardly into demisting layer 5 after the cleaning of cleaning layer 4, the droplet carried secretly in tail gas is removed, on demister top
Provided with technique water washing device, demister, pre- anti-clogging can be not only cleaned, and the ammonia that carried secretly in tail gas can be inhaled again
Receive, reduce ammonia content in discharge tail gas.
Coke oven tail gas is arranged to air after the processing of demisting layer 5 from the top of desulfurizing tower.
The ammoniacal liquor of above-mentioned addition desulfurizing tower is used for the pH value for controlling circulation fluid.Ammonia will not be directly entered gas phase, therefore tail gas goes out
The ammonia content of mouth is very low.
Table 1 below is the treatment effect of each reactant desulfurizing tower under various concentrations, flow.
The treatment effect of the reactant of table 1 desulfurizing tower under various concentrations, flow
From the result of table 1, by desulfurization, washing, demisting, coke oven tail gas outlet SO2Less than 30mg/Nm3, dust (solid
Thing) it is less than 15mg/Nm3, deliver to heat-pipe heat exchanger and exchanged heat with waste-heat recovery device flue gas, lifted temperature to 130 DEG C of left sides
The right side, former smoke stack emission is delivered to ensure that chimney is hot standby.
Embodiment 2：The pre- desulfurization process of coke oven tail gas
Coke oven tail gas is first passed through pre- desulfurizing tower 1, with being pushed up from pre- desulfurizing tower 1 before the desulfurizing tower of embodiment 1 is passed through from bottom
The ammonium sulfite solution adverse current that portion is passed through reacts, and pre- desulfurization tower height degree is (27m).From Jiao derived from the pre- top of desulfurizing tower 1
Furnace exhaust gas is further passed through desulfurizing tower and carries out desulfurization.Table 2 below is the pre- desulfurized effect of coke oven tail gas under the conditions of different disposal.
The pre- desulfurized effect of coke oven tail gas under the conditions of the different disposal of table 2
Embodiment 3：The conversion of desulfurizing tower bottom of towe efflux and oxidation processes
The gross mass percent concentration of ammonium sulfite and ammonium bisulfite in the desulfurizing tower bottom of towe efflux of embodiment 1 reaches
During to 20%, partial desulfurization tower bottom of towe efflux is pumped to static mixer through circulation.Pass through control in static mixer
The addition of ammoniacal liquor adjusts the pH value of mixed solution, so as to which the ammonium bisulfite in desulfurizing tower bottom of towe efflux is converted into Asia
Ammonium sulfate.Solution after conversion is successively sent into two-stage oxidation groove and aoxidized, so as to be ammonium sulfate by sulfite oxidation.
Test result indicates that by the oxidation of two-stage oxidation groove, the oxygenation efficiency of ammonium sulfite reaches more than 95%, aoxidized
Ammonium sulfate concentration afterwards is between 280~350g/L.
Desulfurizing tower internal oxidition and desulfurizing tower external oxidation are the conventional oxidation technologies of the ammonia process of desulfurization, outside desulfurizing tower of the invention
Oxidation is as follows with the Contrast on effect of the desulfurizing tower internal oxidition of prior art：
A, liquid-gas ratio：The larger liquid-gas ratio of tower internal oxidition requirements of process reaches certain desulfuration efficiency, general liquid-gas ratio
Need 2.5:1, even if being so also unable to reach higher desulfuration efficiency.And the tower external oxidation flow of the present invention is flowed out due to bottom of towe
Liquid is to absorb SO2Active ingredient, therefore liquid-gas ratio maintains 1.2~2.0:1 or so can reaches higher desulfuration efficiency.
B, power consumption：Due to the liquid-gas ratio that tower internal oxidition requirements of process is larger, so circulation solution amount is larger, circulating pump
Power consumption it is also higher, and need to set the oxidation fan of relatively high power, therefore power consumption is significantly larger than tower external oxidation flow.
C, the stability of system operation：The requirements of process of tower internal oxidition controls the ammonium sulfate concentrations of solution in tower higher
Operated in concentration range, ammonia sulfate crystal is easily separated out in tower, and ammonia sulfate crystal is more hard, to solution recycle system
Circulating pump, liquid distribution trough, shower nozzle and desulfurizing tower internal structure can cause larger abrasion and greatly shorten service life, sternly
Ghost image rings the long-period stable operation of desulphurization system.
D, oxidation efficiency：The tower external oxidation of the present invention uses twin-stage regenerating oxidation method, using liquid at high speed stream in injector
Oxygen is sucked rear oxidation ammonium sulfite by the dynamic negative pressure formed, and the oxygenation efficiency of sulfite oxidation into ammonium sulfate is high, better than tower
Interior air aeration oxidation, the ammonium sulfate product sulfite ammonium component content after oxidation are very low so that the ammonium sulfate production of recovery
The product rate of recovery is high and quality is pure；And without using the larger oxidation fan of power, reduce power consumption and noise；It is also greatly reduced
The internal circulating load of doctor solution, so as to also reduce power consumption.
Claims (10)
1. a kind of sulfur method of coke oven tail gas, it is characterised in that comprise the following steps：
(1) it is passed through coke oven tail gas from positioned at the bottom of desulfurizing tower bottom spraying layer, and from equal positioned at the top of described spraying layer
Even atomization sprays into ammonium sulfite solution, so that coke oven tail gas reacts with ammonium sulfite solution counter current contacting, desulfurizing tower tower
Bottom efflux, which through circulating pump returns desulfurizing tower and circulated and pass through the ammoniacal liquor added from desulfurizing tower bottom of towe, adjusts whole circulating system
PH value.
2. according to the method for claim 1, it is characterised in that：The height of described spraying layer is 500-800mm.
3. according to the method for claim 1, it is characterised in that：Described desulfurizing tower is additionally provided with clearly on the top of spraying layer
Layer is washed, to remove a small amount of micron order ammonium bisulfite, ammonium sulfate, minute solid particles and free ammonia in tail gas.
4. according to the method for claim 1, it is characterised in that：Described desulfurizing tower is additionally provided with the top of spraying layer and removed
Mist layer, described demisting layer remove the droplet carried secretly in tail gas by the demister being disposed therein.
5. according to the method for claim 4, it is characterised in that：Described demisting layer is further set in the top of demister
There is technique water washing device, the demister for cleaning described prevents from blocking, and the ammonia to being carried secretly in tail gas absorbs again.
6. according to the method described in claim 3-5 any one, it is characterised in that：Described desulfurizing tower is in described spraying layer
Top be disposed with cleaning layer and demisting layer, described tail gas is after described demisting layer processing from described desulfurizing tower
Arrange to air at top.
7. according to the method for claim 1, it is characterised in that described method is before step (1) first by described coke oven
Tail gas passes to pre- desulfurizing tower, sulfurous acid of the described coke oven tail gas with spraying into described pre- desulfurizing tower in described pre- desulfurizing tower
Ammonium salt solution reacts to remove the sulfur dioxide in partial tail gas.
8. according to the method for claim 1, it is characterised in that described method further comprises as follows after step (1)
The step of：
(2) the desulfurizing tower bottom of towe efflux described in returns desulfurizing tower through circulating pump, and when warp, repeatedly circulation makes described desulfurizing tower tower
When the gross mass percent concentration of ammonium sulfite and ammonium bisulfite in the efflux of bottom reaches 20%, by described desulfurizing tower tower
Bottom efflux is pumped to static mixer through circulation, and it is molten to adjust mixing by controlling the addition of ammoniacal liquor in static mixer
The pH value of liquid, so as to which the ammonium bisulfite in desulfurizing tower bottom of towe efflux is converted into ammonium sulfite.
9. according to the method for claim 8, it is characterised in that：Described method further comprises as follows after step (2)
The step of：
(3) solution after step (2) is converted is sent into oxidation trough and aoxidized, so as to be ammonium sulfate by sulfite oxidation.
10. according to the method for claim 9, it is characterised in that：Described oxidation trough shares two-stage, so that described Asia
Ammonium sulfate point two-stage is aoxidized.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710780801.8A CN107335331A (en) | 2017-09-01 | 2017-09-01 | A kind of sulfur method of coke oven tail gas |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710780801.8A CN107335331A (en) | 2017-09-01 | 2017-09-01 | A kind of sulfur method of coke oven tail gas |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107715679A (en) * | 2017-11-22 | 2018-02-23 | 朗盈（成都）化工科技有限公司 | A kind of flue gas desulfurization device |
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| WO2001027027A1 (en) * | 1999-10-12 | 2001-04-19 | Hera, Llc | METHOD AND APPARATUS FOR REDUCING 'AMMONIA SLIP' IN SCR AND/OR SNCR NOx REMOVAL APPLICATIONS |
| CN2568291Y (en) * | 2002-09-09 | 2003-08-27 | 华东理工大学 | Multifunctional desulfurizer |
| CN104998530A (en) * | 2015-03-31 | 2015-10-28 | 武汉宇青环保科技有限公司 | Sulfuric acid tail gas desulphurization device and method |
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2017
- 2017-09-01 CN CN201710780801.8A patent/CN107335331A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001027027A1 (en) * | 1999-10-12 | 2001-04-19 | Hera, Llc | METHOD AND APPARATUS FOR REDUCING 'AMMONIA SLIP' IN SCR AND/OR SNCR NOx REMOVAL APPLICATIONS |
| CN2568291Y (en) * | 2002-09-09 | 2003-08-27 | 华东理工大学 | Multifunctional desulfurizer |
| CN104998530A (en) * | 2015-03-31 | 2015-10-28 | 武汉宇青环保科技有限公司 | Sulfuric acid tail gas desulphurization device and method |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107715679A (en) * | 2017-11-22 | 2018-02-23 | 朗盈（成都）化工科技有限公司 | A kind of flue gas desulfurization device |
| CN107715679B (en) * | 2017-11-22 | 2020-02-21 | 朗盈（成都）化工科技有限公司 | Flue gas desulfurization device |
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Application publication date: 20171110 |