CN106166437B - A kind of cement kiln flue gas desulphurization system and method - Google Patents
A kind of cement kiln flue gas desulphurization system and method Download PDFInfo
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- CN106166437B CN106166437B CN201610581553.XA CN201610581553A CN106166437B CN 106166437 B CN106166437 B CN 106166437B CN 201610581553 A CN201610581553 A CN 201610581553A CN 106166437 B CN106166437 B CN 106166437B
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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
- B01D53/78—Liquid phase processes with gas-liquid contact
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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
- 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
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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
- 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
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- 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
- B01D2251/2062—Ammonia
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- 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
- B01D2258/0233—Other waste gases from cement factories
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- 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
Abstract
A kind of cement kiln flue gas desulphurization system and method, including tank used for storing ammonia, delivery pump, ejecting gun, cement decomposing furnace, cement kiln precalcining system and automatic control system, cement kiln precalcining system includes multistage preheater, the tank used for storing ammonia is connected to by delivery pump with ejecting gun, and the spray site of ejecting gun is located at the exit of second level preheater windspout barrel.The method of the desulfurization, the ammonium hydroxide including one, configuration 15%-25%；Two, real-time detection SO2Concentration, according to SO in flue gas2Concentration is calculated, the amount of injection of adjustment ammonium hydroxide by automatic control system；Three, according to the ammonia water spray amount being calculated in step 2, ammonium hydroxide is injected in cement kiln precalcining system after injecting jet rifle after delivery pump is pressurized, injection is located at the exit of cement kiln second level preheater windspout barrel.For inventive desulfurization efficiency up to 95% or more, desulfuration efficiency is high, and ratio of ammonia-sulfur is 2~2.5, and operating cost is low.
Description
Technical field:
The invention belongs to cement kiln cigarette technical field of desulfurization, and in particular to a kind of using ammonium hydroxide as the cement of desulfurizing agent
De-suphur of kiln fume system and method.
Background technique
A large amount of sulfur dioxide can be generated in the coal-fired utilities production process such as thermal power plant, steel mill, Industrial Boiler, cement plant,
Sulfur dioxide can be oxidized to sulfuric acid mist or sulfate aerosol in an atmosphere, it is the important predecessor for causing acid rain.Thermal power plant,
Steel mill, Industrial Boiler etc. are mostly mating to have desulfurization equipment, and cement plant is due to the most of meeting of sulphur that it is generated in process of production
It is oxidized calcium uptake, so sulfur dioxide emissioning concentration is not high, most of production line can satisfy standard requirements.But some plant areas
Sulfur content of raw material is excessively high, and the concentration of emission of sulfur dioxide is also higher, in 200~2000mg/m3Differ.Country is to environmental protection in recent years
Requirement be increasingly stringenter, according to newest cement production enterprise exhaust emission standard " cement industry atmosphere pollutants emission standards "
(GB4915-2013) regulation in, cement kiln sulfur dioxide maximal emission are no more than 200mg/m3, key area is lower than
100mg/m3.Therefore, the enterprise exceeded for sulfur dioxide, there is an urgent need to the cement kiln desulphurization systems of a set of maturation.
Sulphur in quality coal in cement kiln systems is brought into as raw material and fuel: 1), sulfate present in raw material is in pre-heating system
It is generally do not form SO2Gas generally can all enter kiln system.A portion sulfate height temperate zone can occur to divide in kiln
Solution, the SO of generation2Gas is moved with kiln gas to kiln tail, when reaching the temperature lower regions such as minimum two-stage preheater, is condensate in
On the lower raw material of temperature, and enter in kiln with the heavy collection of raw material, form the circulatory system between preheater and kiln,
And undecomposed sulfate then can leave kiln system with clinker.In raw material otherwise existing sulphur (mainly with sulfide
Form presence), then it can be oxidized at 300~600 DEG C and generate SO2Gas occurs mainly in the second level of five (four) grade preheaters
The third level cyclone cylinder of cyclone cylinder or six grades of preheaters.2), in precalciner system, fuel is fed by kiln hood and dore furnace
Enter.The SO that dore furnace fuel combustion generates2The a large amount of activity CaO existing for furnace that can be decomposed absorb, the CaSO of generation4It is passed through with material
Lowermost level cyclone cylinder is entered in kiln by kiln tail smoke-box.The SO that the fuel of kiln hood feeding generates2Gas can be high in kiln with sulfate
Decompose the SO generated in temperate zone2Gas undergoes similar course.
The SO that sulphur oxidation in raw material generates2It can be partially absorbed when passing through higher level's cyclone cylinder, remaining is then with exhaust gas one
Road is discharged from preheater.If exhaust gas is used for drying material, SO2It is further absorbed in raw material mill.It is lower than 600 in temperature
In the case where DEG C, CaCO3To SO2Absorption efficiency to be far below CaO.CaCO in two-stage preheater above3Resolution ratio is extremely low, and
Only a small amount of CaO is got on by flue gas from high-temperature part band, therefore absorption efficiency is very low.Along with humidity is lower at this time and discharges
The preceding residence time is shorter, SO2Concentration of emission may be very high.If there is organic sulfur compound, oxidation behavior connects with troilite
Closely.
Current main conventional desulfurization technique is divided into dry desulfurization, semi-dry desulphurization and wet desulphurization three classes.Dry desulfurization
Technique includes reactant insufflation, hot raw material insufflation etc., and semi-dry desulphurization is mainly spray dry desulfurization method, wet desulphurization packet
Include the sulfur removal technologies such as the ammonia process of desulfurization, double alkali method desulfurizing, limestone-gypsum method.
Dry method and semi-dry desulfurizing process operating cost are high, and desulfuration efficiency is low, there is very big limitation applied to cement kiln.
Dual alkali, lime stone-gypsum method are widely used in the industries such as thermal power plant, steel mill, Industrial Boiler, and desulfuration efficiency is high, but the type desulfurization
Technique once invests larger, operating cost height, overweight for ordinary cement business burden, is also not suitable for.
Cement producing line has the characteristics that big exhaust gas volumn, material multi preheating, gas residence time are long, furthermore in kiln system
The cyclical effect of also peculiar sulphur, so that conventional sulfur removal technology is not particularly suited for cement kiln.Therefore, it needs to develop a kind of cement
The dedicated low cost of kiln, efficient sulfur removal technology.
Summary of the invention
The purpose of the present invention is to provide a kind of using ammonium hydroxide as the cement kiln flue gas desulphurization system of desulfurizing agent and side
Method solves the low technical problem of cement kiln desulfuration efficiency in the prior art.
In order to solve the technical problem, the present invention adopts the following technical scheme:
A kind of cement kiln flue gas desulphurization system, including tank used for storing ammonia, delivery pump, ejecting gun, cement decomposing furnace, cement kiln
Precalcining system and automatic control system, cement kiln precalcining system include multistage preheater, and the tank used for storing ammonia passes through conveying
Pump is connected to ejecting gun, and the spray site of ejecting gun is located at the exit of second level preheater windspout barrel, the ejecting gun at least one
Branch；Pneumatic control valve is provided on pipeline between the outlet end and ejecting gun of the delivery pump, in cement kiln precalcining system
It is provided with detection device, is electrically connected between detection device and pneumatic control valve and automatic control system.
It is further improved, further includes return pipe, one end of the return pipe is connected to the outlet end of ammonium hydroxide delivery pump, another
End is connected to tank used for storing ammonia, and return valve and ammonium hydroxide discharge pressure table are provided on return pipe.By adjusting reflux valve regulation reflux
For amount to control ammonium hydroxide discharge pressure, the pressure gauge on return pipe shows ammonium hydroxide delivery pressure force value.
It is further improved, the delivery pump is two, and is arranged in parallel, and system is provided between delivery pump and tank used for storing ammonia
Main valve.Two delivery pumps are used alternatingly, and prolong its service life, and when one of damage, another unlatching guarantees de-
Sulphur system can operate normally.
It is further improved, is provided with needle-valve, Electromagnetic Flow on the pipeline between the outlet end and ejecting gun of the delivery pump
Meter, pressure switch, ammonia leak detector and ammonium hydroxide endless tube；Wherein, pneumatic control valve is arranged in parallel with needle-valve, and ammonium hydroxide enters ammonium hydroxide
Each ammonia water spray rifle is evenly distributed to after endless tube.Needle-valve is maintenance bypass valve, in addition, when pneumatic control valve is fully open
Shi Liuliang, which is still unable to satisfy requirement, suitably to supplement flow by needle-valve.The flow monitoring of ammonium hydroxide is detected by electromagnetic flowmeter.
Pressure switch detects the pressure of ammonium hydroxide in whole system, will call the police shutdown system, the detection of ammonia leak detector when hypertonia
Whether entire transportation system has ammonium hydroxide leakage, guarantees the safety of whole system.
It is further improved, further includes compressed air conveying device, including pressure reducing valve, pressure gauge, check-valves and compressed air
Endless tube, compressed air distribute to each ejecting gun through compressed air endless tube, and ejecting gun is double-current spray gun body.Compressed air pressure
Position 0.3Mpa or so guarantees compressed air pressure, the compressed air pressure after pressure gauge display decompression by pressure reducing valve.Non-return
The purpose of valve is to prevent ammonium hydroxide from flowing backward in compressed air pipe.Compressed air after decompression enters compressed air endless tube, passes through ring
Pipe is evenly distributed to every ejecting gun.Using double-current spray gun body, ammonia atomization is sprayed into flue at droplet by compressed air,
Increase the contact area with sulfur dioxide, improves reaction efficiency.
Ammonium hydroxide in groove tank car is transferred in tank used for storing ammonia by ammonium hydroxide by unloading ammonia pump, and SNCR denitration can be had in cement plant
System is equipped with as the denitrating system of reducing agent using ammonium hydroxide and unloads ammonia pump and tank used for storing ammonia, so the present invention unloads ammonia without separately setting
Pump and tank used for storing ammonia are to reduce investment outlay, the equipment that cement kiln flue gas desulphurization system of the present invention can use SNCR denitration system,
Most equipment can be shared with denitrating system, reduce by a cost of investment, and operational management is convenient.
It is further improved, the ejecting gun is more, and spray site is uniformly arranged on the inner wall of second level preheater windspout barrel
On, the spray angle of ejecting gun is 20-40 degree, and ejecting gun is lateral spray type spray gun, and the side spray of all ejecting guns deflects direction phase
Together, deflection angle is 0-30 degree.By setting lateral spray type for ejecting gun, ammonia spraying is made to form circumferential eddy flow stream in flue
, fully ensure that area coverage.Because direct injection spray gun has a biggish blind area near the walling of flue of ring-shaped flue, and center
Domain lap is more, so can reduce blind area and overlapping region using lateral spray type spray gun, increases area coverage.
A method of desulfurization is carried out using cement kiln flue gas desulphurization system, is included the following steps:
Step 1: the ammonium hydroxide of configuration 15%-25%, and be transported in tank used for storing ammonia；
Step 2: setting SO by automatic control system2Concentration preset value, detection device real-time detection cement kiln predecomposition
SO in system flue gas2Concentration, and send measured value to automatic control system, automatic control system is according to preset value and measured value
Deviation calculate in real time, adjust the amount of injection of ammonium hydroxide；
Step 3: according to the ammonia water spray amount being calculated in step 2, by ammonium hydroxide after delivery pump is pressurized injecting jet
Be injected in after rifle in cement kiln precalcining system, injection be located at cement kiln second level preheater windspout barrel exit, second
The temperature in grade preheater exit is 350~500 DEG C；SO in the ammonium hydroxide and flue gas of penetrating2Desulphurization reaction occurs:
SO2Absorption process: 2NH3+H2O+SO2→(NH4)2SO3(1-1)；
Oxidation process: (NH4)2SO3+O2→(NH4)2SO4(1-2)；
Decomposition reaction: 3 (NH4)2SO4→4NH3+N2+3SO2+6H2O (1-3)；
Resorption process: 2SO2+2CaO+O2→2CaSO4(1-4)；
Wherein, SO2Absorption process and (NH4)2SO3Oxidation process occurs in the preheater of the second level, and being rich in flue gas has
10% or so oxygen.Ammonium hydroxide and SO in the cyclone cylinder of the second level2It reacts and generates ammonium sulfite, the sulfurous under excess oxygen
Sour ammonium can be oxidized to ammonium sulfate, and ammonium sulfate is attached on raw material with material to whereabouts, and temperature can increase at this time, and ammonium sulfate exists
280 DEG C start to decompose, and in 500 DEG C or more resolution ratios with higher, decompose completely at 513 DEG C or more, generate NH after decomposition3、
N2、SO2And H2O, the SO of generation2A part is absorbed by CaO in raw material generates CaSO4Into dore furnace, part CaSO4Pyrolytic
Participate in the sulfur cycle process of quality coal in cement kiln systems, undecomposed CaSO4It is discharged kiln system；The SO that another part rises with flue gas2Into
Enter and continue to generate ammonium sulfate with ammonium hydroxide reaction in the preheater of the second level, circulation is formed, up to most SO2All rows of being cured
Out.
The main influence factor of desulfuration efficiency is to spray the position of reaction zone, and main consideration is chosen in the position of ammonia water spray point
Following factor:
1) spray site should be located at kiln system SO2After generating position, according to quality coal in cement kiln systems SO2Mechanism of production, in raw material
Sulfide be oxidized at 300~600 DEG C generate SO2Gas occurs mainly in the second level cyclone cylinder of five (four) grade preheaters
Or the third level cyclone cylinder of six grades of preheaters.
2) desulfurization reaction zone will avoid temperature excessively high, because desulfurization product ammonium sulfate high temperature can decompose moment, cause desulfurization
Efficiency reduces.Desulfurizing agent absorbs SO2Ammonium sulfate, ammonium sulfite are mainly generated afterwards, and ammonium sulfite can be oxidized to ammonium sulfate, sulfuric acid
Ammonium starts to decompose at 280 DEG C, in 500 DEG C or more resolution ratios with higher, decomposes completely at 513 DEG C or more.Cement kiln
Second level cyclone cylinder outlet temperature is generally 350~500 DEG C, and third level cyclone cylinder outlet temperature is 550~650 DEG C.
3) spray site is chosen in cement kiln precalcining system, can bring desulphurization reaction product into next stage with raw material
Cyclone cylinder in, participate in the sulfur cycle of kiln system, or even directly with somehow being expelled directly out, whole system investment and operating cost meeting
It is greatly decreased.
Therefore, the present invention will spray ammonia position be arranged in second level preheater cyclone mouth exit, can meet simultaneously more than
Three requirements achieve the purpose that improve desulfuration efficiency, reduce desulphurization cost.
Sulfur removal technology according to the present invention is after starting to spray ammonium hydroxide, SO2Concentration is down to emission limit by initial value
100mg/m320~30min is needed below, and the ammonium sulfate for being primarily due to desulphurization reaction generation enters more advanced rotation with material
It can generate to decompose at high operating temperatures after in air duct and generate N2、NH3、SO2, decompose generation SO2 moved upwards with flue gas after meeting
Again it is absorbed by ammonium hydroxide, forms a SO2Circulation.Part SO2Production calcium sulfate is absorbed and aoxidizes by the CaO in kiln system, into
Enter the sulfur cycle that kiln system participates in kiln system itself, final solidification discharge.Therefore, start spray ammonium hydroxide after SO2It will not reduce moment,
The reduction of meeting slowly, actual Engineering Projects also turn out so.
In addition, CaCO3Itself is to SO2Absorption efficiency it is very low, but spray into ammonium hydroxide in contain moisture, water and SO2Reaction
Generate sulfurous acid, sulfurous acid and with the CaCO in raw material3It reacts and generates CO2And CaSO3, the presence of water can promote CaCO3It is right
SO2Assimilation effect, CaSO3In O2In the presence of can be oxidized to CaSO4, CaSO4Enter kiln system with material, participates in kiln
The sulfur cycle of system is discharged.Since cement kiln flue-gas temperature is generally relatively high, water and SO2Reaction time is short,
Therefore the amount that part reaction occurs is less.
Compared with prior art, the invention has the following beneficial effects:
1, according to the mechanism of production of cement kiln sulfur dioxide, the sulfide in raw material starts near third level cyclone cylinder
Sulfur dioxide is generated, desulfurizing agent inlet zone will be located at after sulfur dioxide generation position, to guarantee desulfurization effect, while avoid
Inlet zone temperature is excessively high, directly by Decomposition of ammonium sulfate.Therefore inlet zone is normally at the second level outlet of five-stage whirlwind cylinder, improves
Desulfurization effect.For inventive desulfurization efficiency up to 95% or more, desulfuration efficiency is high；It is real-time by automatic control system, detection device
It calculates, the amount of injection of adjustment ammonium hydroxide, SO2It is low with NH3 molar ratio 1:2-1:2.5, operating cost in ammonium hydroxide.
2, sulfur removal technology according to the present invention can adjust in real time ammonium hydroxide flow according to sulfur dioxide emissioning concentration, realize certainly
Dynamicization control, guarantees desulfuration efficiency, while accurately controlling ammonium hydroxide flow, avoids the escaping of ammonia is excessively high equipment is caused to corrode.
3, desulfurizing agent supply unit of the invention is conveyed using centrifugal multistage pump multiple centrifugal pump, and metering distribution system uses pneumatic control valve
Control flow.Conveying and metering distribution system are integrated into a set of equipment, and modularized design, occupied area is small, and the construction period is short, control
System processed can be incorporated into original denitrating system or a set of new system of independent design, and operational management is convenient.
4, the present invention is sprayed into desulfurizing agent in flue by the way of circumferential eddy flow using double-current spray gun body, guarantees covering
Area and residence time are to reach optimal desulfuration efficiency.
5, the present invention is run under the high temperature conditions using ammonium hydroxide as desulfurizing agent, and cost of investment is low, stable, to kiln
The influence of system is smaller.
Detailed description of the invention
Fig. 1 is cement kiln flue gas desulphurization system schematic diagram of the present invention.
Fig. 2 is cement decomposing furnace of the present invention, cement kiln precalcining system schematic diagram.
Fig. 3 is lateral spray type Flow Field Distribution schematic diagram in embodiment one.
Fig. 4 is direct injection Flow Field Distribution schematic diagram in comparative example one.
Specific embodiment
To keep the purpose of the present invention and technical solution clearer, below in conjunction with the embodiment of the present invention to skill of the invention
Art scheme is clearly and completely described.
Embodiment one:
As shown in Figure 1, a kind of cement kiln flue gas desulphurization system, ammonium hydroxide is turned the ammonium hydroxide in groove tank car by unloading ammonia pump 1
It moves in tank used for storing ammonia 2, SNCR denitration system can be had in cement plant, the denitrating system using ammonium hydroxide as reducing agent can be equipped with
Ammonia pump and tank used for storing ammonia are unloaded, so the present invention, which is not set separately generally, unloads ammonia pump 1 and tank used for storing ammonia 2 to reduce investment outlay.In tank used for storing ammonia
Outlet be equipped with open/stop desulphurization system ammonium hydroxide supply main valve 3 and open/stop denitrating system ammonium hydroxide supply the second main valve 4, so as to
When switching not homologous ray ammonium hydroxide supply.
In the present embodiment, desulphurization system conveys ammonium hydroxide, the using and the reserved, by adjusting back using two centrifugation delivery pumps 5
Stream valve 6 adjusts regurgitant volume to control the discharge pressure of ammonium hydroxide, and the ammonium hydroxide discharge pressure table 7 on return pipe shows ammonium hydroxide delivery pressure
Power.The flow of ammonium hydroxide is controlled by adjusting the valve opening of pneumatic control valve 8, can be examined in real time according to kiln tail on-line measuring device
Survey SO2Concentration carry out controlling opening of valve, achieve the purpose that automatic control.Needle-valve 9 is maintenance bypass valve；In addition, when pneumatic
The flow of ammonium hydroxide is still unable to satisfy requirement when 8 ammonium hydroxide of regulating valve conveys fully open, can pass through the suitably supplement ammonia aqua stream of needle-valve 9
Amount.The flow monitoring of ammonium hydroxide is detected by electromagnetic flowmeter 10.Pressure switch 11 detects the pressure of whole system, when hypertonia
It will call the police shutdown system, ammonia leak detector 12 detects whether entire transportation system has ammonium hydroxide leakage, guarantees the peace of whole system
Entirely.
Ammonium hydroxide is evenly distributed to each ejecting gun 18 after entering ammonium hydroxide endless tube 17.Ejecting gun 18 uses double-current spray gun body,
Ammonium hydroxide is sprayed into flue using compressed air.Compressed air pressure position 0.3Mpa or so guarantees to compress by pressure reducing valve 13
Air pressure, the compressed air pressure after the display decompression of pressure gauge 14.15 purpose of check-valves is to prevent ammonium hydroxide from flowing backward to compression sky
In feed channel.Compressed air after decompression enters compressed air endless tube 16, is evenly distributed to every spray gun by endless tube.
When ammonium hydroxide enters inlet zone, according to high temperature ammonia process reaction mechanism and cement kiln SO2Mechanism of production, inlet zone temperature
Cannot be excessively high, Decomposition of ammonium sulfate is prevented, the SO for guaranteeing to generate in all furnaces is also needed2All pass through conversion zone, most suitable position
Setting on second level cyclone cylinder exhaust pass, as shown in Figure 2.
As shown in figure 3, setting six ejecting guns, the diameter of second level preheater windspout barrel is 6m, and ejecting gun atomization distance is equal
3.5m is taken, spray angle is 30 °, and using lateral spray type ejecting gun, deflection angle α is 19 °, then the flue cross section ammonia of six direct-injection rifles
Water spray coverage rate is 44.66%.
The selection mode of side spray rifle spray angle α are as follows: flue diameter is divided by n spray site according to spray gun quantity n, even
Adjacent ejected dots AB is met, the middle line C of AB is taken, connects OC, the line of the midpoint D and spray site A of OC are spray centerline, AD and OA
Angle be jet angle α, by calculating, the area coverage of the jet angle has a distinct increment compared with the area coverage of direct injection spray gun,
To reach raising reaction efficiency, the purpose of ammonium hydroxide consumption is reduced.
Comparative example one:
As shown in figure 4, setting six ejecting guns, being arranged using direct injection, i.e., the diameter of second level preheater windspout barrel is 6m,
Ejecting gun atomization distance takes 3.5m, and spray angle is 30 °, other are identical with embodiment one.It is computed, six direct-injection rifles
Flue cross section ammonia spraying coverage rate is 34.95%.
Embodiment one and comparative example one compare:
By contrast, it is arranged using lateral spray type ejecting gun is opposite with direct injection, coverage rate is increased than direct injection spray gun
9.71%, desulphurization reaction efficiency is improved to reach, reduces the purpose of ammonium hydroxide consumption.
Embodiment two:
A method of desulfurization is carried out using cement kiln flue gas desulphurization system, is included the following steps:
Step 1: the ammonium hydroxide of configuration 15%-25%, and be transported in tank used for storing ammonia；
Step 2: setting SO by automatic control system2Concentration preset value, detection device real-time detection cement kiln predecomposition
SO in system flue gas2Concentration, and send measured value to automatic control system, automatic control system is according to preset value and measured value
Deviation calculate in real time, adjust the amount of injection of ammonium hydroxide；
Step 3: according to the ammonia water spray amount being calculated in step 2, by ammonium hydroxide after delivery pump is pressurized injecting jet
Be injected in after rifle in cement kiln precalcining system, injection be located at cement kiln second level preheater windspout barrel exit, second
The temperature in grade preheater exit is 350~500 DEG C；SO in the ammonium hydroxide and flue gas of penetrating2Desulphurization reaction occurs:
SO2Absorption process: 2NH3+H2O+SO2→(NH4)2SO3(1-1)；
Oxidation process: (NH4)2SO3+O2→(NH4)2SO4(1-2)；
Decomposition reaction: 3 (NH4)2SO4→4NH3+N2+3SO2+6H2O (1-3)；
Resorption process: 2SO2+2CaO+O2→2CaSO4(1-4)；
Wherein, SO2Absorption process and (NH4)2SO3Oxidation process occurs in the preheater of the second level, and being rich in flue gas has
10% or so oxygen.Ammonium hydroxide and SO in the cyclone cylinder of the second level2It reacts and generates ammonium sulfite, the sulfurous under excess oxygen
Sour ammonium can be oxidized to ammonium sulfate, and ammonium sulfate is attached on raw material with material to whereabouts, and temperature can increase at this time, and ammonium sulfate exists
280 DEG C start to decompose, and in 500 DEG C or more resolution ratios with higher, decompose completely at 513 DEG C or more, generate NH after decomposition3、
N2、SO2And H2O, the SO of generation2A part is absorbed by CaO in raw material generates CaSO4Into dore furnace, part CaSO4Pyrolytic
Participate in the sulfur cycle process of quality coal in cement kiln systems, undecomposed CaSO4It is discharged kiln system；The SO that another part rises with flue gas2Into
Enter and continue to generate ammonium sulfate with ammonium hydroxide reaction in the preheater of the second level, circulation is formed, up to most SO2All rows of being cured
Out.
The main influence factor of desulfuration efficiency is to spray the position of reaction zone, and main consideration is chosen in the position of ammonia water spray point
Following factor:
1) spray site should be located at kiln system SO2After generating position, according to quality coal in cement kiln systems SO2Mechanism of production, in raw material
Sulfide be oxidized at 300~600 DEG C generate SO2Gas occurs mainly in the second level cyclone cylinder of five (four) grade preheaters
Or the third level cyclone cylinder of six grades of preheaters.
2) desulfurization reaction zone will avoid temperature excessively high, because desulfurization product ammonium sulfate high temperature can decompose moment, cause desulfurization
Efficiency reduces.Desulfurizing agent absorbs SO2Ammonium sulfate, ammonium sulfite are mainly generated afterwards, and ammonium sulfite can be oxidized to ammonium sulfate, sulfuric acid
Ammonium starts to decompose at 280 DEG C, in 500 DEG C or more resolution ratios with higher, decomposes completely at 513 DEG C or more.Cement kiln
Second level cyclone cylinder outlet temperature is generally 350~500 DEG C, and third level cyclone cylinder outlet temperature is 550~650 DEG C.
3) spray site is chosen in cement kiln precalcining system, can bring desulphurization reaction product into next stage with raw material
Cyclone cylinder in, participate in the sulfur cycle of kiln system, or even directly with somehow being expelled directly out, whole system investment and operating cost meeting
It is greatly decreased.
Therefore, the present invention will spray ammonia position be arranged in second level preheater cyclone mouth exit, can meet simultaneously more than
Three requirements achieve the purpose that improve desulfuration efficiency, reduce desulphurization cost.
Sulfur removal technology according to the present invention is after starting to spray ammonium hydroxide, SO2Concentration is down to emission limit by initial value
100mg/m320~30min is needed below, and the ammonium sulfate for being primarily due to desulphurization reaction generation enters more advanced rotation with material
It can generate to decompose at high operating temperatures after in air duct and generate N2、NH3、SO2, decompose generation SO2 moved upwards with flue gas after meeting
Again it is absorbed by ammonium hydroxide, forms a SO2Circulation.Part SO2Production calcium sulfate is absorbed and aoxidizes by the CaO in kiln system, into
Enter the sulfur cycle that kiln system participates in kiln system itself, final solidification discharge.Therefore, start spray ammonium hydroxide after SO2It will not reduce moment,
The reduction of meeting slowly, actual Engineering Projects also turn out so.
In addition, CaCO3Itself is to SO2Absorption efficiency it is very low, but spray into ammonium hydroxide in contain moisture, water and SO2Reaction
Generate sulfurous acid, sulfurous acid and with the CaCO in raw material3It reacts and generates CO2And CaSO3, the presence of water can promote CaCO3It is right
SO2Assimilation effect, CaSO3In O2In the presence of can be oxidized to CaSO4, CaSO4Enter kiln system with material, participates in kiln
The sulfur cycle of system is discharged.Since cement kiln flue-gas temperature is generally relatively high, water and SO2Reaction time is short,
Therefore the amount that part reaction occurs is less.
Do not done in the present invention illustrate be the prior art or can be realized by the prior art, and the present invention
Described in specific implementation case be only preferable case study on implementation of the invention, practical range not for the purpose of limiting the invention.
Equivalent changes and modifications made by i.e. all contents according to scope of the present invention patent all should be used as technology scope of the invention.
Claims (5)
1. a kind of cement kiln flue gas desulphurization system, which is characterized in that decomposed including tank used for storing ammonia, delivery pump, ejecting gun, cement
Furnace, cement kiln precalcining system and automatic control system, cement kiln precalcining system include multistage preheater, the tank used for storing ammonia
It is connected to by delivery pump with ejecting gun, the spray site of ejecting gun is located at the exit of second level preheater windspout barrel, and ejecting gun is extremely
It is one few；Pneumatic control valve, cement kiln predecomposition system are provided on pipeline between the outlet end and ejecting gun of the delivery pump
It is provided with detection device in system, is electrically connected between detection device and pneumatic control valve and automatic control system；
Ejecting gun is more, and spray site even distribution is on the inner wall of second level preheater windspout barrel, the spray angle of ejecting gun
For 20-40 degree, ejecting gun is lateral spray type spray gun, and the side spray deflection direction of all ejecting guns is identical, and deflection angle is 0-30 degree；
It further include return pipe, one end of the return pipe is connected to the outlet end of ammonium hydroxide delivery pump, and the other end and tank used for storing ammonia connect
It is logical, return valve and ammonium hydroxide discharge pressure table are provided on return pipe.
2. cement kiln flue gas desulphurization system according to claim 1, which is characterized in that the delivery pump is two, and
It is arranged in parallel, system main valve is provided between delivery pump and tank used for storing ammonia.
3. cement kiln flue gas desulphurization system according to claim 2, which is characterized in that the outlet end of the delivery pump with
Needle-valve, electromagnetic flowmeter, pressure switch, ammonia leak detector and ammonium hydroxide endless tube are provided on pipeline between ejecting gun；Wherein,
Pneumatic control valve is arranged in parallel with needle-valve, and ammonium hydroxide is evenly distributed to each ammonia water spray rifle after entering ammonium hydroxide endless tube.
4. cement kiln flue gas desulphurization system according to claim 3, which is characterized in that further include compressed air conveying dress
It sets, including pressure reducing valve, pressure gauge, check-valves and compressed air endless tube, compressed air distribute to each through compressed air endless tube
Ejecting gun, ejecting gun are double-current spray gun body.
5. a kind of method for carrying out desulfurization using cement kiln flue gas desulphurization system described in any one of claim 1-4, special
Sign is, includes the following steps:
Step 1: the ammonium hydroxide of configuration 15%-25%, and be transported in tank used for storing ammonia；
Step 2: setting SO by automatic control system2Concentration preset value, detection device real-time detection cement kiln precalcining system
SO in flue gas2Concentration, and send measured value to automatic control system, automatic control system are inclined according to preset value and measured value
The poor the amount of injection for calculating in real time, adjusting ammonium hydroxide；
Step 3: according to the ammonia water spray amount being calculated in step 2, by ammonium hydroxide after delivery pump is pressurized after injecting jet rifle
It is injected in cement kiln precalcining system, spray site is located at the exit of cement kiln second level preheater windspout barrel, the second level
The temperature in preheater exit is 350 ~ 500 DEG C；SO in the ammonium hydroxide and flue gas of penetrating2Desulphurization reaction occurs:
SO2Absorption process: 2NH3+ H2O+SO2 → (NH4)2SO3(1-1)；
Oxidation process: (NH4)2SO3+ O2 → (NH4)2SO4 (1-2)；
Decomposition reaction: 3 (NH4)2SO4 →4NH3+N2+3SO2+6H2O(1-3)；
Resorption process: 2SO2+2CaO +O2→2CaSO4 (1-4)；
Wherein, SO2Absorption process and (NH4)2SO3(the NH in the preheater of the second level occurs for oxidation process4)2SO4Decomposition reaction
In three-level preheater, resorption process occurs in dore furnace, rich in the oxygen for having 10% or so in flue gas.
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| CN106731465B (en) * | 2016-12-30 | 2019-08-09 | 西安交通大学 | Alkali sulphur absorbs low-temperature corrosion preventing control method when a kind of coal-fired flue-gas depth is cooling |
| CN108079776A (en) * | 2017-11-24 | 2018-05-29 | 北京绿岩环保科技有限责任公司 | A kind of new dry process rotary kiln catalytic desulfurizing agent and its preparation and application |
| CN108014610A (en) * | 2018-01-05 | 2018-05-11 | 靳新令 | Ammonia desulfurizing process and its desulfurizer |
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| CN109865417A (en) * | 2019-03-05 | 2019-06-11 | 南京西普环保科技有限公司 | A kind of denitration integrated device and reducing agent flow rate adjusting method |
| CN109821392A (en) * | 2019-03-05 | 2019-05-31 | 南京西普环保科技有限公司 | A kind of denitrating system and its control method of dry method cement rotary kiln |
| CN111389192A (en) * | 2020-04-13 | 2020-07-10 | 湖南萃智咨询服务有限公司 | Dry-method cement kiln tail flue gas desulfurization method |
| CN114733329B (en) * | 2022-04-02 | 2023-12-08 | 南京西普环保科技有限公司 | Dry desulfurization process and dry desulfurization device for cement clinker |
| CN115974435A (en) * | 2023-01-10 | 2023-04-18 | 福建龙麟环境工程有限公司 | Dynamic sulfur suppression system and method for novel dry-process cement kiln under automatic control of DCS |
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