CN114061321B - Pellet flue gas treatment system based on rotary kiln primary circulation air inlet and flue gas treatment process thereof - Google Patents

Pellet flue gas treatment system based on rotary kiln primary circulation air inlet and flue gas treatment process thereof Download PDF

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CN114061321B
CN114061321B CN202010786182.5A CN202010786182A CN114061321B CN 114061321 B CN114061321 B CN 114061321B CN 202010786182 A CN202010786182 A CN 202010786182A CN 114061321 B CN114061321 B CN 114061321B
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sncr
denitration
pipeline
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flue gas
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CN114061321A (en
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胡兵
叶恒棣
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Zhongye Changtian International Engineering Co Ltd
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    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27FURNACES; KILNS; OVENS; RETORTS
    • F27DDETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS, OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
    • F27D17/00Arrangements for using waste heat; Arrangements for using, or disposing of, waste gases
    • F27D17/008Arrangements for using waste heat; Arrangements for using, or disposing of, waste gases cleaning gases
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27FURNACES; KILNS; OVENS; RETORTS
    • F27DDETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS, OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
    • F27D13/00Apparatus for preheating charges; Arrangements for preheating charges
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27FURNACES; KILNS; OVENS; RETORTS
    • F27DDETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS, OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
    • F27D15/00Handling or treating discharged material; Supports or receiving chambers therefor
    • F27D15/02Cooling
    • F27D15/0206Cooling with means to convey the charge
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27FURNACES; KILNS; OVENS; RETORTS
    • F27DDETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS, OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
    • F27D17/00Arrangements for using waste heat; Arrangements for using, or disposing of, waste gases
    • F27D17/004Systems for reclaiming waste heat

Abstract

The invention discloses a pellet flue gas treatment system based on rotary kiln primary circulation air inlet. And a control method of an SNCR-SCR coupling denitration mathematical model is also established, and the pellet flue gas is treated by adding a composite additive into an SNCR denitration catalyst or providing a novel SNCR composite ammonia agent. The invention optimizes the hot air circulation mechanism of the system, establishes the optimal coupling ultralow NOx emission technology, can effectively ensure the denitration efficiency on the premise of reducing the consumption of SNCR ammonia, can also prolong the service life of the SCR denitration catalyst, and obviously reduces the denitration operation cost and the investment cost of the system. Under the condition of ensuring the quality index of the product, the waste gas treatment capacity is reduced, the fuel consumption is reduced, and the ultralow emission of the smoke pollutants is realized.

Description

Pellet flue gas treatment system based on rotary kiln primary circulation air inlet and flue gas treatment process thereof
Technical Field
The invention relates to a flue gas treatment project, in particular to a pellet flue gas treatment system based on rotary kiln primary circulation air inlet and a flue gas treatment process thereof, belonging to the fields of a grate-rotary kiln flue gas treatment technology, energy conservation and emission reduction.
Background
The pellet ore is used as an important furnace charge for blast furnace ironmaking, has the advantages of high strength, good metallurgical performance and the like, compared with a sintering process, the pellet ore has lower energy consumption and pollution load, and is more suitable for the iron ore resource condition of which the concentrate ore is the main material in China, so the pellet ore is an iron ore agglomeration technology encouraging development. With the development of the steel industry, the yield of pellets in China tends to increase year by year.
The pellet process comprises a shaft furnace, a chain grate machine, a rotary kiln, a ring cooler and a belt type roasting machine, and compared with the other two pellet production processes, the chain grate machine, the rotary kiln and the ring cooler process have lower requirements on heat-resistant materials and fuel heat values, have wider application range on raw materials, and have relatively better quality of finished ore because the pellets are uniformly rolled in the roasting process of the rotary kiln, so the chain grate machine, the rotary kiln and the ring cooler pellet production process is still the most main production process in pellet production in China in a quite period of time. However, the amount of exhaust gas discharged during the pellet generation process of the chain grate machine, the rotary kiln and the annular cooler is large, so that the treatment cost of the exhaust gas is high, the waste heat utilization degree of the discharged exhaust gas is insufficient, and the waste of energy is caused.
For the current chain grate-rotary kiln-circular cooler air flow system and the waste gas treatment process in China, the externally discharged waste gas mainly comprises blast drying section waste gas, exhaust drying section waste gas and transitional preheating section waste gas. Wherein the content of water vapor in the exhaust gas outside the blast drying section is higher, and the content of pollutants is lower. At present, the hot exhaust gases of the induced draft drying section and the transitional preheating section are generally combined and discharged after being purified. The waste gas from the transition preheating section in the discharged waste gas has higher temperature and waste heat recovery value; the exhaust gas is complex in composition and contains a large amount of pollutants such as NOx and SOx, and thus it is necessary to perform treatments such as desulfurization and denitration on the hot exhaust gas. And directly carry out the denitration to the external exhaust gas, there is waste gas treatment volume big, and waste gas temperature is low needs the heating to reach the temperature of SCR denitration, leads to with high costs, pollutant up to standard emission degree of difficulty is big.
The exhaust gas amount of the exhaust drying section and the transition preheating section is large, along with the implementation of the ultralow emission policy, the NOx treatment cost for treating the part of hot exhaust gas is higher and higher, and meanwhile, if the hot exhaust gas temperature of the transition preheating section is higher, the waste of a large amount of energy sources is caused by only treating the exhaust gas without using the hot exhaust gas. Therefore, there is a need to develop more efficient and economical NOx ultra-low emission control technologies.
Existing methods for removing nitrogen oxides in flue gas mainly comprise Selective Catalytic Reduction (SCR) technology and non-selective catalytic reduction (SNCR) technology. Wherein, the selectivity of the SCR denitration technology refers to NH under the action of a catalyst and the presence of oxygen 3 Preferentially carrying out reduction and removal reaction on NOx to generate N 2 And H 2 O, but does not react with oxygen in the flue gas. For SNCR denitration technology, the environmental temperature plays a dominant role, and the temperature range is considered to be more suitable at 800-1100 ℃. When the temperature is too high, NH 3 Oxidation to form NO can cause the concentration of NO to increase, resulting in a decrease in the NOx removal rate; when the temperature is too low, NH 3 The reaction rate of (2) decreases, the NOx removal rate decreases, and NH 3 And the escape amount of (c) increases. In the production process of the chain grate machine-rotary kiln, the temperature range of a preheating section (PH) is 850-1100 ℃ generally, and the conditions of the SNCR denitration technology are met, but optimal control is needed to achieve the optimal emission reduction effect.
NOx is a major cause of photochemical smog, acid rain, and dust haze weather, aggravates ozone layer destruction, and promotes greenhouse effect, and is a great hazard to ecological environment. The generation of NOx in the pellet production process mainly originates from two forms of fuel type and thermal type, although the generation of NOx in the pellet production process of a grate-rotary kiln can be reduced by reducing the pellet yield, namely reducing the injection amount of coal gas or coal dust, reducing the strength requirement of the pellet, namely reducing the temperature of the rotary kiln, adopting the measures of raw materials with lower NOx, fuel and the like, but the environmental protection requirement of ultra-low emission is difficult to meet.
Although pellet enterprises do a great deal of work in the aspect of environmental protection, dust removal and desulfurization are effectively controlled, and emission requirements can be met, the existing NOx has new challenges for pellet industry due to high removal cost and complex process, and partial enterprises have to reduce the production in a great deal even face to be shut down due to exceeding of NOx. From the most pellet mill production, NOx is generally discharged at a concentration of 100-300 mg/m 3 The oxygen content of the exhaust gas is 17-19%, if it canFrom the source and the process, the generation of NOx is reduced, so that the emission requirement can be met, the tail end denitration purification equipment can be omitted, the method has great significance on the production of the pellets of the chain grate machine-rotary kiln, and the method is beneficial to further improving the vitality and the competitiveness of the pellet production.
In order to meet the NOx emission requirements of the chain grate machine-rotary kiln pellet production process, the national energy conservation and emission reduction call is responded, the process flow is started, and meanwhile, the characteristics of the system are utilized, so that the low NOx pellet production is realized on the premise of not adding new terminal treatment equipment. Therefore, a production system with ultra-low NOx emission of pellet flue gas is proposed. According to the system, the SNCR method NOx removal device is arranged at the preheating section of the chain grate machine, so that the content of NOx in pellet flue gas is reduced, meanwhile, the SCR system is additionally arranged at the air outlet of the bottom air box of the preheating section, the content of NOx in the flue gas is further reduced, and therefore ultra-low emission of the pellet flue gas NOx is realized, and the technical problems are solved, and the system has the characteristics of energy conservation, emission reduction and ultra-low NOx production. But the system control mechanism remains to be optimized. So as to reduce SNCR ammonia consumption and SCR catalyst service life, thereby reducing denitration cost. In order to improve the denitration efficiency of the SNCR technology, researchers have proposed many technical solutions. An additive for flue gas SNCR denitration and application thereof (grant No. CN 103252159B) as invented by Wu Zhongbiao et al: discloses an additive for SNCR denitration of flue gas, which consists of cellulose ether and inorganic sodium salt, and is sprayed into the flue gas at 760-850 ℃ for denitration after being mixed with a denitration reducing agent, so that the additive can adapt to different oxygen concentration changes and reduce a byproduct N 2 O is generated, the denitration efficiency reaches 40-70%, the effective denitration temperature area is enlarged, the allowable oxygen amount range is also enlarged, and ammonia escape is reduced. However, the research on additives applied to SNCR technology of grate-rotary kiln oxidized pellet flue gas denitration (the flue gas temperature range is 850-1100 ℃) is less at present.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a pellet flue gas treatment system based on rotary kiln primary circulation air inlet and a flue gas treatment process thereof. Firstly, specific flue gas in a transition preheating section of a chain grate machine is circulated, and meanwhile, non-heating SCR denitration is carried out on the waste gas from the preheating section, so that ultra-low emission of NOx in pellet flue gas is realized. The method comprises the steps that a plurality of bellows which are not communicated with each other are arranged behind a transition preheating section, the bellows are divided into a front bellows and a rear bellows (according to the trend of materials), the division principle is that the bellows are divided according to the content of NOx in flue gas in the bellows, namely, the bellows are sequentially and forwards sampled one by one from the last bellows of the transition preheating section to detect the content of NOx, and when the concentration of NOx in the flue gas in the detected bellows is smaller than the average concentration of NOx in the flue gas in the transition preheating section, the bellows are divided into the front bellows (the front bellows corresponds to an air outlet of the front section of the transition preheating section); similarly, when the detected concentration of NOx in the flue gas in the bellows is greater than or equal to the average concentration of NOx in the flue gas in the transition preheating section, the bellows is classified as a rear bellows (the rear bellows corresponds to the rear air outlet of the transition preheating section). According to different contents of NOx in flue gas in different bellows at the rear end of the transition preheating section, the rear section waste gas with high content of NOx is circulated into the rotary kiln through a primary combustion-supporting air pipe, so that the temperature of hot air entering the rotary kiln is improved, the waste heat of the transition preheating section can be fully utilized to reduce and balance the flame temperature of the rotary kiln, and the thermal NOx production is reduced. Meanwhile, the circulating hot exhaust gas of the bellows at the rear section of the transition preheating section is used as primary combustion supporting air of the central burner of the rotary kiln, so that the oxygen content of primary mixed air (the oxygen content in normal air is about 21 percent, and the oxygen content in the circulating hot exhaust gas is about 18 percent) is reduced, the generation amount of NOx is further reduced (namely, the generation amount of thermal NOx is reduced from the source), and the NOx in the circulating hot exhaust gas is reacted in partial CO formed in the central burner and is further converted into nitrogen, so that the consumption of amino reducing agent can be reduced. The scheme ensures that the hot air circulation of the system is more reasonable, namely, the waste gas treatment capacity is reduced, the fuel consumption is reduced and the ultralow emission of the smoke pollutants is realized under the condition of ensuring the quality index of the product.
Secondly, a control method of an SNCR-SCR coupling denitration system is adopted, a source, process and tail end control coupling denitration mathematical model is established by adopting a comprehensive weighting evaluation method of a multi-index test, and the matching relation among technologies (technological parameters, cost, technical economic indexes and the like and the optimal denitration rate) is comprehensively considered, so that the pellet coupling denitration optimal control method is formed. By adopting the method, the optimal coupling ultralow NOx emission technology can be formed, the denitration efficiency can be effectively ensured on the premise of reducing the SNCR ammonia consumption, the service life of the SCR denitration catalyst can be prolonged, and the denitration operation cost and the investment cost of the system are obviously reduced.
Finally, a compound additive of the SNCR denitration catalyst is also provided, namely, the compound additive is added into a flue gas denitration reducing agent (generally ammonia water) so as to improve the stability and the denitration rate when the SNCR technology is applied in the production process of the grate-rotary kiln pellets, improve the utilization efficiency of the flue gas denitration reducing agent and reduce NH (NH) 3 Escape amount. Or provides an SNCR composite catalyst (composite ammonia agent) to improve the utilization efficiency of the flue gas denitration reducing agent and reduce NH 3 Escape amount.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
According to a first embodiment of the invention, a pellet flue gas treatment system based on rotary kiln primary circulation air intake is provided, and comprises a chain grate machine, a rotary kiln and an SCR denitration device. According to the trend of the materials, the chain grate machine is sequentially provided with an air blast drying section, an air draft drying section, a transition preheating section and a preheating section. The rotary kiln is provided with a central burner. The central burner is communicated with the fuel pipeline. And the fuel pipeline is also provided with a primary combustion-supporting air pipe. The air outlet of the rotary kiln is communicated to the air inlet of the preheating section through a first pipeline. And the air outlet of the preheating section is communicated with the air inlet of the induced draft drying section through a second pipeline. The air outlet of the transition preheating section is divided into a front section air outlet and a rear section air outlet. And an air outlet at the rear section of the transition preheating section is communicated to an air inlet of the primary combustion-supporting air pipe through a third pipeline. And an air outlet at the front section of the transition preheating section is communicated with a fourth pipeline. And an air outlet of the air draft drying section is communicated to a fourth pipeline through a fifth pipeline. And the second pipeline is provided with an SCR denitration device.
Preferably, the bottom of the transition preheating section is provided with J bellows, and the air outlet of each bellows in the J bellows is simultaneously connected with a third pipeline and a fourth pipeline through a switching valve. The air outlet of each bellows is controlled to be communicated with the third pipeline only or the fourth pipeline only by switching the valve.
Preferably, the numbers of J bellows in the transition preheating section TPH are 1,2,3, J in sequence according to the trend of the materials. Wherein, the 1 st to the j-th bellows are used as front bellows and are communicated with the fourth pipeline. The (j+1) th to the (J) th windboxes are used as the rear-stage windboxes and are all communicated with the third pipeline. J is more than or equal to 1 and less than or equal to J.
Preferably, J is 1 to 50, preferably 2 to 20, more preferably 2 to 10.
Preferably, the system further comprises a circular cooler. According to the trend of the materials, the annular cooler is sequentially provided with an annular cooling first section, an annular cooling second section and an annular cooling third section. And an air outlet of the annular cooling section is communicated to an air inlet of the rotary kiln through a sixth pipeline. And the air outlet of the annular cooling second section is communicated with the air inlet of the transition preheating section through a seventh pipeline. And the air outlet of the annular cooling three sections is communicated with the air inlet of the forced air drying section through an eighth pipeline. And an air outlet of the forced air drying section is communicated to a chimney through a ninth pipeline.
Preferably, the system further comprises an SNCR denitration device. The SNCR denitration device is arranged in the preheating section and/or the first pipeline.
Preferably, the system further comprises a NOx concentration detection means, said NOx concentration detection means being arranged in the windbox. And the J bellows at the bottom of the transition preheating section are respectively and independently provided with a NOx concentration detection device.
Preferably, the SNCR denitration device comprises a first spraying device and a high-pressure atomization mixing device. The first spraying device is arranged in the preheating section and is connected with the high-pressure atomization mixing device through a tenth pipeline.
Preferably, the SNCR denitration device further comprises a second spraying device. The second spraying device is arranged in the first pipeline and is connected with the high-pressure atomization mixing device through an eleventh pipeline.
Preferably, the eleventh pipeline is a bypass pipeline branched from the tenth pipeline.
Preferably, the high-pressure atomization mixing device is provided with a vanadium-titanium catalyst conveying pipe, an ammonia water conveying pipe, a urea conveying pipe, a soluble sodium salt conveying pipe, an ethanol conveying pipe and a nano zero-valent iron or SBA-15 conveying pipeline.
Preferably, the system further comprises a mixing device. The mixing device is provided with a vanadium-titanium catalyst conveying pipe, an ammonia water conveying pipe, a urea conveying pipe, a soluble sodium salt conveying pipe and a nano zero-valent iron or SBA-15 conveying pipeline. The mixing device is communicated with the high-pressure atomization mixing device through a twelfth pipeline.
Preferably, the system further comprises a dust removal device arranged on the second conduit and upstream of the SCR denitration device. Preferably, the fourth pipeline is also provided with a dust removing device.
Preferably, the system further comprises a desulfurization device. The desulfurization device is arranged on the fourth pipeline. Preferably, a dust removing device is further provided on the fourth pipe, and the dust removing device is located upstream of the desulfurizing device.
Preferably, the third pipeline and the ninth pipeline are optionally provided with or not provided with dust removal devices.
According to a second embodiment of the present invention, there is provided a flue gas treatment process or a process for treating flue gas using the pellet flue gas treatment system based on rotary kiln primary circulation air intake according to the first embodiment, the process comprising the steps of:
1) According to the trend of the materials, raw balls enter a chain grate machine and are conveyed into a rotary kiln for oxidative roasting after sequentially passing through a blast drying section, an induced draft drying section, a transitional preheating section and a preheating section on the chain grate machine.
2) According to the flow direction of the hot air, the hot air in the rotary kiln is conveyed into the preheating section through the first pipeline. The hot air exhausted from the preheating section is firstly subjected to dust removal treatment by a dust removal device, and then is subjected to SCR denitration treatment by an SCR denitration device and then is conveyed into an air draft drying section. The hot air exhausted by the wind boxes at the front sections of the induced draft drying section and the transition preheating section is firstly subjected to dust removal treatment by a dust removal device, and then is exhausted after desulfurization treatment by a desulfurization device. The hot air discharged by the air box at the rear section of the transition preheating section is conveyed into the primary combustion-supporting air pipe after being subjected to dust removal treatment by the dust removal device.
Preferably, the process further comprises the steps of:
3) In the annular cooler, hot air discharged by one section of annular cooler is conveyed into the rotary kiln through a sixth pipeline. The hot air discharged from the annular cooling two sections is conveyed into the transitional preheating section through a seventh pipeline. The hot air discharged from the annular cooling three sections is conveyed into the blast drying section through an eighth pipeline.
4) Spraying an SNCR catalyst in the preheating section and/or in a first pipeline connected between an air inlet of the preheating section and an air outlet of the rotary kiln, and carrying out SNCR denitration reaction on NOx and the SNCR catalyst in hot air in the preheating section and/or the first pipeline.
5) The hot air discharged from the forced air drying section is optionally discharged via a ninth duct after dust removal treatment.
Preferably, the dividing mode of the front section bellows and the rear section bellows of the transition preheating section is specifically as follows:
301 Detecting the concentration of NOx in the flue gas in J bellows in real time to be H sequentially through NOx concentration detection devices arranged in J bellows 1 ,H 2 ,…,H J ,mg/m 3
302 Calculating the average NOx concentration in J of said windboxes in the transitional preheating section: h Average of =(H 1 +H 2 +…+H J ) J. Then successively judging the concentration of NOx and H in J pieces of said bellows Average of Is of a size of (a) and (b).
303 When H j <H Average of And H is j+1 ≥H Average of And when the preheating section is in the preheating state, the 1 st to the j th windboxes are the front windboxes of the transitional preheating section. The (j+1) th to the J th windboxes are the posterior windboxes of the transitional preheating section.
After the bellows is dispensed, return to step 301) continues the test.
Preferably, the process further comprises the steps of:
a) An SNCR denitration system is arranged in the preheating section and/or a first pipeline between the preheating section and the rotary kiln. Meanwhile, an SCR denitration system is arranged behind the air outlet of the preheating section. And establishing an SNCR-SCR coupling denitration mechanism.
b) And detecting and collecting parameter information of the initial concentration of NOx before SNCR denitration, the ammonia nitrogen ratio of SNCR ammonia injection, the window temperature of SNCR ammonia injection, the concentration of NOx before SCR denitration, the ammonia nitrogen ratio of SCR ammonia injection and the number of layers of the SCR catalyst bed in real time.
c) And establishing an SNCR-SCR coupling denitration mathematical model according to the detected parameter information.
d) And calculating and adjusting the minimum SNCR ammonia injection amount according to the SNCR-SCR coupling denitration mathematical model, so that the NOx content in the flue gas meets the emission condition.
Preferably, the SNCR-SCR coupling denitration mathematical model is as follows:
y=A·y x +B·y m +C·y t +D·y z +E·y n +F·y c .. formula I.
In the formula I, y is the SNCR-SCR coupling denitration rate. y is x Is the denitration rate based on the initial concentration of NOx before SNCR denitration. y is m Is the denitration rate based on the ammonia nitrogen ratio of SNCR ammonia injection. y is t Is the denitration rate based on the window temperature of SNCR ammonia injection. y is z Is the denitration rate based on the NOx concentration before SCR denitration. y is n Is the denitration rate based on the ammonia nitrogen ratio of SCR ammonia injection. y is c Is the denitration rate based on the number of SCR catalyst beds. A is the influence factor weight of the initial concentration x of NOx before SNCR denitration. B is the influence factor weight of ammonia nitrogen ratio m of SNCR ammonia injection. C is the influence factor weight of the window temperature t of SNCR ammonia injection. D is the influence factor weight of the NOx concentration z before SCR denitration. E is the influence factor weight of ammonia nitrogen ratio n of SCR ammonia injection. F is the influence factor weight of the number c of the SCR catalyst beds. And a+b+c+d+e+f=1.
Preferably, A is from 0.02 to 0.4, preferably from 0.05 to 0.2.B is 0.1 to 0.8, preferably 0.2 to 0.5.C is 0.05-0.5. Preferably 0.1 to 0.3.D is 0.01-0.3, preferably 0.02-0.2.E is 0.05 to 0.4, preferably 0.1 to 0.3.F is 0.05 to 0.5, preferably 0.1 to 0.4.
Preferably, the denitration rate y is based on the initial concentration of NOx before SNCR denitration x The method comprises the following steps:
Figure BDA0002622035560000061
in the formula II, x is the initial concentration of NOx before SNCR denitration, mg/m 3 . i is the power of x. I is more than or equal to 0 and less than or equal to N x 。N x To the highest power of x. a, a xi The coefficient to the ith power of x.
Preferably, the denitration rate y based on the ammonia nitrogen ratio of SNCR ammonia injection m The method comprises the following steps:
Figure BDA0002622035560000062
in the formula III, m is the ammonia nitrogen ratio of SNCR ammonia injection. Beta is the power of m. Beta is more than or equal to 0 and less than or equal to N m 。N m To the highest power of m. a, a The coefficient to the power of m.
Preferably, the denitration rate y based on the window temperature of SNCR ammonia injection t The method comprises the following steps:
Figure BDA0002622035560000071
in formula IX, t is the window temperature of SNCR ammonia injection, DEG C. Delta is the power of t. Delta is more than or equal to 0 and less than or equal to N t 。N t To the highest power of t. a, a The coefficient to the power delta of t.
Preferably, the denitration rate y is based on the NOx concentration before SCR denitration z The method comprises the following steps:
Figure BDA0002622035560000072
in the formula V, z is the concentration of NOx before SCR denitration, mg/m 3 . Gamma is the power of z. Gamma is more than or equal to 0 and less than or equal to N z 。N z To the highest power of z. a, a The coefficient to the power of z.
Preferably, the denitration rate y based on the ammonia nitrogen ratio of SCR ammonia injection n The method comprises the following steps:
Figure BDA0002622035560000073
in the formula VI, n is the ammonia nitrogen ratio of SCR ammonia injection. Lambda is the power of n. Lambda is more than or equal to 0 and less than or equal to N n 。N n To the highest power of n. a, a Is the coefficient to the lambda th power of n.
Preferably, the denitration rate y based on the number of SCR catalyst beds c The method comprises the following steps:
Figure BDA0002622035560000074
in formula VII, c is the number of SCR catalyst beds. θ is the power of c. θ is more than or equal to 0 and less than or equal to N c 。N c To the highest power of c. a, a The coefficient to the θ th power of c.
Preferably, formula II-VII is substituted into formula I to obtain:
Figure BDA0002622035560000075
further conversion of formula VIII gives formula I.
Preferably, step d) is specifically:
d1 When x.1-y is less than or equal to 50mg/m 3 When (1). Reducing ammonia nitrogen ratio of SNCR ammonia injection, m' =m-STEP m . Iterative calculations are carried out according to formula VIII until x.cndot.1-y > 50mg/m are exactly satisfied 3 . Then the value of m at this time is executed.
d2 When x.1-y > 50mg/m 3 When (1). Increasing the ammonia nitrogen ratio of SNCR ammonia injection, m' =m+STEP m . Iterative calculations are carried out according to formula VIII until x.cndot.1-y is just less than or equal to 50mg/m 3 . The value of m' at this time is then performed.
Wherein: m is the ammonia nitrogen ratio of SNCR ammonia injection at the current calculation. m' is the ammonia nitrogen ratio of SNCR ammonia spraying calculated in the next step. STEP (STEP) m The value of (2) is 0.01-0.5. Preferably 0.03 to 0.3. More preferably 0.05 to 0.1.
Preferably, the SNCR catalyst is an SNCR catalyst containing a composite additive comprising or consisting of: urea, soluble sodium salt, ethanol, vanadium-titanium catalyst, SBA-15. Or alternatively
The SNCR catalyst is a compound ammonia agent, and the compound ammonia agent comprises or consists of the following components: ammonia water, urea, soluble sodium salt, ethanol, vanadium-titanium catalyst and nano zero-valent iron-kaolin material.
Preferably, the composite additive in the SNCR catalyst containing the composite additive comprises the following components:
40-70 parts by weight, preferably 45-65 parts by weight, more preferably 50-60 parts by weight of urea.
The soluble sodium salt is 10 to 30 parts by weight, preferably 12 to 25 parts by weight, more preferably 15 to 20 parts by weight.
8-28 parts by weight of ethanol, preferably 10-25 parts by weight, more preferably 12-22 parts by weight.
The vanadium-titanium catalyst is 1 to 12 parts by weight, preferably 2 to 10 parts by weight, more preferably 3 to 8 parts by weight.
SBA-15 is 0.1 to 5 parts by weight, preferably 0.3 to 4 parts by weight, more preferably 0.5 to 3 parts by weight.
Preferably, the compound ammonia agent comprises the following components:
60 to 90 parts by weight, preferably 65 to 85 parts by weight, more preferably 70 to 80 parts by weight of aqueous ammonia.
8-30 parts by weight, preferably 10-25 parts by weight, more preferably 15-25 parts by weight of urea.
The soluble sodium salt is 0.05 to 1 part by weight, preferably 0.1 to 0.8 part by weight, more preferably 0.15 to 0.5 part by weight.
Ethanol 0.05 to 1.2 parts by weight, preferably 0.1 to 1 part by weight, more preferably 0.15 to 0.8 part by weight.
The vanadium-titanium catalyst is 0.01 to 0.1 part by weight, preferably 0.02 to 0.08 part by weight, more preferably 0.03 to 0.05 part by weight.
The nano zero-valent iron-kaolin material is 0.5 to 10 parts by weight, preferably 0.8 to 8 parts by weight, more preferably 1 to 6 parts by weight.
Preferably, in step 4), the specific method of spraying the SNCR catalyst is: to the denitration reducing agent (for example, ammonia water having a concentration of 20% to 25%), 0.1 to 2.0% by weight (preferably 0.3 to 1.2% by weight, more preferably 0.5 to 1.0% by weight) of a complex additive is added based on the total addition amount of the denitration reducing agent. Stirring and mixing uniformly. And then spraying the SNCR catalyst containing the composite additive after being uniformly mixed in the preheating section and/or in a first pipeline connected between an air inlet of the preheating section and an air outlet of the rotary kiln.
Or the compound ammonia agent is directly sprayed in the preheating section and/or in a first pipeline connected between the air inlet of the preheating section and the air outlet of the rotary kiln.
Preferably, the preparation method of the compound ammonia agent comprises the following steps: firstly, urea, soluble sodium salt, vanadium-titanium catalyst and nano zero-valent iron-kaolin material are all ground into powder. And then uniformly stirring and mixing powdery urea, soluble sodium salt, vanadium-titanium catalyst and nano zero-valent iron-kaolin material according to a proportion to obtain a powder mixture. Finally, the ethanol is measured separately according to the proportion to obtain the wet material. And adding the wet material and the powder mixture into ammonia water, and uniformly mixing to obtain the composite ammonia agent.
Preferably, the vanadium-titanium catalyst is selected from any V-TiO 2 Is a catalyst. The granularity of the vanadium-titanium catalyst is-0.074 mm or more than 80%, preferably-0.074 mm or more than 90%.
Preferably, the soluble sodium salt is NaCl or Na 2 CO 3
Preferably, the desulfurization treatment is dry desulfurization, semi-dry desulfurization or wet desulfurization. The desulfurization treatment is preferably performed using lime.
Preferably, the dust removing treatment is a bag dust removing treatment or an electric dust removing treatment.
In the prior art, in the three-machine pellet flue gas treatment process of the chain grate machine, the rotary kiln and the annular cooler, the externally discharged waste gas mainly comprises blast drying section waste gas, exhaust drying section waste gas and transitional preheating section waste gas. Wherein the content of water vapor in the exhaust gas outside the blast drying section is higher, and the content of pollutants is lower. At present, the hot exhaust gases of the induced draft drying section and the transitional preheating section are generally combined and discharged after being purified. The waste gas from the transition preheating section in the discharged waste gas has higher temperature and waste heat recovery value; the exhaust gas is complex in composition and contains a large amount of pollutants such as NOx and SOx, and thus it is necessary to perform treatments such as desulfurization and denitration on the hot exhaust gas. And directly carry out the denitration to the external exhaust gas, there is waste gas treatment volume big, and waste gas temperature is low needs the heating to reach the temperature of SCR denitration, leads to with high costs, pollutant up to standard emission degree of difficulty is big. The exhaust gas amount of the exhaust drying section and the transition preheating section is large, along with the implementation of the ultralow emission policy, the NOx treatment cost for treating the part of hot exhaust gas is higher and higher, and meanwhile, if the hot exhaust gas temperature of the transition preheating section is higher, the waste of a large amount of energy sources is caused by only treating the exhaust gas without using the hot exhaust gas. Meanwhile, because of the wind channeling phenomenon of the adjacent wind boxes of the preheating section and the transitional preheating section, the content of NOx in the wind box at the rear section of the transitional preheating section is high, and if the NOx is directly discharged, the ultra-low emission requirement cannot be met.
In the invention, the air outlet of the transitional preheating section is divided into a front section air outlet and a rear section air outlet. The hot air output by the air outlet at the rear section of the transition preheating section is conveyed into the primary combustion-supporting air pipe through the third pipeline under the action of the circulating fan, and then is conveyed into the rotary kiln through the primary combustion-supporting air pipe. Through circulating the rear-section exhaust gas with high NOx content in the rear-section part of the transition preheating section into the rotary kiln through the primary combustion-supporting air pipe, the temperature of hot air entering the rotary kiln is further improved, the waste heat of the transition preheating section can be fully utilized to reduce the flame temperature of the rotary kiln, the thermal NOx generation amount is reduced, and meanwhile, the NOx in the part of the flue gas can be circulated into the SNCR and/or the SCR denitration device for denitration treatment again. Furthermore, the circulating hot exhaust gas of the bellows at the rear section of the transition preheating section is used as primary combustion supporting air of the central burner of the rotary kiln, so that the oxygen content of primary mixed air (the oxygen content in normal air is about 21 percent, and the oxygen content in the circulating hot exhaust gas is about 18 percent) is reduced, the generation amount of NOx is further reduced (namely, the generation amount of thermal NOx is reduced from the source), and the NOx in the circulating hot exhaust gas is reacted in partial CO formed in the central burner and is further converted into nitrogen, so that the consumption of amino reducing agent can be reduced. According to the scheme, the hot air circulation of the system is more reasonable, namely, under the condition of ensuring the quality index of the product, the waste gas treatment capacity is reduced, the fuel consumption is reduced, the ammonia escape is reduced, and therefore ultralow emission is realized.
In the invention, J bellows are arranged at the bottom of the transition preheating section, and the air outlet of each bellows in the J bellows is simultaneously connected with a third pipeline and a fourth pipeline through a switching valve. The air outlet of any one bellows is controlled to be communicated with the third pipeline only or the fourth pipeline only by switching the valve. According to the trend of the materials, the numbers of J bellows in the transition preheating section are 1,2,3, … and J in sequence. Wherein, the 1 st to the j-th bellows are used as front bellows and are communicated with the fourth pipeline. The (j+1) th to the (J) th windboxes are used as the rear-stage windboxes and are all communicated with the third pipeline. J is more than or equal to 1 and less than or equal to J. J is 1 to 50, preferably 2 to 20, more preferably 2 to 10. Further, at least one NOx concentration detecting device is provided in each of the J windboxes to detect the content (mg/m) of NOx in the hot air in each windbox in real time 3 ) And then dividing the transition preheating section bellows into a front section bellows and a rear section bellows according to the content of NOx in each bellows. The division mode of the front section bellows and the rear section bellows of the transition preheating section is specifically as follows:
301 Real-time detection of the concentration of NOx in the flue gas in J windboxes to be H sequentially through each independent NOx concentration detection device arranged in J windboxes 1 ,H 2 ,…,H J ,mg/m 3
302 Calculating the average NOx concentration in J of said windboxes in the transitional preheating section: h Average of =(H 1 +H 2 +…+H J ) J. Then successively judging the concentration of NOx and H in the flue gas in J air boxes Average of Is of a size of (a) and (b).
303 When H j <H Average of And H is j+1 ≥H Average of And when the preheating section is in the preheating state, the 1 st to the j th windboxes are the front windboxes of the transitional preheating section. The (j+1) th to the J th windboxes are the posterior windboxes of the transitional preheating section.
After the bellows is dispensed, return to step 301) continues the test.
It should be noted that, in general, according to the trend of the materials, the concentration of NOx in the flue gas in the windbox at the rear of the transition preheating section is gradually increased. (the preheating section can blow-by to the transitional preheating section, thereby leading the concentration of NOx in the flue gas in the rear-section bellows to be higher than that in the flue gas in the front-section bellows)
In the invention, in general, after dust removal of the rear-section bellows exhaust gas of the transitional preheating section by the multi-pipe dust remover, the exhaust gas is circulated into the rotary kiln through the circulating fan, and the circulated exhaust gas is directly conveyed into the rotary kiln as primary combustion air, so that on one hand, the flame temperature in the rotary kiln can be reduced and balanced, the thermal NOx generation amount (NOx generation in the process) can be reduced, on the other hand, the exhaust gas of the transitional preheating section also contains a certain concentration of NOx, and part of the exhaust gas is directly circulated into the rotary kiln, so that the denitration treatment of the subsequent working procedure (SNCR and/or SCR) can be carried out along with the hot gas generated in the rotary kiln, the removal efficiency of the NOx can be improved, and meanwhile, the carrying amount of the NOx in the pellets can be increased after the part of the hot exhaust gas containing the NOx is contacted with the pellets of the annular cooling section can be avoided, and the escape amount of the NOx can be reduced. Through directly circulating the rear section hot waste gas of the transition preheating section to the rotary kiln, the hot air circulation of the system is more reasonable, namely, the waste gas treatment capacity is reduced, the fuel consumption is reduced and the ultralow emission of the smoke pollutants is realized under the condition of ensuring the quality index of products. The exhaust gas circulation amount accounts for 30% -50% of the total volume of the exhaust gas of the transitional preheating section. Meanwhile, after the flue gas of the transitional preheating section is circulated, the air quantity introduced in the first section of the annular cooling is converted into the air quantity under the standard condition or the same air quantity as before circulation, the air quantity of the second section of the annular cooling is increased by 3% -10%, the air quantity of the third section of the annular cooling is increased by 5% -10%, and the temperature of the pellets discharged from the annular cooling machine is ensured to be lower than 150 ℃. The hot gas from the first annular cooling section is led into the rotary kiln, the hot gas from the second annular cooling section is led into the transitional preheating section of the chain grate machine, and the hot gas from the third annular cooling section is led into the blast drying section of the chain grate machine. Further, since the exhaust gas of the transitional preheating section circulates into the rotary kiln, the hot gas led out from the annular cooling section is optionally discharged or not discharged, and when the discharged hot gas is required (the discharged hot gas amount is consistent with the exhaust gas amount circulated into the rotary kiln by the transitional preheating section), the part of discharged hot gas can be directly discharged, and the part of discharged hot gas can also be circulated into the chain grate machine blast drying section and/or the induced draft drying section and/or the transitional preheating section to realize the waste heat recycling of the hot gas.
In the invention, the waste gas from the preheating section is subjected to non-heating SCR denitration, and the smoke from the transitional preheating section is circulated to reduce the coal injection amount or the gas injection amount of the rotary kiln by about 3-10%, so as to ensure the O of the gas in the rotary kiln 2 The content is not less than 18 percent, and the temperature of the exhaust gas from the preheating section is 280-380 ℃. And then directly carrying out SCR denitration treatment on the waste gas in the preheating section pipeline, and is characterized in that the waste gas is not required to be heated, and a medium Wen Fanji catalyst is adopted as the catalyst. Before SCR denitration, a multi-pipe dust remover can be used for removing dust from the waste gas, so that the dust content of the waste gas is reduced to 20mg/m 3 The following is given. The energy consumption of pellets is reduced and the treatment capacity of waste gas in the subsequent purification process is reduced by optimizing the operation parameters of a chain grate machine, a rotary kiln and a circular cooler; meanwhile, the waste gas from the preheating section is subjected to non-heating SCR denitration treatment, so that NOx can be efficiently removed under the condition that the waste gas is not heated. After the transition preheating later-stage bellows waste gas circulation is adopted, the invention can reduce the consumption of gases such as coal dust or coal gas or solid fuel in the rotary kiln, such as the mass ratio of the coal dust and the volume reduction of the coal gas by about 3-10 percent.
At present, in order to meet the NOx emission requirement of the production process of the pellets of the chain grate machine-rotary kiln, namely, the pellet roasting flue gas is required to have the average emission concentration of NOx of not more than 50mg/m in the condition of 18% of the standard oxygen content 3 . If the oxygen content is higher than 18%, the NOx concentration is checked as a value converted to a reference oxygen content. In order to achieve the purpose, the existing technology realizes the production of the pellets with low NOx on the premise of not adding new terminal treatment equipment by starting from the technological process and utilizing the characteristics of the system. The device for removing NOx by SNCR method is arranged at the preheating section of the system grate machine, so that the content of NOx in the pellet flue gas is reduced, and meanwhile, the air box is arranged at the bottom of the preheating sectionAn SCR system is additionally arranged at the air outlet of the pellet flue gas, so that the content of NOx in the flue gas is further reduced, and the ultra-low emission of the pellet flue gas NOx is realized. Although the SNCR-SCR combined process can realize ultralow emission of NOx, the SNCR denitration mechanism and the SCR denitration mechanism cannot be perfectly combined due to the fact that a corresponding optimal control mechanism does not exist at present, so that the SNCR has larger ammonia consumption (correspondingly, the problem of increasing ammonia escape) or the service life of the SCR denitration catalyst is shorter, and the SCR denitration catalyst needs to be replaced frequently to meet denitration requirements, so that the problem of higher production investment cost is caused. If the ammonia injection amount is reduced or the catalyst is not replaced in time, the problem of exceeding the standard of NOx emission is caused.
At present, in the chain grate machine-rotary kiln denitration system, when the SNCR technology is adopted in the PH section or the transition section (the transition section between the PH section and the rotary kiln, namely, in the first pipeline), the concentration of NOx entering the SCR technology is greatly reduced, the consumption of a catalyst is reduced, and the activity of the catalyst is prolonged. In general, the catalyst activity is required to be maintained at 60% or more. Catalyst activity was maintained for about 3 years when denitration was performed using SCR only, and extended to about 3.6 years when sncr+scr system was used. The service life of the catalyst activity in different denitration systems is detailed in the specification and attached figure 3. By adopting the SNCR+SCR system, the engineering investment can be reduced by about 1000 ten thousand yuan, and the catalyst replacement cost can be reduced by about 20 ten thousand yuan/year. The comparison of investment and maintenance costs of different denitration processes is shown in figure 4 of the specification.
In the invention, key parameters in the SNCR-SCR coupling denitration system are monitored and collected in real time, namely, parameter information of the initial concentration of NOx before SNCR denitration, the ammonia nitrogen ratio of SNCR ammonia injection, the window temperature of SNCR ammonia injection, the concentration of NOx before SCR denitration, the ammonia nitrogen ratio of SCR ammonia injection and the number of SCR catalyst beds are detected and collected in real time. Then, reasonable weight distribution is carried out according to the influence of each key parameter on the denitration effect, based on experimental research and engineering application experience, an SNCR-SCR coupling denitration mathematical model is established by adopting a comprehensive weighted scoring method of a multi-index experiment, an optimization control mechanism is established through the mathematical model, and the optimization control can be carried out on different chain grate machine-rotary kiln SNCR-SCR coupling denitration systems, so that Is obtained after meeting the requirement of ultra-low emission (not more than 50mg/m of NOx 3 ) On the premise of ensuring that the system can achieve the optimal combination mechanism of the minimum SNCR ammonia injection amount and the longest service life of the SCR catalyst, thereby ensuring the denitration efficiency of the denitration system, reducing the input cost and obtaining the optimal economic benefit.
In the invention, aiming at a chain grate machine-rotary kiln NCR-SCR coupling denitration system, the first step is as follows: mainly considering the influence of the initial concentration (x) of NOx, the ammonia nitrogen ratio (m) of SNCR ammonia injection and the window temperature (t) of SNCR ammonia injection on the denitration rate before SNCR denitration (preheating section and/or transition section between the preheating section and the rotary kiln), and then determining an SNCR denitration efficiency mathematical model through data analysis and data curve fitting:
first, the denitration rate y for the initial NOx concentration before SNCR denitration x The method comprises the following steps:
Figure BDA0002622035560000121
in the formula II, x is the initial concentration of NOx before SNCR denitration, mg/m 3 . i is the power of x. I is more than or equal to 0 and less than or equal to N x 。N x To the highest power of x. a, a xi The coefficient to the ith power of x.
Secondly, denitration rate y for ammonia nitrogen ratio based on SNCR ammonia injection m The method comprises the following steps:
Figure BDA0002622035560000122
in the formula III, m is the ammonia nitrogen ratio of SNCR ammonia injection. Beta is the power of m. Beta is more than or equal to 0 and less than or equal to N m 。N m To the highest power of m. a, a The coefficient to the power of m.
Finally, denitration rate y for window temperature based on SNCR ammonia injection t The method comprises the following steps:
Figure BDA0002622035560000123
in formula IX, t is the window temperature of SNCR ammonia injection, DEG C. Delta is the power of t. Delta is more than or equal to 0 and less than or equal to N t 。N t To the highest power of t. a, a The coefficient to the power delta of t.
Further, the SNCR denitration rate obtained by combining weight distribution has the following formula:
y SNCR =A1·y x +B1·y m +C1·y t ...(1)。
equation (1) is further developed as:
Figure BDA0002622035560000131
in the formula (2), y SNCR Is SNCR denitration rate; a1 is an influence weight factor considering only a key parameter x during SNCR denitration; b1 is an influence weight factor considering only the key parameter m during SNCR denitration; c1 is an influence weight factor considering only the key parameter t during SNCR denitration; a1+b1+c1=1 (weight ratio of A1, B1, C1 is determined to be reasonably adjusted and distributed according to actual working conditions); i. beta and delta are the powers of the key parameters x, m and t respectively. N (N) x 、N m 、N t The highest power of the key parameters x, m and t respectively. a, a xi 、a 、a The coefficients corresponding to the secondary sides of the key parameters x, m and t are respectively obtained.
When only SNCR denitration is considered, the influence of each key parameter (x, m and t) on the SNCR denitration rate is obtained by adopting a single variable form and adopting a big data fitting method, and then an SNCR denitration mathematical model is established according to a comprehensive weighting scoring method of a multi-index test.
In the invention, aiming at a chain grate machine-rotary kiln NCR-SCR coupling denitration system, the second step is as follows: the method mainly considers the influence of the concentration (z) of NOx before SCR denitration after multiple tubes, the ammonia nitrogen ratio (n) of SCR ammonia injection and the number (c) of SCR catalyst beds on the denitration rate, and then determines an SCR denitration efficiency mathematical model through data analysis and data curve fitting:
first, the denitration rate y for the NOx concentration before SCR denitration z The method comprises the following steps:
Figure BDA0002622035560000132
in the formula V, z is the concentration of NOx before SCR denitration, mg/m 3 . Gamma is the power of z. Gamma is more than or equal to 0 and less than or equal to N z 。N z To the highest power of z. a, a The coefficient to the power of z.
Secondly, denitration rate y for ammonia nitrogen ratio based on SCR ammonia injection n The method comprises the following steps:
Figure BDA0002622035560000133
in the formula VI, n is the ammonia nitrogen ratio of SCR ammonia injection. Lambda is the power of n. Lambda is more than or equal to 0 and less than or equal to N n 。N n To the highest power of n. a, a Is the coefficient to the lambda th power of n.
Finally, the denitration rate y based on the number of SCR catalyst beds c The method comprises the following steps:
Figure BDA0002622035560000134
in formula VII, c is the number of SCR catalyst beds. θ is the power of c. θ is more than or equal to 0 and less than or equal to N c 。N c To the highest power of c. a, a The coefficient to the θ th power of c.
Further, the formula for obtaining the SCR denitration rate by combining weight distribution is as follows:
y SCR =D1·y z +E1·y n +F1·y c ...(3)。
equation (3) is further developed as:
Figure BDA0002622035560000141
in the formula (2), y SCR The denitration rate is SCR; d1 is an influence weight factor considering only the key parameter z during SCR denitration; e1 is the influence right considering only the key parameter n in SCR denitration A heavy factor; f1 is an influence weight factor considering only the key parameter c during SCR denitration; d1+e1+f1=1 (weight ratio of D1, E1, F1 is determined to be reasonably adjusted and distributed according to actual working conditions); gamma, lambda and theta are the powers of the key parameters z, n and c respectively. N (N) z 、N n 、N c The highest power of the key parameters z, n, c, respectively. a, a 、a 、a The coefficients corresponding to the secondary sides of the key parameters z, n and c are respectively obtained.
When only considering SCR denitration, the influence of each key parameter (z, n, c) on the SCR denitration rate is obtained by adopting a single variable form and adopting a big data fitting method, and then an SCR denitration mathematical model is established according to a comprehensive weighting evaluation method of a multi-index test.
Further, based on experimental study and engineering application experience, a comprehensive weighted scoring method of a multi-index experiment is adopted to establish a process (SNCR technology) and end control (SCR technology) coupling denitration mathematical model, namely an SNCR-SCR coupling denitration mathematical model:
y=A·y x +B·y m +C·y t +D·y z +E·y n +F·y c .. formula I.
Formula I is further evolved to:
Figure BDA0002622035560000142
in formula VIII, a is the influence factor weight of the initial NOx concentration x before SNCR denitration. B is the influence factor weight of ammonia nitrogen ratio m of SNCR ammonia injection. C is the influence factor weight of the window temperature t of SNCR ammonia injection. D is the influence factor weight of the NOx concentration z before SCR denitration. E is the influence factor weight of ammonia nitrogen ratio n of SCR ammonia injection. F is the influence factor weight of the number c of the SCR catalyst beds. And a+b+c+d+e+f=1. Wherein A is 0.02 to 0.4, preferably 0.05 to 0.2.B is 0.1 to 0.8, preferably 0.2 to 0.5.C is 0.05-0.5. Preferably 0.1 to 0.3.D is 0.01-0.3, preferably 0.02-0.2.E is 0.05 to 0.4, preferably 0.1 to 0.3.F is 0.05 to 0.5, preferably 0.1 to 0.4.X is the initial concentration of NOx before SNCR denitration, mg/m 3 . m is ammonia of SNCR ammonia injectionNitrogen ratio. t is the window temperature of SNCR ammonia injection, deg.C. z is the concentration of NOx before SCR denitration, mg/m 3 . n is the ammonia nitrogen ratio of SCR ammonia injection. And c is the number of the beds of the SCR catalyst. i. Beta, delta, gamma, lambda and theta are the powers of the denitration key parameters x, m, t, z, n, c respectively. N (N) x To the highest power of x. a, a xi The coefficient to the ith power of x. N (N) m To the highest power of m. a, a The coefficient to the power of m. N (N) t To the highest power of t. a, a The coefficient to the power delta of t. N (N) z To the highest power of z. a, a The coefficient to the power of z. N (N) n To the highest power of n. a, a Is the coefficient to the lambda th power of n. N (N) c To the highest power of c. a, a The coefficient to the θ th power of c.
In the present invention, N x The value of (2) is in the range of 0 to 5, preferably 1 to 3.N (N) m The value of (2) is in the range of 0 to 5, preferably 1 to 3.N (N) t The value of (2) is in the range of 0 to 5, preferably 1 to 3.N (N) z The value of (2) is in the range of 0 to 5, preferably 1 to 3.N (N) n The value of (2) is in the range of 0 to 5, preferably 1 to 3.N (N) c The value of (2) is in the range of 0 to 5, preferably 1 to 3.
Further, the SNCR-SCR coupling denitration mathematical model can be obtained by further conversion of the formula VIII:
y=A·y x +B·y m +C·y t +D·y z +E·y n +F·y c .. formula I.
In the invention, the average emission concentration of NOx in pellet roasting flue gas under the condition of 18 percent of standard oxygen content according to national requirements is not higher than 50mg/m 3 . If the oxygen content is higher than 18%, the NOx concentration is checked as a value converted to a reference oxygen content. Namely, the concentration of x (1-y) is less than or equal to 50mg/m 3 The lower the cost of this condition, the better and the higher the economic value. The cost is reflected in two aspects, namely the amount of SNCR ammonia injection. And secondly, the activity duration of the SCR catalyst. Under the condition of ensuring the denitration requirement, the smaller the ammonia injection amount is, the more economical the ammonia injection amount is, and the longer the catalyst activity duration is, the better the catalyst activity duration is.
When x.cndot.1-y is less than or equal to 50mg/m 3 When (1). The value of m is reduced to calculate, and the STEP length of calculation is STEP m . I.e. continuously performing m=m-STEP on formula VIII m Until just satisfying x (1-y) > 50mg/m 3 (i.e., x.1-y.ltoreq.50 mg/m is just not satisfied) 3 ) At this time, i.e. the minimum critical point of ammonia injection, we execute m=m+step on the basis of the m value at this time for safety m . To ensure that x (1-y) is less than or equal to 50mg/m 3 The condition is the most economical ammonia spraying amount. The point ensures that the SNCR ammonia injection amount is minimum, the activity duration of the SCR catalyst can be prolonged to the greatest extent, and simultaneously, the ultralow NOx emission condition is met, so that the method is the most economical choice.
When x.cndot.1-y > 50mg/m 3 When (1). Increasing the value of m to calculate, wherein the STEP length of calculation is STEP m . I.e. continuously performing m=m+step on formula VIII m Until just satisfying x.1-y.ltoreq.50 mg/m 3 . Then the value of m at this time is executed. To ensure that x (1-y) is less than or equal to 50mg/m 3 The condition is the most economical ammonia spraying amount. The point ensures that the SNCR ammonia injection amount is minimum, the activity duration of the SCR catalyst can be prolonged to the greatest extent, and simultaneously, the ultralow NOx emission condition is met, so that the method is the most economical choice.
Wherein the STEP size STEP m The value of (2) is 0.01-0.5. Preferably 0.03 to 0.3. More preferably 0.05 to 0.1. The design can be reasonably adjusted according to the actual working condition.
Generally, for SNCR denitration techniques, a temperature range of 800℃to 1100℃is considered preferable. The SNCR denitration technology is generally adopted in the production process of the chain grate machine-rotary kiln pellets, and a reducing agent (ammonia water or urea) is sprayed into the flue gas at a preheating section (the temperature range is 850-1100 ℃) to carry out flue gas denitration, but optimal control is needed to achieve the optimal emission reduction effect. However, the effect of the SNCR technique is sensitive to factors such as temperature, reducing agent usage, etc. NH when fluctuations in the production process occur, e.g. when the temperature is too high 3 Oxidation to form NO may cause the concentration of NO to increase, resulting in a decrease in the removal rate of NOx, NH when the temperature is too low 3 The reaction rate of (2) decreases, the NOx removal rate also decreases, and NH simultaneously 3 And the escape amount of (c) increases.
In the invention, urea, soluble sodium salt (such as sodium chloride or sodium carbonate), ethanol, vanadium-titanium catalyst, SBA-15 or ammonia water, urea, soluble sodium salt (such as sodium chloride or sodium carbonate), ethanol, vanadium-titanium catalyst and nano zero-valent iron-kaolin material are weighed according to a specific mass ratio and stirred uniformly to obtain a primary mixture, wherein the ethanol is required to be weighed and placed for standby. And then the primary mixture and ethanol are subjected to high-pressure atomization and mixing to obtain a composite additive (vanadium-titanium composite additive) or a composite ammonia agent (vanadium-titanium composite ammonia agent) which is sprayed into the high NOx flue gas to carry out SNCR denitration reaction. Because ethanol is a flammable, volatile and colorless transparent liquid, the ethanol is required to be weighed and placed separately, and is mixed with other raw materials to form the vanadium-titanium compound ammonia agent for denitration in the production process.
In the invention, the vanadium-titanium composite additive is formed by compounding urea, soluble sodium salt, ethanol, vanadium-titanium catalyst and SBA-15. Wherein urea decomposes at high temperature to release ammonia gas, which is NH 3 The reducing agent can be slowly released in a certain period of time when the nitrogen oxides are reduced, so that the denitration reduction reaction is continuously carried out, and the conversion rate of the nitrogen oxides is improved. The soluble sodium salt and ethanol can generate a large number of active groups such as-H, -CH, -OH and the like through reaction or decomposition after entering high-temperature flue gas, and activate a denitration reaction chain at a lower temperature, so that the sensitivity of SNCR denitration to the reaction temperature is obviously reduced, the SNCR optimal reaction temperature zone is downwards moved, the denitration reaction temperature window is enlarged, and the flue gas denitration rate is improved. In addition, the vanadium-titanium catalyst in the composite additive has the effect of promoting the flue gas denitration reaction, and can obviously promote the SNCR denitration reaction. Therefore, under the synergistic effect of several components, the vanadium-titanium composite additive greatly improves the high-temperature denitration efficiency of the oxidized pellet flue gas of the grate-rotary kiln.
Further, the main component of the SBA-15 mesoporous material is SiO 2 Has a two-dimensional straight pore channel hexagonal system structure, the pore wall thickness can reach 6.4nm, the thermal stability reaches 900 ℃, and the specific surface area is 700-1100m 2 Per gram, pore volume 0.6-1.3cm 2 And/g. The dispersibility in water and ethanol is good. In the invention, the SBA-15 mesoporous material is added to improve the contact area of the composite ammonia agent and NOx, thereby providing the ammonia agent and NOxA better reaction site, thereby accelerating the catalytic reduction reaction.
Further, the concentration of the aqueous ammonia is 15 to 35%, preferably 20 to 25%. The purity of the urea is more than or equal to 99 percent, and the purity is preferably more than or equal to 99.5 percent. The granularity of the urea is-0.074 mm or more than 90%, preferably-0.074 mm or more than 95%. The purity of NaCl is more than or equal to 99 percent, preferably the purity of NaCl is more than or equal to 99.5 percent. The granularity of NaCl is-0.074 mm not less than 90%, preferably-0.074 mm not less than 95%. The vanadium-titanium catalyst is selected from any V-TiO 2 Is a catalyst. The granularity of the vanadium-titanium catalyst is-0.074 mm or more than 80%, preferably-0.074 mm or more than 80%. The ethanol is absolute ethanol. The purity of the absolute ethyl alcohol is more than or equal to 99 percent, and the purity is preferably more than or equal to 99.7 percent.
Furthermore, the adsorption method adopting the nano zero-valent iron-kaolin composite material has the advantages of simple operation, flexible method, low energy consumption, wide material source and low cost. The nano zero-valent iron has strong reducibility, and the iron oxide generated on the surface has strong adsorptivity. However, because the easy agglomeration can affect the removal efficiency, the agglomeration can be reduced, the dispersibility of nano zero-valent iron can be improved, the surface area can be increased, and the reaction efficiency can be improved by loading the nano zero-valent iron on other solids. The kaolin (kaolinite) is a natural product, does not cause secondary pollution, has an environmental buffering effect, is stable in property and has certain adsorptivity, so that the kaolin is used as a carrier of nano zero-valent iron. Meanwhile, in the invention, the nano zero-valent iron-kaolin composite material can further improve the contact area of the ammonia agent and the NOx, and provides a better reaction place for the ammonia agent and the NOx, thereby accelerating the occurrence of catalytic reduction reaction.
In the present invention, the pipe diameter of the first pipe is 0.5 to 5m, preferably 0.8 to 4m, more preferably 1 to 3m. The mixing device is a box body, a sphere or a tank body, and the volume of the mixing device is 0.5-5m 3 Preferably 0.8-4m 3 More preferably 1-3m 3 . The width of the bellows (in the direction of the material run) is 0.1 to 5m, preferably 0.2 to 4m, more preferably 0.3 to 3m. The length of the transitional preheating section is 1-30m, preferably 3-20m, more preferably 5-15m. The above limitation is only thatThe preferred embodiments of the invention are not to be taken as limiting the invention.
In the invention, the compound ammonia agent is compounded by ammonia water, urea, soluble sodium salt, ethanol and vanadium-titanium catalyst. Wherein urea decomposes at high temperature to release ammonia gas, which is NH 3 The reducing agent can be slowly released in a certain period of time when the nitrogen oxides are reduced, so that the denitration reduction reaction is continuously carried out, and the conversion rate of the nitrogen oxides is improved. The soluble sodium salt and ethanol can generate a large number of active groups such as-H, -CH, -OH and the like through reaction or decomposition after entering high-temperature flue gas, and activate a denitration reaction chain at a lower temperature, so that the sensitivity of SNCR denitration to the reaction temperature is obviously reduced, the SNCR optimal reaction temperature zone is downwards moved, the denitration reaction temperature window is enlarged, and the flue gas denitration rate is improved. In addition, the vanadium-titanium catalyst in the composite ammonia agent has the effect of promoting the flue gas denitration reaction, and can obviously promote the SNCR denitration reaction. Therefore, under the synergistic effect of multiple components, the high-temperature denitration efficiency of the oxidized pellet flue gas of the grate-rotary kiln is greatly improved.
In the invention, vanadium-titanium compound ammonia agent is introduced into and fully mixed with high-NOx smoke under the atomizing condition of high pressure (0.1-2 MPa, preferably 0.15-1.5MPa, more preferably 0.18-1 MPa). Ensures the reaction time (generally 0.1 to 1 s) under the condition of high temperature (850 to 1100 ℃) to realize the reducing agent NH 3 Effectively reacts with NOx and is converted into N 2 And non-NOx toxic substances are added, and simultaneously under the catalysis of soluble sodium salt, the dosage of an ammonia agent reducer can be reduced, the denitration efficiency is improved, and the ammonia escape is reduced. The denitration rate can be improved from about 40% to 60% of the ammonia agent reducer.
Further, the invention also tests whether soluble sodium salt exists in the vanadium-titanium compound ammonia agent (NaCl is taken as an example here), and the effect comparison after flue gas denitration is carried out by adopting the system disclosed by the invention:
TABLE 1 influence of NaCl on denitration rate and ammonia slip
Figure BDA0002622035560000171
In the invention, the pellets are further utilized (the effect of the hematite pellets is poorer, the effect of the magnetite pellets is better as the oxidation degree of the magnetite pellets is higher, because of the new Fe 2 O 3 Better phase activity) layer carrier, and the synergistic catalysis of the vanadium-titanium catalyst and high molecular ethanol, further converting the residual NOx into N 2 And non-NOx toxic substances can be removed, so that the denitration rate is over 80 percent. Meanwhile, the system provided by the invention is also adopted to test the influence (high temperature) of the pellet ore and the catalyst on the flue gas denitration rate and ammonia escape:
TABLE 2 influence of pellets and catalysts on flue gas denitration rate and ammonia slip (high temperature)
Figure BDA0002622035560000181
According to the invention, the characteristics of the grate-rotary kiln oxidized pellet production system are not only utilized, the high-temperature denitration agent is sprayed on the transition section between the grate and the rotary kiln and/or the preheating section of the grate, so that low NOx emission in pellet production can be realized, the denitration rate can reach over 60-80%, and meanwhile, the dust removal system, the desulfurization system and the SCR denitration system are sequentially arranged at the tail end, so that the flue gas subjected to the vanadium-titanium compound ammonia agent denitration treatment is further subjected to dust removal, desulfurization and denitration treatment, the remarkable flue gas purification effect is achieved, the ammonia agent consumption is reduced, and the secondary pollution of ammonia escape to the environment is reduced.
In the present invention, "optionally" means either with or without, with or without selection, setting or not setting.
Compared with the prior art, the invention has the following beneficial technical effects:
1. the invention utilizes the waste heat in the waste gas through the waste gas of the air box at the rear section of the cyclic transition preheating section, and improves the heat utilization efficiency on the premise of not influencing the pellet yield and the pellet quality through the integral optimization of the pellet production process, thereby reducing the energy consumption of the pellet production process by about 3-5%. Meanwhile, the treatment capacity of the discharged waste gas is reduced, and the investment cost and the operation cost of waste gas treatment are reduced.
2. According to the invention, the hot waste gas of the bellows at the rear section of the transition preheating section is directly circulated into the rotary kiln as primary combustion-supporting air, so that on one hand, the waste heat of the flue gas can be fully utilized, the heat required by fuel combustion can be reduced, and meanwhile, the waste heat of part of the hot waste gas can be fully utilized to reduce the flame temperature in the rotary kiln, reduce the generation amount of thermal NOx and reduce the generation amount of NOx in the process. On the other hand, the oxygen content of the primary mixed wind (the oxygen content in normal air is about 21 percent, and the oxygen content in circulated hot exhaust gas is about 18 percent) can be reduced, so that the generation amount of NOx is reduced (namely, the generation amount of thermal NOx is reduced from the source).
3. According to the invention, through circulating the hot exhaust gas with high NOx content, on one hand, the NOx content in the exhaust gas is reduced, on the other hand, the NOx in the exhaust gas can be ensured to be removed by SNCR and SCR denitration in the preheating section, and the NOx content in the exhaust gas is reduced again, so that the NOx concentration in the exhaust gas of the grate machine-rotary kiln pellet production procedure specified in the opinion about ultra-low emission of the propulsion implementation steel industry is lower than 50mg/m 3 Is not limited.
3. A process (SNCR technology) and end control (SCR technology) coupling denitration mathematical model is established; by applying the model, the denitration process parameters can be optimized, and the investment, operation and maintenance costs of denitration of the pellet mill can be reduced.
4. The method can effectively control the SNCR-SCR denitration system of the chain grate machine-rotary kiln to achieve the most economical ammonia injection amount. The SNCR ammonia injection amount is guaranteed to be minimum, the activity duration of the SCR catalyst can be prolonged to the greatest extent, simultaneously the NOx ultra-low emission condition is met, the investment and maintenance cost is reduced, and the economic benefit is remarkably improved.
5. The control method disclosed by the invention is simple to operate, convenient to establish the parameter sources of the SNCR-SCR coupling denitration mathematical model, free from additionally adding large-scale control equipment and a large number of operators, and good in popularization value.
6. The composite additive provided by the invention takes urea, soluble sodium salt and ethanol as main raw materials, and a small amount of vanadium-titanium catalyst and SBA-15 material are matched to form the composite additive when in use, so that the consumption of an ammonia agent reducer can be reduced, the denitration efficiency can be improved, and the ammonia escape can be reduced.
7. The composite ammonia agent provided by the invention is prepared from ammonia water, urea, soluble sodium salt and ethanol serving as main raw materials, and a small amount of vanadium-titanium catalyst and nano zero-valent iron-kaolin material are matched to form the composite ammonia agent, so that the high-temperature denitration efficiency of the grate-rotary kiln oxidized pellet flue gas can be effectively improved, the flue gas denitration rate can reach 80%, and the difficulty and cost of subsequent flue gas treatment are greatly reduced.
8. The raw materials added into the composite additive or the composite ammonia agent have the effects of slow release of ammonia components, catalytic reduction and the like, can realize the denitration effect under the condition of higher ammonia nitrogen ratio under the condition of lower ammonia nitrogen ratio, improve the use efficiency of ammonia water during flue gas denitration, reduce the ammonia nitrogen ratio and ammonia escape, and reduce the ammonia escape concentration to less than 2mg/m 3 Greatly reduces secondary pollution.
9. The composite additive and the composite ammonia agent raw materials are all from the market, and have the advantages of wide raw material sources, low cost, simple preparation process and the like, and are easy to realize large-scale production.
10. The process adopts the SNCR denitration mechanism in the process and combines the processes of terminal dedusting, desulfurization and SCR denitration mechanism, so that the flue gas dedusting, desulfurization and denitration effects are good, the ammonia escape amount is small, the process flow is simple, the investment is low, and the method is suitable for popularization.
Drawings
FIG. 1 is a block diagram of a flue gas treatment system according to the present invention.
Fig. 2 is a block diagram of a prior art flue gas treatment system.
FIG. 3 is a graph of denitration catalyst activity versus age in different denitration systems.
FIG. 4 is a graph of investment and maintenance costs versus various denitration processes.
FIG. 5 is a block diagram of a flue gas treatment system with a circular cooler according to the present invention.
FIG. 6 is a control flow chart of the method for dividing the bellows of the transitional preheating section.
FIG. 7 is a control flow diagram of the SNCR-SCR coupled denitration mathematical model method of the present invention.
FIG. 8 is a diagram showing the distribution structure of a transition preheating section bellows of the flue gas circulation coupling treatment system of the present invention.
FIG. 9 is a diagram showing the trend connection structure of a transition preheating section bellows of the flue gas circulation coupling treatment system of the present invention.
Fig. 10 is a block diagram of a flue gas treatment system having an SNCR denitration device according to the present invention.
Fig. 11 is a block diagram of a flue gas treatment system with a mixing device according to the present invention.
FIG. 12 shows the initial NOx removal rate y before SNCR denitration in example 4 of the method of the present invention x Is fit to the graph.
FIG. 13 shows the denitration rate y of the ammonia nitrogen ratio of SNCR ammonia injection in example 4 of the method of the present invention m Is fit to the graph.
FIG. 14 shows the denitration rate y of the window temperature of SNCR ammonia injection in example 4 of the method of the present invention t Is fit to the graph.
FIG. 15 shows the NOx removal rate y of the NOx concentration before SCR denitration in example 4 of the method of the present invention z Is fit to the graph.
FIG. 16 shows the denitration rate y of the ammonia nitrogen ratio of SCR ammonia injection in example 4 of the method of the present invention n Is fit to the graph.
FIG. 17 shows the denitration rate y of the number of SCR catalyst beds in example 4 of the method of the present invention c Is fit to the graph.
Reference numerals: 1: a chain grate machine; 2: a rotary kiln; 3: a ring cooler; 4: a dust removal device; 5: an SCR denitration device; 6: a desulfurizing device; 7: a wind box; 8: SNCR denitration device; 9: a mixing device; UDD: a blast drying section; DDD: an air draft drying section; TPH: a transitional preheating section; PH: a preheating section; 701: switching the valve; 801: a first spraying device; 802: a second spraying device; 803: a high-pressure atomization mixing device; c1: ring cooling for one section; c2: a second ring cooling section; and C3: ring cooling three sections; l1: a first pipe; l2: a second pipe; l3: a third conduit; l4: a fourth conduit; l5: a fifth pipe; l6: a sixth conduit; l7: a seventh pipe; l8: an eighth conduit; l9: a ninth conduit; l10: a tenth pipe; l11: an eleventh conduit; l12: a twelfth duct; h: a NOx concentration detection device; s1: a vanadium-titanium catalyst delivery tube; s2: ammonia water conveying pipe; s3: a urea delivery pipe; s4: a soluble sodium salt delivery tube; s5: an ethanol delivery pipe; s6: a nano zero-valent iron or SBA-15 conveying pipeline; f1: a first fan; f2: a second fan; f3: a third fan; f4: and a fourth fan.
Detailed Description
The following examples illustrate the technical aspects of the invention, and the scope of the invention claimed includes but is not limited to the following examples.
According to a first embodiment of the invention, a pellet flue gas treatment system based on rotary kiln primary circulation air intake is provided, and comprises a chain grate machine 1, a rotary kiln 2 and an SCR denitration device 5. According to the trend of the materials, the chain grate machine 1 is sequentially provided with a blowing drying section UDD, an air draft drying section DDD, a transitional preheating section TPH and a preheating section PH. The air outlet of the rotary kiln 2 is communicated with the air inlet of the preheating section PH through a first pipeline L1. The rotary kiln 2 is provided with a central burner 201. The central burner 201 communicates with a fuel conduit 203. The fuel pipeline 203 is also provided with a primary combustion-supporting air pipe 202. The air outlet of the preheating section PH is communicated with the air inlet of the induced draft drying section DDD through a second pipeline L2. The air outlet of the transition preheating section TPH is divided into a front section air outlet and a rear section air outlet. The air outlet of the rear section of the transition preheating section TPH is communicated to the air inlet of the primary combustion-supporting air pipe 202 through a third pipeline L3. And an air outlet of the front section of the transition preheating section TPH is communicated with a fourth pipeline L4. And an air outlet of the air draft drying section DDD is communicated to a fourth pipeline L4 through a fifth pipeline L5. And the second pipeline L2 is provided with an SCR denitration device 5.
Preferably, the bottom of the transitional preheating section TPH is provided with J bellows 7,J, and the air outlet of each bellows 7 of the J bellows 7 is simultaneously connected to the third pipeline L3 and the fourth pipeline L4 through a switching valve 701. The outlet of each bellows 7 is controlled by the switching valve 701 to communicate only with the third duct L3 or only with the fourth duct L4.
Preferably, the numbers of J bellows 7 in the transition preheating section TPH are 1,2,3, J in sequence according to the trend of the materials. Of these, the 1 st to j-th windboxes 7 are used as front-stage windboxes and are all communicated with the fourth duct L4. The (j+1) th to the J-th windboxes 7 are used as the rear-stage windboxes and are all communicated with the third duct L3. J is more than or equal to 1 and less than or equal to J.
Preferably, J is 1 to 50, preferably 2 to 20, more preferably 2 to 10.
Preferably, the system further comprises a circular cooler 3. According to the trend of the materials, the annular cooler 3 is sequentially provided with an annular cooling first section C1, an annular cooling second section C2 and an annular cooling third section C3. An air outlet of the annular cooling first section C1 is communicated to an air inlet of the rotary kiln 2 through a sixth pipeline L6. And an air outlet of the annular cooling two-section C2 is communicated with an air inlet of the transitional preheating section PTH through a seventh pipeline L7. And an air outlet of the annular cooling three-section C3 is communicated with an air inlet of the forced air drying section UDD through an eighth pipeline L8. The air outlet of the forced air drying section UDD is communicated to a chimney through a ninth pipeline L9.
Preferably, the system further comprises an SNCR denitrification device 8. The SNCR denitration device 8 is arranged in the preheating section PH and/or the first pipeline L1.
Preferably, the system further comprises a NOx concentration detection means H, which is arranged in the windbox 7. And the J bellows 7 at the bottom of the transition preheating section TPH are respectively and independently provided with a NOx concentration detection device H.
Preferably, the SNCR denitration device 8 includes a first spraying device 801 and a high-pressure atomization mixing device 803. The first spraying device 801 is arranged in the preheating section PH and is connected with the high-pressure atomization mixing device 803 through a tenth pipeline L10.
Preferably, the SNCR denitration device 8 further includes a second spraying device 802. The second spraying device 802 is disposed in the first pipeline L1 and is connected to the high-pressure atomized material mixing device 803 through an eleventh pipeline L11.
Preferably, the eleventh duct L11 is a bypass duct branched from the tenth duct L10.
Preferably, the high-pressure atomization mixing device 803 is provided with a vanadium-titanium catalyst conveying pipe S1, an ammonia conveying pipe S2, a urea conveying pipe S3, a soluble sodium salt conveying pipe S4, an ethanol conveying pipe S5 and a nano zero-valent iron or SBA-15 conveying pipeline S6.
Preferably, the system further comprises a mixing device 9. The mixing device 9 is provided with a vanadium-titanium catalyst conveying pipe S1, an ammonia conveying pipe S2, a urea conveying pipe S3, a soluble sodium salt conveying pipe S4 and a nano zero-valent iron or SBA-15 conveying pipeline S6. The mixing device 9 is communicated with the high-pressure atomization mixing device 803 through a twelfth pipeline L12.
Preferably, the system further comprises a dust removal device 4, said dust removal device 4 being arranged on the second conduit L2 and upstream of the SCR denitration device 5. Preferably, the fourth duct L4 is also provided with a dust removal device 4.
Preferably, the third duct L3 and the ninth duct L9 are each optionally provided with or without a dust-removing device 4.
Preferably, the system further comprises a desulfurization device 6. The desulfurization device 6 is disposed on the fourth pipe L4. Preferably, a dust removing device 4 is further provided on the fourth pipe L4, and the dust removing device 4 is located upstream of the desulfurization device 6.
According to a second embodiment of the present invention, there is provided a flue gas treatment process or a process for flue gas treatment using the grate-rotary kiln pellet flue gas recirculation treatment system of the first embodiment, the process comprising the steps of:
1) According to the trend of the materials, raw pellets enter the chain grate machine 1 and are conveyed into the rotary kiln 2 for oxidative roasting after sequentially passing through a blowing drying section UDD, an exhausting drying section DDD, a transitional preheating section TPH and a preheating section PH on the chain grate machine 1.
2) According to the flow direction of the hot air, the hot air in the rotary kiln 2 is conveyed into the preheating section PH through the first pipeline L1. The hot air exhausted from the preheating section PH is firstly subjected to dust removal treatment by a dust removal device 4, and then is subjected to SCR denitration treatment by an SCR denitration device 5 and then is conveyed into an exhaust drying section DDD. The hot air exhausted from the DDD and TPH front-section bellows of the induced draft drying section is firstly dedusted by a dedusting device 4, and then is exhausted after being desulfurized by a desulfurizing device 6. The hot air discharged from the bellows at the rear section of the transition preheating section TPH is subjected to dust removal treatment by the dust removal device 4 and then is conveyed into the primary combustion-supporting air pipe 202.
Preferably, the process further comprises the steps of:
3) In the annular cooler 3, hot air discharged from the annular cooling section C1 is sent to the rotary kiln 2 through the sixth duct L6. The hot air discharged from the annular cooling two-stage C2 is conveyed into the transitional preheating stage TPH through a seventh pipeline L7. The hot air discharged from the annular cooling three sections C3 is conveyed into the forced air drying section UDD through an eighth pipeline L8.
4) Spraying an SNCR catalyst in the preheating section PH and/or in a first pipeline L1 connected between an air inlet of the preheating section PH and an air outlet of the rotary kiln 2, and carrying out SNCR denitration reaction on NOx and the SNCR catalyst in hot air in the preheating section PH and/or the first pipeline L1.
5) The hot air discharged from the forced air drying section UDD is optionally discharged via a ninth conduit L9 after dust removal treatment.
Preferably, the division mode of the front section bellows and the rear section bellows of the transition preheating section TPH specifically comprises the following steps:
301 Real-time detection of the concentration of NOx in the flue gas in J bellows 7 by means of the mutually independent NOx concentration detection devices H arranged in J bellows 7, which are in turn H 1 ,H 2 ,…,H J ,mg/m 3
302 Calculating the average NOx concentration in J of said windboxes 7 in the transitional preheating section TPH): h Average of =(H 1 +H 2 +…+H J ) J. Then successively judging the concentration of NOx and H in J of said windboxes 7 Average of Is of a size of (a) and (b).
303 When H j <H Average of And H is j+1 ≥H Average of The 1 st to j-th windboxes 7 are the front windboxes of the transitional preheating section TPH. The (j+1) th to the J-th windboxes 7 are the latter windboxes of the transitional preheating section TPH.
After the dispensing of the bellows 7 is completed, return to step 301) continues the detection.
Preferably, the process further comprises the steps of:
a) An SNCR denitration system is arranged in the preheating section PH and/or the first pipeline L1 between the preheating section PH and the rotary kiln 2. Meanwhile, an SCR denitration system is arranged behind the PH air outlet of the preheating section. And establishing an SNCR-SCR coupling denitration mechanism.
b) And detecting and collecting parameter information of the initial concentration of NOx before SNCR denitration, the ammonia nitrogen ratio of SNCR ammonia injection, the window temperature of SNCR ammonia injection, the concentration of NOx before SCR denitration, the ammonia nitrogen ratio of SCR ammonia injection and the number of layers of the SCR catalyst bed in real time.
c) And establishing an SNCR-SCR coupling denitration mathematical model according to the detected parameter information.
d) And calculating and adjusting the minimum SNCR ammonia injection amount according to the SNCR-SCR coupling denitration mathematical model, so that the NOx content in the flue gas meets the emission condition.
Preferably, the SNCR-SCR coupling denitration mathematical model is as follows:
y=A·y x +B·y m +C·y t +D·y z +E·y n +F·y c .. formula I.
In the formula I, y is the SNCR-SCR coupling denitration rate. y is x Is the denitration rate based on the initial concentration of NOx before SNCR denitration. y is m Is the denitration rate based on the ammonia nitrogen ratio of SNCR ammonia injection. y is t Is the denitration rate based on the window temperature of SNCR ammonia injection. y is z Is the denitration rate based on the NOx concentration before SCR denitration. y is n Is the denitration rate based on the ammonia nitrogen ratio of SCR ammonia injection. y is c Is the denitration rate based on the number of SCR catalyst beds. A is the influence factor weight of the initial concentration x of NOx before SNCR denitration. B is the influence factor weight of ammonia nitrogen ratio m of SNCR ammonia injection. C is the influence factor weight of the window temperature t of SNCR ammonia injection. D is the influence factor weight of the NOx concentration z before SCR denitration. E is the influence factor weight of ammonia nitrogen ratio n of SCR ammonia injection. F is the influence factor weight of the number c of the SCR catalyst beds. And a+b+c+d+e+f=1.
Preferably, A is from 0.02 to 0.4, preferably from 0.05 to 0.2.B is 0.1 to 0.8, preferably 0.2 to 0.5.C is 0.05-0.5. Preferably 0.1 to 0.3.D is 0.01-0.3, preferably 0.02-0.2.E is 0.05 to 0.4, preferably 0.1 to 0.3.F is 0.05 to 0.5, preferably 0.1 to 0.4.
Preferably, the denitration rate y is based on the initial concentration of NOx before SNCR denitration x The method comprises the following steps:
Figure BDA0002622035560000231
in the formula II, x is the initial concentration of NOx before SNCR denitration, mg/m 3 . i is the power of x. I is more than or equal to 0 and less than or equal to N x 。N x To the highest power of x. a, a xi The coefficient to the ith power of x.
Preferably, the denitration rate y based on the ammonia nitrogen ratio of SNCR ammonia injection m The method comprises the following steps:
Figure BDA0002622035560000232
in the formula III, m is the ammonia nitrogen ratio of SNCR ammonia injection. Beta is the power of m. Beta is more than or equal to 0 and less than or equal to N m 。N m To the highest power of m. a, a The coefficient to the power of m.
Preferably, the denitration rate y based on the window temperature of SNCR ammonia injection t The method comprises the following steps:
Figure BDA0002622035560000233
in formula IX, t is the window temperature of SNCR ammonia injection, DEG C. Delta is the power of t. Delta is more than or equal to 0 and less than or equal to N t 。N t To the highest power of t. a, a The coefficient to the power delta of t.
Preferably, the denitration rate y is based on the NOx concentration before SCR denitration z The method comprises the following steps:
Figure BDA0002622035560000241
in the formula V, z is the concentration of NOx before SCR denitration, mg/m 3 . Gamma is the power of z. Gamma is more than or equal to 0 and less than or equal to N z 。N z To the highest power of z. a, a The coefficient to the power of z.
Preferably, the denitration rate y based on the ammonia nitrogen ratio of SCR ammonia injection n The method comprises the following steps:
Figure BDA0002622035560000242
in the formula VI, n is the ammonia nitrogen ratio of SCR ammonia injection. Lambda is the power of n. Lambda is more than or equal to 0 and less than or equal to N n 。N n To the highest power of n. a, a Is the coefficient to the lambda th power of n.
Preferably, the denitration rate y based on the number of SCR catalyst beds c The method comprises the following steps:
Figure BDA0002622035560000243
in formula VII, c is the number of SCR catalyst beds. θ is the power of c. θ is more than or equal to 0 and less than or equal to N c 。N c To the highest power of c. a, a The coefficient to the θ th power of c.
Preferably, formula II-VII is substituted into formula I to obtain:
Figure BDA0002622035560000244
further conversion of formula VIII gives formula I.
Preferably, step d) is specifically:
d1 When x.1-y is less than or equal to 50mg/m 3 When (1). Reducing ammonia nitrogen ratio of SNCR ammonia injection, m' =m-STEP m . Iterative calculations are carried out according to formula VIII until x.cndot.1-y > 50mg/m are exactly satisfied 3 . Then the value of m at this time is executed.
d2 When x.1-y > 50mg/m 3 When (1). Increasing the ammonia nitrogen ratio of SNCR ammonia injection, m' =m+STEP m . Iterative calculations are carried out according to formula VIII until x.cndot.1-y is just less than or equal to 50mg/m 3 . The value of m' at this time is then performed.
Wherein: m is the ammonia nitrogen ratio of SNCR ammonia injection at the current calculation. m' is the ammonia nitrogen ratio of SNCR ammonia spraying calculated in the next step. STEP (STEP) m The value of (2) is 0.01-0.5. Preferably 0.03 to 0.3. More preferably 0.05 to 0.1.
Preferably, the SNCR catalyst is an SNCR catalyst containing a composite additive comprising or consisting of: urea, soluble sodium salt, ethanol, vanadium-titanium catalyst, SBA-15. Or alternatively
The SNCR catalyst is a compound ammonia agent, and the compound ammonia agent comprises or consists of the following components: ammonia water, urea, soluble sodium salt, ethanol, vanadium-titanium catalyst and nano zero-valent iron-kaolin material.
Preferably, the composite additive in the SNCR catalyst containing the composite additive comprises the following components:
40-70 parts by weight, preferably 45-65 parts by weight, more preferably 50-60 parts by weight of urea.
The soluble sodium salt is 10 to 30 parts by weight, preferably 12 to 25 parts by weight, more preferably 15 to 20 parts by weight.
8-28 parts by weight of ethanol, preferably 10-25 parts by weight, more preferably 12-22 parts by weight.
The vanadium-titanium catalyst is 1 to 12 parts by weight, preferably 2 to 10 parts by weight, more preferably 3 to 8 parts by weight.
SBA-15 is 0.1 to 5 parts by weight, preferably 0.3 to 4 parts by weight, more preferably 0.5 to 3 parts by weight.
Preferably, the compound ammonia agent comprises the following components:
60 to 90 parts by weight, preferably 65 to 85 parts by weight, more preferably 70 to 80 parts by weight of aqueous ammonia.
8-30 parts by weight, preferably 10-25 parts by weight, more preferably 15-25 parts by weight of urea.
The soluble sodium salt is 0.05 to 1 part by weight, preferably 0.1 to 0.8 part by weight, more preferably 0.15 to 0.5 part by weight.
Ethanol 0.05 to 1.2 parts by weight, preferably 0.1 to 1 part by weight, more preferably 0.15 to 0.8 part by weight.
The vanadium-titanium catalyst is 0.01 to 0.1 part by weight, preferably 0.02 to 0.08 part by weight, more preferably 0.03 to 0.05 part by weight.
The nano zero-valent iron-kaolin material is 0.5 to 10 parts by weight, preferably 0.8 to 8 parts by weight, more preferably 1 to 6 parts by weight.
Preferably, in step 4), the specific method of spraying the SNCR catalyst is: to the denitration reducing agent (for example, ammonia water having a concentration of 20% to 25%), 0.1 to 2.0% by weight (preferably 0.3 to 1.2% by weight, more preferably 0.5 to 1.0% by weight) of a complex additive is added based on the total addition amount of the denitration reducing agent. Stirring and mixing uniformly. And then spraying the SNCR catalyst containing the composite additive after being uniformly mixed in the preheating section PH and/or in a first pipeline L1 connected between an air inlet of the preheating section PH and an air outlet of the rotary kiln 2.
Or the compound ammonia agent is directly sprayed in the preheating section PH and/or in a first pipeline L1 connected between the inlet of the preheating section PH and the outlet of the rotary kiln 2.
Preferably, the preparation method of the compound ammonia agent comprises the following steps: firstly, urea, soluble sodium salt, vanadium-titanium catalyst and nano zero-valent iron-kaolin material are all ground into powder. And then uniformly stirring and mixing powdery urea, soluble sodium salt, vanadium-titanium catalyst and nano zero-valent iron-kaolin material according to a proportion to obtain a powder mixture. Finally, the ethanol is measured separately according to the proportion to obtain the wet material. And adding the wet material and the powder mixture into ammonia water, and uniformly mixing to obtain the composite ammonia agent.
Preferably, the vanadium-titanium catalyst is selected from any V-TiO 2 Is a catalyst. The granularity of the vanadium-titanium catalyst is-0.074 mm or more than 80%, preferably-0.074 mm or more than 90%.
Preferably, the soluble sodium salt is NaCl or Na 2 CO 3
Preferably, the desulfurization treatment is dry desulfurization, semi-dry desulfurization or wet desulfurization. The desulfurization treatment is preferably performed using lime.
Preferably, the dust removing treatment is a bag dust removing treatment or an electric dust removing treatment.
Example 1
As shown in fig. 1, a grate-rotary kiln pellet flue gas circulation treatment system comprises a grate 1, a rotary kiln 2 and an SCR denitration device 5. According to the trend of the materials, the chain grate machine 1 is sequentially provided with a blowing drying section UDD, an air draft drying section DDD, a transitional preheating section TPH and a preheating section PH. The rotary kiln 2 is provided with a central burner 201. The central burner 201 communicates with a fuel conduit 203. The fuel pipeline 203 is also provided with a primary combustion-supporting air pipe 202. The air outlet of the rotary kiln 2 is communicated with the air inlet of the preheating section PH through a first pipeline L1. The air outlet of the preheating section PH is communicated with the air inlet of the induced draft drying section DDD through a second pipeline L2. The air outlet of the transition preheating section TPH is divided into a front section air outlet and a rear section air outlet. The air outlet of the rear section of the transition preheating section TPH is communicated to the air inlet of the primary combustion-supporting air pipe 202 through a third pipeline L3. And an air outlet of the front section of the transition preheating section TPH is communicated with a fourth pipeline L4. And an air outlet of the air draft drying section DDD is communicated to a fourth pipeline L4 through a fifth pipeline L5. And the second pipeline L2 is provided with an SCR denitration device 5.
Example 2
Example 1 was repeated, and as shown in fig. 7 and 8, the bottom of the transitional preheating section TPH was provided with J windboxes 7,J, the air outlet of each of which was simultaneously connected to the third duct L3 and the fourth duct L4 by a switching valve 701. The outlet of each bellows 7 is controlled by the switching valve 701 to communicate only with the third duct L3 or only with the fourth duct L4.
According to the trend of the materials, the numbers of J bellows 7 in the transition preheating section TPH are 1,2,3, J in sequence. Of these, the 1 st to j-th windboxes 7 are used as front-stage windboxes and are all communicated with the fourth duct L4. The (j+1) th to the J-th windboxes 7 are used as the rear-stage windboxes and are all communicated with the third duct L3. J is more than or equal to 1 and less than or equal to J. J is 1-50.
Example 3
Example 2 is repeated except that the system further comprises a circular cooler 3. According to the trend of the materials, the annular cooler 3 is sequentially provided with an annular cooling first section C1, an annular cooling second section C2 and an annular cooling third section C3. An air outlet of the annular cooling first section C1 is communicated to an air inlet of the rotary kiln 2 through a sixth pipeline L6. And an air outlet of the annular cooling two-section C2 is communicated with an air inlet of the transitional preheating section PTH through a seventh pipeline L7. And an air outlet of the annular cooling three-section C3 is communicated with an air inlet of the forced air drying section UDD through an eighth pipeline L8. The air outlet of the forced air drying section UDD is communicated to a chimney through a ninth pipeline L9.
Example 4
Example 3 was repeated except that the system also included an SNCR denitrification facility 8. The SNCR denitration device 8 is arranged in the preheating section PH and the first pipeline L1.
Example 5
Example 4 is repeated except that the system further comprises a NOx concentration detection means H, which is provided in the windbox 7. The J bellows 7 are provided with NOx concentration detection means H.
Example 6
Example 5 is repeated except that the SNCR denitration device 8 includes a first spraying device 801 and a high-pressure atomization compounding device 803. The first spraying device 801 is arranged in the preheating section PH and is connected with the high-pressure atomization mixing device 803 through a tenth pipeline L10.
The SNCR denitration device 8 further includes a second spraying device 802. The second spraying device 802 is disposed in the first pipeline L1 and is connected to the high-pressure atomized material mixing device 803 through an eleventh pipeline L11.
The eleventh pipe L11 is a bypass pipe branched from the tenth pipe L10.
Example 7
Example 6 was repeated except that the high-pressure atomization mixing device 803 was provided with a vanadium-titanium catalyst delivery pipe S1, an ammonia water delivery pipe S2, a urea delivery pipe S3, a soluble sodium salt delivery pipe S4, an ethanol delivery pipe S5, and a nano zero-valent iron or SBA-15 delivery pipe S6.
Example 8
Example 7 is repeated except that the system further comprises a mixing device 9. The mixing device 9 is provided with a vanadium-titanium catalyst conveying pipe S1, an ammonia conveying pipe S2, a urea conveying pipe S3, a soluble sodium salt conveying pipe S4 and a nano zero-valent iron or SBA-15 conveying pipeline S6. The mixing device 9 is communicated with the high-pressure atomization mixing device 803 through a twelfth pipeline L12.
Example 9
Example 8 is repeated except that the system further comprises a dust removal device 4, said dust removal device 4 being arranged on the second conduit L2 and upstream of the SCR denitration device 5. The fourth pipeline L4 is also provided with a dust removing device 4.
Example 10
Example 9 is repeated except that the dust removing device 4 is optionally provided or not provided on both the third duct L3 and the ninth duct L9.
Example 11
Example 10 is repeated except that the system further comprises a desulphurisation device 6. The desulfurization device 6 is disposed on the fourth pipe L4. A dust removing device 4 is further provided on the fourth pipe L4, and the dust removing device 4 is located upstream of the desulfurization device 6.
Application example 1
Aiming at the pellet preparation process of the chain grate machine-rotary kiln-ring cooler, the adopted raw material is magnetite, SNCR denitration is adopted in a preheating section, and a SNCR catalyst adopts a compound ammonia agent (the molar ratio of ammonia nitrogen is 1.1:1; the compound ammonia agent consists of 78wt% of ammonia water, 20.45wt% of urea and Na 2 CO 3 0.5wt%, 1.0wt% of ethanol and 0.05wt% of vanadium-titanium catalyst; the average concentration of NOx in the exhaust gas of the transition preheating section is 70ppm, the exhaust gas of the rear-section bellows with the concentration of NOx higher than 70ppm of the transition preheating section is circulated to the rotary kiln as primary combustion air, the exhaust gas of the rear-section bellows accounts for 30% of the total amount of the exhaust gas of the transition preheating section, the average temperature of the circulating exhaust gas is 230 ℃, the circulating exhaust gas of the rear-section bellows is pumped into a primary combustion air pipe of a central burner by a circulating fan after being dedusted by a plurality of pipes, the introduced air quantity (standard condition) of a cooling section is kept unchanged from that of the exhaust gas before circulation, and part of hot air (the discharged hot air quantity is equal to the circulating air quantity of the transition preheating section circulated to the rotary kiln) is discharged outside of hot air discharged from a section of circular cooling; the cooling second section improves the air quantity by 3 percent, the cooling third section improves the air quantity by 5 percent, and the temperature of the pellets discharged from the annular cooler is 146 ℃; after the flue gas of the air box at the rear section of the transition preheating section is circulated, the coal injection amount of the rotary kiln is reduced by 3%, and the O of the gas in the rotary kiln is reduced 2 The content is 18 percent, and the temperature of the waste gas from the preheating section is 309 ℃; the waste gas of the preheating section pipeline is dedusted by a multi-pipe deduster, and the dust content of the waste gas is reduced to 15mg/m 3 Then SCR denitration treatment is adopted, and a medium Wen Fanji catalyst is adopted as the SCR catalyst. The external detection is carried out by adopting the invention to circularly couple the hot waste gas with the non-heating SCR denitration The NOx emission concentration of the exhaust gas is reduced to 34mg/Nm 3 Reaching the ultra-low emission condition.
Application example 2
Aiming at the technology of preparing pellets by a chain grate machine-rotary kiln-ring cooling machine, the adopted raw materials are 80 percent of magnetite and 20 percent of hematite, the average concentration of NOx in waste gas of a transitional preheating section is 76ppm, SNCR denitration is adopted in the preheating section, a SNCR catalyst adopts a compound ammonia agent (the molar ratio of ammonia nitrogen is 1.1:1; the compound ammonia agent consists of 78 weight percent of ammonia water, 20.45 weight percent of urea and Na 2 CO 3 0.5wt%, 1.0wt% of ethanol and 0.05wt% of vanadium-titanium catalyst; circulating the rear-section bellows waste gas with the concentration of NOx higher than 76ppm in the transitional preheating section to the rotary kiln as primary combustion supporting air, wherein the rear-section bellows waste gas accounts for 40% of the total amount of the transitional preheating section waste gas, the average temperature of the circulating waste gas is 220 ℃, the circulating waste gas of the rear-section bellows is pumped into a primary combustion supporting air pipe of a central burner by a circulating fan after multi-pipe dust removal, the air quantity (standard condition) led in by the cooling section is kept unchanged from that before circulation, and part of hot air (the external exhaust air quantity is equal to that of the circulating air quantity of the transitional preheating section to the rotary kiln) is discharged outside in hot air discharged by the annular cooling section; the cooling second section improves the air quantity by 5%, the cooling third section improves the air quantity by 5%, and the temperature of the pellets discharged from the annular cooler is 140 ℃; after the flue gas of the air box at the rear section of the transition preheating section is circulated, the coal injection amount of the rotary kiln is reduced by 4%, and the O of the gas in the rotary kiln is reduced 2 The content is 18.2 percent, and the temperature of the waste gas from the preheating section is 312 ℃; the waste gas of the preheating section pipeline is dedusted by a multi-pipe deduster, and the dust content of the waste gas is reduced to 15mg/m 3 Then SCR denitration treatment is adopted, and a medium Wen Fanji catalyst is adopted as the SCR catalyst. By adopting the invention to circularly couple the hot waste gas with the non-heating SCR denitration, the NOx emission concentration of the discharged waste gas is detected to be reduced to 32mg/Nm 3 Reaching the ultra-low emission condition.
Application example 3
Aiming at the technology of preparing pellets by a chain grate machine-rotary kiln-ring cooling machine, the adopted raw materials are 70 percent of magnetite and 30 percent of hematite, the average concentration of NOx in waste gas of a transitional preheating section is 81ppm, SNCR denitration is adopted in the preheating section, and an SNCR catalyst adopts a catalyst containing a composite additive (ammonia nitrogen mol)The ratio is 1.1:1; the composite additive comprises the following components: 52wt% of urea, 20wt% of NaCl, 20wt% of ethanol and 8wt% of vanadium-titanium catalyst; circulating the rear-section bellows waste gas with the NOx concentration higher than 81ppm in the transitional preheating section to the rotary kiln as primary combustion-supporting air, wherein the rear-section bellows waste gas accounts for 50% of the total amount of the transitional preheating section waste gas, the average temperature of the circulating waste gas is 200 ℃, the circulating waste gas of the rear-section bellows is pumped into a primary combustion-supporting air pipe of a central burner by a circulating fan after multi-pipe dust removal, the air quantity (standard condition) led in by the cooling section is kept unchanged from that before circulation, and part of hot air is discharged outside in hot air discharged by the annular cooling section (the discharged hot air quantity equals to that of circulating air in the transitional preheating section to the rotary kiln); the cooling second section improves the air quantity by 5 percent, the cooling third section improves the air quantity by 8 percent, and the temperature of the pellets discharged from the annular cooler is 146 ℃; after the flue gas of the air box at the rear section of the transition preheating section is circulated, the coal injection amount of the rotary kiln is reduced by 5%, and O of the gas in the rotary kiln is reduced 2 The content is 18.4 percent, and the temperature of the waste gas from the preheating section is 335 ℃; the waste gas of the preheating section pipeline is dedusted by a multi-pipe deduster, and the dust content of the waste gas is reduced to 15mg/m 3 Then SCR denitration treatment is adopted, and a medium Wen Fanji catalyst is adopted as the SCR catalyst. By adopting the invention to circularly couple the hot waste gas with the non-heating SCR denitration, the NOx emission concentration of the discharged waste gas is detected to be reduced to 31mg/Nm 3 Reaching the ultra-low emission condition.
Comparative example 1
Aiming at the technology of preparing pellets by a chain grate machine, a rotary kiln and a ring cooler, wherein magnetite is adopted as a raw material, the average temperature of circulating waste gas is 230 ℃, the first cooling section is maintained, the second cooling section is maintained, the cooling air quantity is unchanged (under standard conditions), and the temperature of the pellets discharged from the ring cooler is 143 ℃; and directly circulating the exhaust gas of the preheating section pipeline to the exhaust drying section, and then sequentially carrying out dust removal treatment, desulfurization treatment and SCR denitration treatment on the hot air output by the exhaust drying section and the transitional preheating section, wherein a medium Wen Fanji catalyst is adopted as the catalyst. The dust concentration of the discharged waste gas is detected to be 15mg/m 3 NOx emission concentration was 61mg/Nm 3
Comparative example 2
Pellet preparation for chain grate machine-rotary kiln-ring coolerThe technology comprises the steps of adopting raw materials of 70% magnetite and 30% hematite circulation waste gas, wherein the average temperature is 240 ℃, maintaining the first cooling section, the second cooling section and the third cooling air volume unchanged (under standard conditions), and the temperature of pellets discharged from a circular cooler is 140 ℃; and directly circulating the exhaust gas of the preheating section pipeline to the exhaust drying section, and then sequentially carrying out dust removal treatment, desulfurization treatment and SCR denitration treatment on the hot air output by the exhaust drying section and the transitional preheating section, wherein a medium Wen Fanji catalyst is adopted as the catalyst. The dust concentration of the discharged waste gas is detected to be 17mg/m 3 NOx emission concentration was 65mg/Nm 3
Application example 4
The SNCR method NOx removal system is arranged for a chain grate machine-rotary kiln NOx removal system, mainly considers the influence of initial concentration (x) of NOx before SNCR denitration, ammonia nitrogen ratio (m) of SNCR ammonia injection and window temperature (t) of SNCR ammonia injection on the denitration rate, and determines an SNCR denitration efficiency formula through data analysis and data curve fitting:
(1) Determination of denitration Rate y based on initial concentration of NOx before SNCR denitration x The method comprises the following steps:
Figure BDA0002622035560000291
NOx initial concentration x, mg/m before SNCR denitration 3 Denitration rate y x
270 26.30%
407 48.40%
424 59.00%
670 67.20%
The empirical equation was performed according to the above table data: as shown in figure 12 of the specification. Fitting through an empirical equation to obtain:
y x =-0.000003x 2 +0.0043x-0.6646。
(2) Determining denitration rate y of ammonia nitrogen ratio based on SNCR ammonia injection m The method comprises the following steps:
Figure BDA0002622035560000301
ammonia nitrogen ratio m of SNCR ammonia injection Denitration rate y m
0.7:1 7.3%
1.0:1 67.20%
1.3:1 70.60%
1.7:1 83.30%
The empirical equation was performed according to the above table data: as shown in fig. 13 of the specification. Fitting through an empirical equation to obtain:
y m =-0.118m 2 +0.8214m-0.5975。
(3) Determining denitration rate y of window temperature based on SNCR ammonia injection t The method comprises the following steps:
Figure BDA0002622035560000302
window temperature t, DEG C of SNCR ammonia injection Denitration rate y t
1006 12.10%
980 10.70%
924 48.40%
890 71.30%
831 60.80%
The empirical equation was performed according to the above table data: as shown in fig. 13 of the specification. Fitting through an empirical equation to obtain:
y t =-0.00003t 2 +0.043t-17.62。
(4) Determination of the denitration Rate y based on the NOx concentration before SCR denitration z The method comprises the following steps:
Figure BDA0002622035560000303
Figure BDA0002622035560000304
Figure BDA0002622035560000311
the empirical equation was performed according to the above table data: as shown in fig. 15 of the specification. Fitting through an empirical equation to obtain:
y z =-0.0001z+0.97。
(5) Determining denitration rate y of ammonia nitrogen ratio based on SCR ammonia injection n The method comprises the following steps:
Figure BDA0002622035560000312
ammonia nitrogen ratio n of SCR ammonia injection Denitration rate y n
1.5:1 89.00%
1.4:1 90.00%
1.3:1 91.00%
1.2:1 92.00%
1.15:1 93.00%
1.1:1 94.00%
1.05:1 95.00%
The empirical equation was performed according to the above table data: as shown in figure 16 of the specification. Fitting through an empirical equation to obtain:
y n =0.1643n 2 -0.5482n+1.3437。
(6) Determining denitration rate y based on number of SCR catalyst beds c The method comprises the following steps:
Figure BDA0002622035560000313
SCR catalyst bed number c Denitration rate y c
4 89.00%
4 90.00%
3 91.00%
3 92.00%
3 93.00%
2 94.00%
2 95.00%
The empirical equation was performed according to the above table data: as shown in figure 17 of the specification. Fitting through an empirical equation to obtain:
y c =0.9979*10 -0.027c
combining steps (1) - (6), formula VIII is converted to:
y=A·(-0.000003x 2 +0.0043x-0.6446)+B·(-0.118m 2 +0.8214m-0.5975)+C·(-0.00003t 2 +0.043t-17.62)+D·(-0.0001z+0.97)+E·(0.1643n 2 -0.5482n+1.3437)+F·(0.9979e -0.027c )。
in this embodiment, the weight values of the parameters are as follows: a=0.1, b=0.25, c=0.15, d=0.15, e=0.1, f=0.25. Then, the calculation formula of the SNCR-SCR coupling denitration rate y obtained after fitting is as follows:
y=0.1·(-0.000003x 2 +0.0043x-0.6446)+0.25·(-0.118m 2 +0.8214m-0.5975)+0.15·(-0.00003t 2 +0.043t-17.62)+0.15·(-0.0001z+0.97)+0.1·(0.1643n 2 -0.5482n+1.3437)+0.25·(0.9979e -0.027c )。
(7) Setting a set of initial reference values for each parameter: x=897 mg/m 3 ,m=1.0,t=924℃,z=295mg/m 3 N=1.05, c=2; at this time, the denitration rate by the SNCR technique was 68.3%, the denitration rate by the SCR technique was 94.5%, and the coupling denitration rate was 100%.
(8) On the premise of stable working condition of a chain grate machine-rotary kiln system, namely on the premise that the initial concentration x of NOx before SNCR denitration and the window temperature t of SNCR ammonia injection are relatively stable, the ammonia nitrogen ratio m of the SNCR ammonia injection is gradually reduced, and the STEP length STEP is obtained m 0.1. Calculating through a calculation formula of the SNCR-SCR coupling denitration rate y obtained after fitting;
Figure BDA0002622035560000321
On the basis of the above reference parameters, even if the ammonia nitrogen ratio m of SNCR ammonia injection is reduced from 1.0 to 0.9, the NOx emission concentration is 48.92mg/m 3 <50mg/m 3 . The NOx emission concentration is in accordance with national ultra-low emission standards.
It should be noted that when the N content in the pulverized coal used in the rotary kiln increases and the current combustion state is kept unchanged, the concentration of NOx in the tail gas increases, that is, the initial concentration x of NOx before SNCR denitration increases, the corresponding denitration rate will be in an ascending trend, and when the SNCR system keeps the ammonia nitrogen ratio m and the window temperature t of SNCR ammonia injection unchanged, the denitration rate is maintained at 66-67%, thereby meeting the process requirements. The ammonia nitrogen ratio m is kept unchanged, the total amount of NOx in the flue gas is increased, the actual ammonia spraying amount is increased, and the denitration cost is correspondingly increased.
Figure BDA0002622035560000331
It should be further noted that when the working condition of the grate-rotary kiln system changes, the coal injection amount increases, so that the temperature in the kiln increases, the temperature of the tail gas of the kiln increases, and the NOx content in the tail gas increases, namely, the initial concentration x of NOx before the SNCR denitration and the window temperature t of the SNCR ammonia injection increase simultaneously. At this time, the SNCR denitration rate increases with the increase of the concentration x, and decreases with the increase of the temperature t, and the influence of the temperature t becomes a main factor for limiting the denitration rate, and measures for reducing the window temperature should be taken in time. (typically, the temperature t is reduced to within 1000 ℃ C.)
Figure BDA0002622035560000332
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The technological proposal after the analysis of the comprehensive results is as follows:
Figure BDA0002622035560000341
application example 5
And selecting a grate-rotary kiln oxidized pellet process flue gas denitration system, wherein SNCR catalyst is sprayed in the preheating section PH and/or in a first pipeline L1 connected between an air inlet of the preheating section PH and an air outlet of the rotary kiln 2. The SNCR catalyst is an SNCR catalyst added with a composite additive. And then, adjusting different proportions of each component in the composite additive to perform flue gas denitration treatment. The specific process is shown in the following table:
Figure BDA0002622035560000342
/>
Figure BDA0002622035560000351
application example 6
And selecting a grate-rotary kiln oxidized pellet process flue gas denitration system, wherein SNCR catalyst is sprayed in the preheating section PH and/or in a first pipeline L1 connected between an air inlet of the preheating section PH and an air outlet of the rotary kiln 2. The SNCR catalyst is a compound ammonia agent. And then, adjusting different proportions of each component in the composite additive to perform flue gas denitration treatment. The specific process is shown in the following table:
Figure BDA0002622035560000352
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Figure BDA0002622035560000361
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Figure BDA0002622035560000371
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Claims (48)

1. pellet flue gas treatment system based on rotary kiln primary circulation air inlet, its characterized in that: the system comprises a chain grate machine (1), a rotary kiln (2) and an SCR denitration device (5); according to the trend of the materials, the chain grate machine (1) is sequentially provided with a blowing drying section (UDD), an air draft drying section (DDD), a transitional preheating section (TPH) and a preheating section (PH); a central burner (201) is arranged on the rotary kiln (2); the central burner (201) is communicated with a fuel pipeline (203); the fuel pipeline (203) is also provided with a primary combustion-supporting air pipe (202); an air outlet of the rotary kiln (2) is communicated with an air inlet of the preheating section (PH) through a first pipeline (L1); an air outlet of the preheating section (PH) is communicated with an air inlet of the air draft drying section (DDD) through a second pipeline (L2); the air outlet of the transition preheating section (TPH) is divided into a front section air outlet and a rear section air outlet; an air outlet at the rear section of the transition preheating section (TPH) is communicated with an air inlet of the primary combustion-supporting air pipe (202) through a third pipeline (L3); the front section air outlet of the transition preheating section (TPH) is communicated with a fourth pipeline (L4); an air outlet of the air draft drying section (DDD) is communicated with a fourth pipeline (L4) through a fifth pipeline (L5); an SCR denitration device (5) is arranged on the second pipeline (L2); j bellows (7) are arranged at the bottom of the transition preheating section (TPH), the bellows at the front section corresponds to the air outlet at the front section of the transition preheating section, and the bellows at the rear section corresponds to the air outlet at the rear section of the transition preheating section; the concentration of NOx in the flue gas in J bellows (7) is detected to be H in sequence in real time through a NOx concentration detection device (H) arranged in the J bellows (7) 1 ,H 2 ,…,H J ,mg/m 3 The method comprises the steps of carrying out a first treatment on the surface of the Calculating the average NOx concentration in all J of said windboxes (7) in the transitional preheating section (TPH): h Average of =(H 1 +H 2 +…+H J ) J; then successively judging J bellows (7)NOx concentration and H of (2) Average of Is of a size of (2); when H is j <H Average of And H is j+1 ≥H Average of When the preheating section (TPH) is in the preheating section, the 1 st to the j-th windboxes (7) are the front-section windboxes of the transitional preheating section (TPH); the (j+1) th to the (J) th windboxes (7) are the rear windboxes of the transitional preheating section (TPH).
2. The system according to claim 1, wherein: the air outlet of each air box (7) of the J air boxes (7) is simultaneously connected with a third pipeline (L3) and a fourth pipeline (L4) through a switching valve (701); the air outlet of each air box (7) is further controlled to be communicated with the third pipeline (L3) or the fourth pipeline (L4) through a switching valve (701); .
3. The system according to claim 2, wherein: according to the trend of the materials, the numbers of J bellows (7) in the transition preheating section (TPH) are 1,2,3, … and J in sequence; wherein the 1 st to the j-th bellows (7) are used as front bellows and are communicated with the fourth pipeline (L4); the (j+1) th to the (J) th bellows (7) are used as back bellows and are communicated with a third pipeline (L3); j is more than or equal to 1 and less than or equal to J.
4. A system according to claim 3, characterized in that: j is 2-50.
5. The system according to claim 4, wherein: j is 2-20.
6. The system according to claim 5, wherein: j is 2-10.
7. The system according to any one of claims 1-6, wherein: the system also comprises a circular cooler (3); according to the trend of the materials, the annular cooler (3) is sequentially provided with an annular cooling first section (C1), an annular cooling second section (C2) and an annular cooling third section (C3); an air outlet of the annular cooling section (C1) is communicated with an air inlet of the rotary kiln (2) through a sixth pipeline (L6); the air outlet of the annular cooling second section (C2) is communicated with the air inlet of the transitional preheating section (PTH) through a seventh pipeline (L7); the air outlet of the annular cooling three section (C3) is communicated with the air inlet of the forced air drying section (UDD) through an eighth pipeline (L8); the air outlet of the forced air drying section (UDD) is communicated to a chimney through a ninth pipeline (L9).
8. The system according to any one of claims 1-6, wherein: the system also comprises an SNCR denitration device (8); the SNCR denitration device (8) is arranged in the preheating section (PH) and/or the first pipeline (L1); and/or
The system also comprises a NOx concentration detection device (H), wherein the NOx concentration detection device (H) is arranged in the bellows (7); and a NOx concentration detection device (H) is independently arranged in J bellows (7) at the bottom of the transition preheating section (TPH).
9. The system according to claim 7, wherein: the system also comprises an SNCR denitration device (8); the SNCR denitration device (8) is arranged in the preheating section (PH) and/or the first pipeline (L1); and/or
The system also comprises a NOx concentration detection device (H), wherein the NOx concentration detection device (H) is arranged in the bellows (7); and a NOx concentration detection device (H) is independently arranged in J bellows (7) at the bottom of the transition preheating section (TPH).
10. The system according to claim 8, wherein: the SNCR denitration device (8) comprises a first spraying device (801) and a high-pressure atomization mixing device (803); the first spraying device (801) is arranged in the preheating section (PH) and is connected with the high-pressure atomization mixing device (803) through a tenth pipeline (L10).
11. The system according to claim 9, wherein: the SNCR denitration device (8) comprises a first spraying device (801) and a high-pressure atomization mixing device (803); the first spraying device (801) is arranged in the preheating section (PH) and is connected with the high-pressure atomization mixing device (803) through a tenth pipeline (L10).
12. The system according to claim 10 or 11, characterized in that: the SNCR denitration device (8) further comprises a second spraying device (802); the second spraying device (802) is arranged in the first pipeline (L1) and is connected with the high-pressure atomization mixing device (803) through an eleventh pipeline (L11).
13. The system according to claim 12, wherein: the eleventh pipeline (L11) is a bypass pipeline separated from the tenth pipeline (L10).
14. The system according to any one of claims 10-11, 13, characterized in that: the high-pressure atomization mixing device (803) is provided with a vanadium-titanium catalyst conveying pipe (S1), an ammonia water conveying pipe (S2), a urea conveying pipe (S3), a soluble sodium salt conveying pipe (S4), an ethanol conveying pipe (S5) and a nano zero-valent iron or SBA-15 conveying pipeline (S6).
15. The system according to claim 14, wherein: the system also comprises a mixing device (9); the mixing device (9) is provided with a vanadium-titanium catalyst conveying pipe (S1), an ammonia water conveying pipe (S2), a urea conveying pipe (S3), a soluble sodium salt conveying pipe (S4) and a nano zero-valent iron or SBA-15 conveying pipeline (S6); the mixing device (9) is communicated with the high-pressure atomization mixing device (803) through a twelfth pipeline (L12).
16. The system according to claim 7, wherein: the system also comprises a dust removing device (4), wherein the dust removing device (4) is arranged on the second pipeline (L2) and is positioned at the upstream of the SCR denitration device (5); and/or
The third pipeline (L3) and the ninth pipeline (L9) are optionally provided with or not provided with a dust removing device (4); and/or
The system also comprises a desulfurization device (6); the desulfurization device (6) is arranged on the fourth pipeline (L4).
17. The system according to claim 9 or 11, characterized in that: the system also comprises a dust removing device (4), wherein the dust removing device (4) is arranged on the second pipeline (L2) and is positioned at the upstream of the SCR denitration device (5); and/or
The third pipeline (L3) and the ninth pipeline (L9) are optionally provided with or not provided with a dust removing device (4); and/or
The system also comprises a desulfurization device (6); the desulfurization device (6) is arranged on the fourth pipeline (L4).
18. The system according to claim 16, wherein: the fourth pipeline (L4) is also provided with a dust removing device (4), and the dust removing device (4) is positioned at the upstream of the desulfurization device (6).
19. The system according to claim 17, wherein: the fourth pipeline (L4) is also provided with a dust removing device (4), and the dust removing device (4) is positioned at the upstream of the desulfurization device (6).
20. A flue gas treatment process using the rotary kiln primary circulation air intake-based pellet flue gas treatment system according to any one of claims 1 to 19, characterized in that: the process comprises the following steps:
1) According to the trend of the materials, raw balls enter a chain grate machine (1), and are conveyed into a rotary kiln (2) for oxidative roasting after sequentially passing through a blast drying section (UDD), an induced draft drying section (DDD), a transitional preheating section (TPH) and a preheating section (PH) on the chain grate machine (1);
2) According to the flow direction of hot air, the hot air in the rotary kiln (2) is conveyed into a preheating section (PH) through a first pipeline (L1); the hot air exhausted from the preheating section (PH) is firstly subjected to dust removal treatment by a dust removal device (4), then is subjected to SCR denitration treatment by an SCR denitration device (5), and is conveyed into an exhaust drying section (DDD); the hot air exhausted by the front-section bellows of the induced draft drying section (DDD) and the transition preheating section (TPH) is firstly subjected to dust removal treatment by a dust removal device (4), and then is exhausted after desulfurization treatment by a desulfurization device (6); the hot air discharged from the air box at the rear section of the transition preheating section (TPH) is subjected to dust removal treatment by a dust removal device (4) and then is conveyed into a primary combustion-supporting air pipe (202).
21. The flue gas treatment process according to claim 20, wherein: the process further comprises the steps of:
3) In the annular cooler (3), hot air discharged by the annular cooling section (C1) is conveyed into the rotary kiln (2) through a sixth pipeline (L6); hot air discharged from the annular cooling second section (C2) is conveyed into the transitional preheating section (TPH) through a seventh pipeline (L7); hot air discharged from the annular cooling three section (C3) is conveyed into the forced air drying section (UDD) through an eighth pipeline (L8); and/or
4) Spraying an SNCR catalyst in the preheating section (PH) and/or in a first pipeline (L1) connected between an air inlet of the preheating section (PH) and an air outlet of the rotary kiln (2), and carrying out SNCR denitration reaction on NOx and the SNCR catalyst in hot air in the preheating section (PH) and/or in the first pipeline (L1); and/or
5) The hot air discharged from the forced air drying section (UDD) is optionally discharged via a ninth conduit (L9) after dust removal treatment.
22. The flue gas treatment process according to claim 20 or 21, wherein: the division mode of the front section bellows and the rear section bellows of the transition preheating section (TPH) is specifically as follows:
301 Real-time detection of the concentration of NOx in the flue gas in J windboxes (7) by means of a NOx concentration detection device (H) arranged in J windboxes (7) is H in turn 1 ,H 2 ,…,H J ,mg/m 3
302 Calculating the average NOx concentration in all J of said windboxes (7) in the transitional preheating section (TPH): h Average of =(H 1 +H 2 +…+H J ) J; then successively judging the concentration of NOx and H in J bellows (7) Average of Is of a size of (2);
303 When H j <H Average of And H is j+1 ≥H Average of When the preheating section (TPH) is in the preheating section, the 1 st to the j-th windboxes (7) are the front-section windboxes of the transitional preheating section (TPH); the (j+1) th to the (J) th windboxes (7) are the rear windboxes of the transitional preheating section (TPH);
after the distribution of the bellows (7) is completed, the flow returns to step 301 to continue the detection.
23. The flue gas treatment process according to claim 22, wherein: the process further comprises the steps of:
a) An SNCR denitration system is arranged in the preheating section (PH) and/or a first pipeline (L1) between the preheating section (PH) and the rotary kiln (2); meanwhile, an SCR denitration system is arranged behind an air outlet of the preheating section (PH); establishing an SNCR-SCR coupling denitration mechanism;
b) Detecting and collecting parameter information of the initial concentration of NOx before SNCR denitration, the ammonia nitrogen ratio of SNCR ammonia injection, the window temperature of SNCR ammonia injection, the concentration of NOx before SCR denitration, the ammonia nitrogen ratio of SCR ammonia injection and the number of layers of an SCR catalyst bed in real time;
c) Establishing an SNCR-SCR coupling denitration mathematical model according to the detected parameter information;
d) And calculating and adjusting the minimum SNCR ammonia injection amount according to the SNCR-SCR coupling denitration mathematical model, so that the NOx content in the flue gas meets the emission condition.
24. The flue gas treatment process according to claim 23, wherein: the SNCR-SCR coupling denitration mathematical model is as follows:
y=A·y x +B·y m +C·y t +D·y z +E·y n +F·y c .. formula I;
in the formula I, y is SNCR-SCR coupling denitration rate; y is x Denitration rate based on initial concentration of NOx before SNCR denitration; y is m Denitration rate based on ammonia nitrogen ratio of SNCR ammonia injection; y is t Denitration rate based on window temperature of SNCR ammonia injection; y is z Denitration rate based on NOx concentration before SCR denitration; y is n Is the denitration rate based on the ammonia nitrogen ratio of SCR ammonia injection; y is c Is the denitration rate based on the number of SCR catalyst beds; a is the influence factor weight of the initial concentration x of NOx before SNCR denitration; b is the influence factor weight of ammonia nitrogen ratio m of SNCR ammonia injection; c is the influence factor weight of the window temperature t of SNCR ammonia injection; d is the influence factor weight of the NOx concentration z before SCR denitration; e is the influence factor weight of ammonia nitrogen ratio n of SCR ammonia injection; f is the influence factor weight of the number c of the SCR catalyst beds; and a+b+c+d+e+f=1.
25. The flue gas treatment process according to claim 24, wherein: a is 0.02-0.4; b is 0.1-0.8; c is 0.05-0.5; d is 0.01-0.3; e is 0.05-0.4; f is 0.05-0.5.
26. The flue gas treatment process according to claim 25, wherein: a is 0.05-0.2; b is 0.2-0.5; c is 0.1-0.3; d is 0.02-0.2; e is 0.1-0.3; f is 0.1-0.4.
27. The flue gas treatment process according to claim 24, wherein: denitration rate y based on initial concentration of NOx before SNCR denitration x The method comprises the following steps:
Figure FDA0004241016930000051
in the formula II, x is the initial concentration of NOx before SNCR denitration, mg/m 3 The method comprises the steps of carrying out a first treatment on the surface of the i is the power of x; i is more than or equal to 0 and less than or equal to N x ;N x Is the highest power of x; a, a xi The coefficient to the ith power of x.
28. The flue gas treatment process according to claim 24, wherein: denitration rate y of ammonia nitrogen ratio based on SNCR ammonia injection m The method comprises the following steps:
Figure FDA0004241016930000052
in the formula III, m is the ammonia nitrogen ratio of SNCR ammonia injection; beta is the power of m; beta is more than or equal to 0 and less than or equal to N m ;N m Is the highest power of m; a, a The coefficient to the power of m.
29. The flue gas treatment process according to claim 24, wherein: denitration rate y of window temperature based on SNCR ammonia injection t The method comprises the following steps:
Figure FDA0004241016930000053
in the formula IX, t is the window temperature of SNCR ammonia injection and DEG C; delta is the power of t; delta is more than or equal to 0 and less than or equal to N t ;N t Is the highest power of t; a, a The coefficient to the power delta of t.
30. The flue gas treatment process according to any one of claims 24 to 29, wherein: denitration rate y based on NOx concentration before SCR denitration z The method comprises the following steps:
Figure FDA0004241016930000054
in the formula V, z is the concentration of NOx before SCR denitration, mg/m 3 The method comprises the steps of carrying out a first treatment on the surface of the Gamma is the power of z; gamma is more than or equal to 0 and less than or equal to N z ;N z To the highest power of z; a, a The coefficient to the power of z.
31. The flue gas treatment process of claim 30, wherein: denitration rate y of ammonia nitrogen ratio based on SCR ammonia injection n The method comprises the following steps:
Figure FDA0004241016930000055
in the formula VI, n is the ammonia nitrogen ratio of SCR ammonia spraying; lambda is the power of n; lambda is more than or equal to 0 and less than or equal to N n ;N n Is the highest power of n; a, a Is the coefficient to the lambda th power of n.
32. The flue gas treatment process of claim 31, wherein: denitration rate y based on SCR catalyst bed number c The method comprises the following steps:
Figure FDA0004241016930000061
in the formula VII, c is the number of SCR catalyst beds; θ is the power of c; 0.ltoreq.0θ≤N c ;N c To the highest power of c; a, a The coefficient to the θ th power of c.
33. The flue gas treatment process of claim 32, wherein: substituting the formulas II-VII into the formula I to obtain the following formula I:
Figure FDA0004241016930000062
further conversion of formula VIII gives formula I.
34. The flue gas treatment process of claim 33, wherein: the step d) is specifically as follows:
d1 When x.1-y is less than or equal to 50mg/m 3 When in use; reducing ammonia nitrogen ratio of SNCR ammonia injection, m' =m-STEP m The method comprises the steps of carrying out a first treatment on the surface of the Iterative calculations are carried out according to formula VIII until x.cndot.1-y > 50mg/m are exactly satisfied 3 The method comprises the steps of carrying out a first treatment on the surface of the Then executing the m value at the moment;
d2 When x.1-y > 50mg/m 3 When in use; increasing the ammonia nitrogen ratio of SNCR ammonia injection, m' =m+STEP m The method comprises the steps of carrying out a first treatment on the surface of the Iterative calculations are carried out according to formula VIII until x.cndot.1-y is just less than or equal to 50mg/m 3 The method comprises the steps of carrying out a first treatment on the surface of the Then executing the m' value at the moment;
wherein: m is the ammonia nitrogen ratio of SNCR ammonia injection in the current calculation; m' is the ammonia nitrogen ratio of SNCR ammonia spraying calculated in the next step; STEP (STEP) m The value of (2) is 0.01-0.5.
35. The flue gas treatment process of claim 34, wherein: STEP (STEP) m The value of (2) is 0.03-0.3.
36. The flue gas treatment process of claim 35, wherein: STEP (STEP) m The value of (2) is 0.05-0.1.
37. The flue gas treatment process according to claim 21, wherein: the SNCR catalyst is an SNCR catalyst containing a composite additive, wherein the composite additive comprises or consists of the following components: urea, soluble sodium salt, ethanol, vanadium-titanium catalyst, SBA-15; or alternatively
The SNCR catalyst is a compound ammonia agent, and the compound ammonia agent comprises or consists of the following components: ammonia water, urea, soluble sodium salt, ethanol, vanadium-titanium catalyst and nano zero-valent iron-kaolin material.
38. The flue gas treatment process according to claim 37, wherein: the composite additive in the SNCR catalyst containing the composite additive comprises the following components: 40-70 parts of urea; 10-30 parts by weight of soluble sodium salt; 8-28 parts of ethanol; 1-12 parts by weight of vanadium-titanium catalyst; SBA-15 0.1-5 weight portions.
39. The flue gas treatment process according to claim 38, wherein: the composite additive in the SNCR catalyst containing the composite additive comprises the following components: 45-65 parts of urea; 12-25 parts by weight of soluble sodium salt; 10-25 parts of ethanol; 2-10 parts by weight of vanadium-titanium catalyst; SBA-15 0.3-4 weight portions.
40. The flue gas treatment process according to claim 39, wherein: the composite additive in the SNCR catalyst containing the composite additive comprises the following components: 50-60 parts of urea; 15-20 parts by weight of soluble sodium salt; 12-22 parts of ethanol; 3-8 parts by weight of vanadium-titanium catalyst; 0.5 to 3 parts by weight of SBA-15.
41. The flue gas treatment process according to claim 37, wherein: the compound ammonia agent comprises the following components: 60-90 parts of ammonia water; 8-30 parts of urea; 0.05-1 parts by weight of soluble sodium salt; ethanol 0.05-1.2 weight portions; 0.01 to 0.1 weight portion of vanadium-titanium catalyst; 0.5 to 10 parts by weight of nano zero-valent iron-kaolin material.
42. The flue gas treatment process according to claim 41, wherein: the compound ammonia agent comprises the following components: 65-85 parts of ammonia water; 10-25 parts of urea; 0.1 to 0.8 weight parts of soluble sodium salt; ethanol 0.1-1 weight parts; 0.02-0.08 part by weight of vanadium-titanium catalyst; 0.8-8 parts by weight of nano zero-valent iron-kaolin material.
43. The flue gas treatment process according to claim 42, wherein: the compound ammonia agent comprises the following components: 70-80 parts of ammonia water; 15-25 parts of urea; 0.15-0.5 parts by weight of soluble sodium salt; 0.15-0.8 part by weight of ethanol; 0.03-0.05 parts by weight of vanadium-titanium catalyst; 1-6 parts by weight of nano zero-valent iron-kaolin material.
44. The flue gas treatment process according to any one of claims 20 to 21, 23 to 29, 31 to 43, wherein: the desulfurization treatment is dry desulfurization, semi-dry desulfurization or wet desulfurization; and/or
The dust removing treatment is cloth bag dust removing treatment or electric dust removing treatment.
45. The flue gas treatment process according to claim 22, wherein: the desulfurization treatment is dry desulfurization, semi-dry desulfurization or wet desulfurization; and/or
The dust removing treatment is cloth bag dust removing treatment or electric dust removing treatment.
46. The flue gas treatment process of claim 30, wherein: the desulfurization treatment is dry desulfurization, semi-dry desulfurization or wet desulfurization; and/or
The dust removing treatment is cloth bag dust removing treatment or electric dust removing treatment.
47. The flue gas treatment process according to claim 44, wherein: the desulfurization treatment is carried out by lime.
48. The flue gas treatment process of claim 45 or 46, wherein: the desulfurization treatment is carried out by lime.
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