CN115055040A - Low-temperature denitration and sulfur fixation method and system based on cement clinker production line - Google Patents
Low-temperature denitration and sulfur fixation method and system based on cement clinker production line Download PDFInfo
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- CN115055040A CN115055040A CN202210872285.2A CN202210872285A CN115055040A CN 115055040 A CN115055040 A CN 115055040A CN 202210872285 A CN202210872285 A CN 202210872285A CN 115055040 A CN115055040 A CN 115055040A
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 239000011593 sulfur Substances 0.000 title claims abstract description 41
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 41
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 37
- 239000004568 cement Substances 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 32
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 79
- 239000003546 flue gas Substances 0.000 claims abstract description 79
- 239000002994 raw material Substances 0.000 claims abstract description 63
- 239000000428 dust Substances 0.000 claims abstract description 47
- UKLNMMHNWFDKNT-UHFFFAOYSA-M sodium chlorite Chemical compound [Na+].[O-]Cl=O UKLNMMHNWFDKNT-UHFFFAOYSA-M 0.000 claims abstract description 43
- 229960002218 sodium chlorite Drugs 0.000 claims abstract description 43
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 42
- 230000023556 desulfurization Effects 0.000 claims abstract description 29
- 238000001816 cooling Methods 0.000 claims abstract description 27
- 239000000463 material Substances 0.000 claims abstract description 24
- 239000002893 slag Substances 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 13
- 230000018044 dehydration Effects 0.000 claims abstract description 11
- 239000002912 waste gas Substances 0.000 claims abstract description 9
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 24
- GBAOBIBJACZTNA-UHFFFAOYSA-L calcium sulfite Chemical group [Ca+2].[O-]S([O-])=O GBAOBIBJACZTNA-UHFFFAOYSA-L 0.000 claims description 24
- 235000010261 calcium sulphite Nutrition 0.000 claims description 24
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 17
- 235000012054 meals Nutrition 0.000 claims description 16
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 15
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 15
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 15
- 230000008569 process Effects 0.000 claims description 13
- 238000005507 spraying Methods 0.000 claims description 12
- 239000000779 smoke Substances 0.000 claims description 10
- 239000000047 product Substances 0.000 claims description 9
- 239000000292 calcium oxide Substances 0.000 claims description 8
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 8
- 238000002485 combustion reaction Methods 0.000 claims description 8
- 239000007921 spray Substances 0.000 claims description 8
- 238000000354 decomposition reaction Methods 0.000 claims description 7
- 229910021529 ammonia Inorganic materials 0.000 claims description 6
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 6
- 239000006227 byproduct Substances 0.000 claims description 5
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 5
- 239000000920 calcium hydroxide Substances 0.000 claims description 5
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 5
- 239000000446 fuel Substances 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- 230000009471 action Effects 0.000 claims description 3
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 3
- 238000004886 process control Methods 0.000 claims 1
- 230000001965 increasing effect Effects 0.000 description 16
- 239000011575 calcium Substances 0.000 description 10
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 238000010531 catalytic reduction reaction Methods 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 230000003009 desulfurizing effect Effects 0.000 description 3
- JTJMJGYZQZDUJJ-UHFFFAOYSA-N phencyclidine Chemical class C1CCCCN1C1(C=2C=CC=CC=2)CCCCC1 JTJMJGYZQZDUJJ-UHFFFAOYSA-N 0.000 description 3
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 3
- 239000004480 active ingredient Substances 0.000 description 2
- OSVXSBDYLRYLIG-UHFFFAOYSA-N dioxidochlorine(.) Chemical compound O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000012946 outsourcing Methods 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 239000004155 Chlorine dioxide Substances 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 235000019398 chlorine dioxide Nutrition 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 125000001741 organic sulfur group Chemical group 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- VISKNDGJUCDNMS-UHFFFAOYSA-M potassium;chlorite Chemical compound [K+].[O-]Cl=O VISKNDGJUCDNMS-UHFFFAOYSA-M 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
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-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/75—Multi-step processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
- B01D53/50—Sulfur oxides
- B01D53/508—Sulfur oxides by treating the gases with solids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/54—Nitrogen compounds
- B01D53/56—Nitrogen oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/77—Liquid phase processes
- B01D53/78—Liquid phase processes with gas-liquid contact
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/81—Solid phase processes
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23J—REMOVAL OR TREATMENT OF COMBUSTION PRODUCTS OR COMBUSTION RESIDUES; FLUES
- F23J15/00—Arrangements of devices for treating smoke or fumes
- F23J15/003—Arrangements of devices for treating smoke or fumes for supplying chemicals to fumes, e.g. using injection devices
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23J—REMOVAL OR TREATMENT OF COMBUSTION PRODUCTS OR COMBUSTION RESIDUES; FLUES
- F23J15/00—Arrangements of devices for treating smoke or fumes
- F23J15/02—Arrangements of devices for treating smoke or fumes of purifiers, e.g. for removing noxious material
- F23J15/022—Arrangements of devices for treating smoke or fumes of purifiers, e.g. for removing noxious material for removing solid particulate material from the gasflow
- F23J15/027—Arrangements of devices for treating smoke or fumes of purifiers, e.g. for removing noxious material for removing solid particulate material from the gasflow using cyclone separators
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23J—REMOVAL OR TREATMENT OF COMBUSTION PRODUCTS OR COMBUSTION RESIDUES; FLUES
- F23J15/00—Arrangements of devices for treating smoke or fumes
- F23J15/08—Arrangements of devices for treating smoke or fumes of heaters
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/20—Reductants
- B01D2251/206—Ammonium compounds
- B01D2251/2062—Ammonia
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/40—Alkaline earth metal or magnesium compounds
- B01D2251/404—Alkaline earth metal or magnesium compounds of calcium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/60—Inorganic bases or salts
- B01D2251/604—Hydroxides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
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- Biomedical Technology (AREA)
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- Oil, Petroleum & Natural Gas (AREA)
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Abstract
The invention discloses a low-temperature denitration and sulfur fixation method and system based on a cement clinker production line, which comprises a decomposing furnace self-denitration, SNCR denitration, on-line desulfurizer taking, self-desulfurization, low-temperature denitration and sulfur fixation, waste gas dehydration and desulfurization slag conveying, wherein active heat raw materials with the temperature of 800-950 ℃ are extracted from a preheater unit and are divided into two strands; cooling a strand of active heat raw material to below 150 ℃, and performing desulfurization reaction on the strand of active heat raw material and the flue gas which is subjected to heat exchange in a preheater unit in a reactor; the material enters an air pipe along with the desulfurized flue gas after exiting the reactor, and sodium chlorite solution is sprayed into the air pipe to carry out denitration and sulfur fixation reaction; after denitration, the flue gas moves to a dust collector, and the other active hot raw material is sprayed into the air duct to absorb water and then enters the dust collector; the collected desulfurized slag is fed into a preheater unit, and the flue gas after dust removal is discharged. The invention realizes low-temperature deep denitration, has high denitration efficiency, can realize low-temperature sulfur fixation and realize resource utilization of the desulfurized slag.
Description
Technical Field
The invention relates to the technical field of desulfurization and denitrification of cement processes, in particular to a low-temperature denitration and sulfur fixation method and system based on a cement clinker production line.
Background
The flue gas of the cement clinker production line contains harmful gases such as nitric oxide, sulfur dioxide and the like, and NO is actively controlled for enhancing environmental protection x 、SO 2 And the like, and strict emission standards are set.
NO in cement kiln flue gas x Mainly generated in the combustion process of fuel in a rotary kiln and a decomposing furnace, wherein NO generated in the rotary kiln is used x Mainly comprises the following steps. At present, the cement industry at home and abroad mostly adopts the combination of a decomposition furnace fuel combustion self-denitrification technology and a selective non-catalytic reduction (SNCR) denitrification or Selective Catalytic Reduction (SCR) denitrification technology to reduce NO in discharged flue gas x The concentration of (c). With partial area of NO x Emission standards are further improved, and the dosage of ammonia water used as a denitration agent of an SNCR (selective non-catalytic reduction) system or an SCR (selective catalytic reduction) system needs to be increased, but the ammonia escape amount is increased, and the production risk is increased. In the actual industrial production process, when the aqueous ammonia quantity reaches a certain value, increase the aqueous ammonia again, denitration effect increases unobviously, then can only guarantee to satisfy NO through reducing production line output x And (4) emission indexes.
In the production process of cement clinker, when the raw material contains more low-valence sulfur such as organic sulfur or sulfide, the low-valence sulfur is released to generate SO by high-temperature oxidation in the preheater 2 A gas. At present, the cement industry at home and abroad is already favorableThe self-desulfurization of the hot raw material decomposed in the preheater during the production of cement clinker is carried out by digesting the active ingredient CaO of the hot raw material with SO in the flue gas 2 And reacting to achieve the effect of desulfurization. The calcium circulation desulfurization technology does not need to purchase a desulfurizing agent, has high desulfurization efficiency and has the main reaction formula:
CaO+H 2 O→Ca(OH) 2
Ca(OH) 2 +SO 2 →CaSO 3 ·1/2H 2 O+1/2H 2 O
the cement self-desulfurization technology generates a large amount of desulfurization byproducts (also called desulfurization ash) which are difficult to be comprehensively utilized due to the large amount of calcium sulfite. In a cement production line, calcium sulfite can be returned to a decomposing furnace and enters a kiln to be calcined to generate clinker, but the calcium sulfite is easily decomposed to form SO under a high-temperature environment 2 Result in SO 2 And (4) secondary escape.
In summary, the problems of the prior art are as follows:
(1) with NO x Further improvement of emission standards requires increasing the amount of ammonia water used as a denitration agent in an SNCR system or an SCR system, but the ammonia slip amount is increased, and the production risk is increased.
(2) In the production process, when the ammonia water amount reaches a certain value, the ammonia water amount is increased, the denitration effect is not obviously increased, and the requirement of NO can be ensured only by reducing the yield of the production line x And (4) emission indexes.
(3) The main component of the generated desulphurization slag is calcium sulfite, and the desulphurization slag is returned to a decomposing furnace to be easily decomposed again to generate SO 2 。
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a low-temperature denitration and sulfur fixation method and system based on a cement clinker production line. The sodium chlorite solution is adopted to realize low-temperature sulfur fixation and the cement raw meal is self-desulfurized in the processThe generated desulfurized slag calcium sulfite is oxidized into calcium sulfate, and then is fed into the preheater to enter the kiln to be calcined to obtain clinker, thereby not only realizing self-sufficiency of the desulfurizer, but also realizing resource utilization of the desulfurized slag, and solving the problem that the calcium sulfite is easy to decompose under a high-temperature environment to cause SO 2 Secondary escape.
The invention is realized in this way, a low-temperature denitration and sulfur fixation method based on a cement clinker production line, which comprises the steps of decomposing furnace self-denitration and SNCR denitration; wherein, the decomposing furnace is self-denitrating: the smoke discharged from the rotary kiln enters a decomposing furnace through a kiln tail smoke chamber, and NO in the smoke discharged from the rotary kiln is removed through reaction with reducing gas generated by fuel combustion in the decomposing furnace x (ii) a The SNCR denitration comprises the following steps: ammonia water is sprayed onto an outlet air pipe of the decomposing furnace, so that the concentration of nitrogen oxides in the flue gas is reduced;
also comprises on-line desulfurizer taking, self-desulfuration, low-temperature denitration and sulfur fixation, waste gas dehydration and desulfuration residue conveying; wherein,
and the online desulfurizer taking: extracting active thermal raw meal from a preheater unit, dividing the extracted active thermal raw meal into two streams, wherein one stream of active thermal raw meal is cooled to below 150 ℃;
the self-desulfuration comprises the following steps: the flue gas out of the preheater unit enters a reactor through a high-temperature fan after heat exchange under the action of the high-temperature fan, and undergoes a desulfurization reaction with active raw materials which are cooled and then enter the reactor, the active raw materials react with water in the flue gas to generate active calcium hydroxide and then react with sulfur dioxide, and a desulfurization byproduct is calcium sulfite;
and (3) low-temperature denitration and sulfur fixation: the calcium sulfite enters an air pipe connected with an outlet of the reactor along with the desulfurized flue gas, and a sodium chlorite solution is sprayed into the air pipe close to the outlet of the reactor, fully contacts with the flue gas out of the reactor, and respectively carries out denitration and sulfur fixation reactions with nitrogen oxide and calcium sulfite to reduce the concentration of NOx in the flue gas, oxidize the calcium sulfite into calcium sulfate, and the concentration of NOx in the flue gas after low-temperature denitration is 20-50 ppm;
dehydrating the waste gas: after denitration, the flue gas continuously moves to the inlet of the dust collector, and the other active hot raw material is sprayed into an air pipe close to the inlet of the dust collector to absorb the water increased by spraying the sodium chlorite solution into the air pipe, and then enters the dust collector;
conveying the desulfurization slag: and the desulfurized slag collected by the dust collector is fed into a preheater unit through a conveying system, and then enters a rotary kiln to be calcined to obtain clinker, and the flue gas after dust removal is discharged.
Preferably, in the process of taking the desulfurizing agent on line, the amount of the extracted active heat raw material accounts for 0.1-5% of the total amount of the raw material, the ignition loss of the taken active heat raw material is less than 5%, the content of calcium oxide is more than 50%, and the temperature of the active heat raw material at a material taking point is 800-950 ℃; the cooling method of the active thermal raw material is air cooling.
Preferably, in the self-desulfurization process, the moisture content of the flue gas discharged from the preheater unit is 5% -10%; the speed of the flue gas entering the bottom of the reactor is 20-50 m/s.
Preferably, in the low-temperature denitration sulfur fixation process, the mass fraction of sodium chlorite in the sodium chlorite solution is 3-10%; the sodium chlorite solution is fully atomized by spray guns and then sprayed into the air duct, and the number of the spray guns is 1 to 4.
Preferably, the amount of the sodium chlorite solution is based on NO in the flue gas x And SO 2 Concentration adjustment, the concrete adjustment mode is:
in the formula, V is the volume of spraying sodium chlorite solution into the air duct, and the unit is L; omega is the mass fraction of the sodium chlorite solution; rho is the density of the sodium chlorite solution and is expressed in kg/m 3 ;[NO x ] i 、[SO 2 ] i Respectively NO in the flue gas of the high-temperature fan x And SO 2 In ppm; [ NO ] x ] j NO to meet emission requirements x Concentration; k is a radical of 1 Is NO x Concentration correction coefficient is 1 x-1.5 x, wherein x is NO x The number of middle O; k is a radical of 2 Is SO 2 And correcting the coefficient of concentration by taking 1.5-2.5.
Preferably, in the waste gas dehydration process, the temperature of the flue gas is controlled to be higher than 80 ℃ before the flue gas enters the dust collector, and the phenomenon that water vapor in the flue gas is changed into dew to influence the dust collector and conveying system equipment is avoided.
Preferably, the desulfurization slag comprises desulfurization product calcium sulfate, denitration product calcium nitrate and dehydration product calcium hydroxide.
Preferably, the decomposition furnace is a gradient combustion self-denitration decomposition furnace, the self-denitration efficiency is more than 60%, and the concentration of NOx in the flue gas discharged from the decomposition furnace is 500-800 ppm;
preferably, the SNCR denitration is carried out by controlling the ammonia escape amount to be less than 10ppm by using the ammonia water.
A low-temperature denitration and sulfur fixation system based on a cement clinker production line comprises a preheater unit, a heat exchange system and a high-temperature fan, wherein the preheater unit comprises a cyclone cylinder and a decomposing furnace which are arranged in a multistage manner, and an outlet air pipe of a first-stage cyclone cylinder of the preheater unit is sequentially provided with the heat exchange system and the high-temperature fan;
the system comprises a preheater unit, a cooling system, a reactor, a dust collector and a conveying system, wherein the preheater unit comprises a last-stage cyclone cylinder, a feed pipe, a thermal raw material pipeline I and a thermal raw material pipeline II;
the first hot raw material pipeline is connected with an inlet of a cooling system, the cooling system is used for cooling active hot raw materials in the first hot raw material pipeline to be below 150 ℃, an outlet of the cooling system is connected with a material inlet at the bottom of the reactor, and a flue gas inlet at the bottom of the reactor is connected with an outlet of a high-temperature fan;
an outlet at the top of the reactor is connected with a dust collector through an air pipe, a sodium chlorite solution spraying port is arranged on the air pipe close to the outlet of the reactor, and an outlet of the hot raw material pipeline II is connected with the air pipe close to the inlet of the dust collector, so that the temperature of flue gas at the inlet of the dust collector is higher than 80 ℃ before entering the dust collector; and a discharge port of the dust collector is connected with the preheater unit through a conveying system.
The invention has the advantages and positive effects that:
1. the invention utilizes the characteristic that the hot raw material decomposed by the preheater unit has high desulfurization activity, adopts the cement kiln to self-heat the raw material, and utilizes the characteristic that the flue gas discharged from the preheater unit has high water content to digest CaO in the raw material into Ca (OH) 2 With SO in flue gas 2 The reaction solves the problem of the emission of sulfur dioxide in flue gas, realizes the self-sufficiency of the desulfurizer and saves the cost of outsourcing the desulfurizer.
2. The invention adopts the sodium chlorite solution to carry out low-temperature deep denitration, is safe and high in denitration efficiency, ensures the yield of a production line, and solves the problem that NO is generated when NO is used x When the emission requirement is strict, the problem of increased ammonia escape amount caused by increasing the using amount of the ammonia water serving as the denitration agent of the SNCR system is solved, and the problem that when the denitration effect is limited due to increased using amount of the ammonia water, the NO can be ensured to be met only by reducing the yield of a production line when the denitration effect is limited is solved x The problem of discharge.
3. According to the invention, a sodium chlorite solution is adopted for low-temperature sulfur fixation, calcium sulfite in the desulfurization slag is oxidized into calcium sulfate, and then the calcium sulfate is fed into a preheater unit and then enters a kiln to be calcined to obtain clinker, SO that the resource utilization of the desulfurization slag is realized, and the problem that SO is easily decomposed in a high-temperature environment due to the fact that the calcium sulfite is easily decomposed is solved 2 Secondary escape.
4. The invention dehydrates the hot raw material decomposed by the preheater unit, on one hand, the problems of reduced dust removal efficiency and equipment blockage caused by increased moisture due to the spraying of sodium chlorite solution are solved, on the other hand, the temperature of the flue gas before entering the dust collector is controlled to be more than 80 ℃ by utilizing the high temperature of the hot raw material and the heat released by dehydration reaction, and the water vapor in the flue gas is prevented from becoming dew, thereby preventing the dust collector and the conveying system equipment from being influenced.
5. The invention adopts the sodium chlorite solution to realize low-temperature deep denitration and sulfur fixation, does not influence the production of a normal production line, and has simple system and convenient operation.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a process flow diagram of a low-temperature denitration sulfur fixation system based on a cement clinker production line provided by an embodiment of the invention.
Wherein: 1. a preheater unit; 1-1, a decomposing furnace; 1-2, last stage cyclone; 1-3, a primary cyclone cylinder; 2. a heat exchange system; 3. a high temperature fan; 4. an online material taking system; 4-1, taking a material pipe; 4-2, a material distributing valve; 4-3, a first hot raw material pipeline; 4-4, a second hot raw material pipeline; 5. a cooling system; 6. a reactor; 7. a dust collector; 8. a delivery system; 9. a kiln tail smoke chamber; 10. a rotary kiln;
a. cement raw meal; b. a sodium chlorite solution;
the dotted line with an arrow is the airflow direction; the solid line with arrows is the direction of flow.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the accompanying drawings, and it should be understood that the described embodiments are some, but not all embodiments of the present invention. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
In the description of the present invention, it should be noted that, unless otherwise explicitly specified or limited, the terms "mounted," "connected," and "connected" are to be construed broadly, e.g., as meaning either a fixed connection, a removable connection, or an integral connection; can be mechanically or electrically connected; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meanings of the above terms in the present invention can be understood in specific cases to those skilled in the art.
Example 1
Referring to fig. 1, the embodiment provides a low-temperature denitration and sulfur fixation system based on a cement clinker production line, which includes a preheater unit 1, a heat exchange system 2, a high-temperature fan 3, an online material taking system 4, a cooling system 5, a reactor 6, a dust collector 7, and a conveying system 8.
The preheater unit 1 comprises cyclones arranged in multiple stages and a decomposing furnace 1-1, and a heat exchange system 2 and a high-temperature fan 3 are sequentially arranged on an outlet air pipe of a primary cyclone 1-3 of the preheater unit 1; the preheater unit 1 is provided with 3-6 stages of cyclones, and the embodiment is provided with five stages of cyclones.
The on-line material taking system 4 comprises a material taking pipe 4-1, a material distributing valve 4-2, a hot raw material pipeline I4-3 and a hot raw material pipeline II 4-4, wherein an inlet of the material taking pipe 4-1 is connected with a material discharging pipe of a last-stage cyclone 1-2 of the preheater unit 1 or an outlet air pipe of the decomposing furnace 1-1, so that the temperature of active hot raw materials taken out of the material taking pipe 4-1 is 800-950 ℃, an outlet of the material taking pipe 4-1 is connected with the material distributing valve 4-2, and an outlet of the material distributing valve 4-2 is respectively connected with the hot raw material pipeline I4-3 and the hot raw material pipeline II 4-4.
The material taking point is the position of a discharging pipe of the last-stage cyclone 1-2 or the position of an air pipe between the decomposing furnace 1-1 and the last-stage cyclone 1-2, and the material taking point in the embodiment is the position of the discharging pipe of the last-stage cyclone 1-2.
The hot raw material pipeline I4-3 is connected with an inlet of a cooling system 5, the cooling system 5 is air-cooled, the cooling system 5 is used for cooling active hot raw materials in the hot raw material pipeline I4-3 to a temperature below 150 ℃, an outlet of the cooling system 5 is connected with a material inlet at the bottom of the reactor 6, a flue gas inlet at the bottom of the reactor 6 is connected with an outlet of the high-temperature fan 3, a desulfurization reaction occurs in the reactor 6, and a desulfurization byproduct is calcium sulfite.
An outlet at the top of the reactor 6 is connected with a dust collector 7 through an air pipe, a sodium chlorite solution b spraying port is arranged on the air pipe close to the outlet of the reactor 6, an outlet of a second 4-4 hot raw material pipeline is connected with the air pipe close to the inlet of the dust collector 7, hot raw materials are sprayed into the air pipe close to the inlet of the dust collector 7, the hot raw materials decomposed by the preheater unit 1 are dehydrated, moisture increased by spraying the sodium chlorite solution into the air pipe is absorbed, the temperature of flue gas at the inlet of the dust collector is higher than 80 ℃ before entering the dust collector 7, and water vapor in the flue gas is prevented from becoming dew.
And a discharge hole of the dust collector 7 is connected with the preheater unit 1 through a conveying system 8. The conveying mode of the conveying system 8 is pneumatic conveying or mechanical conveying. The desulfurized slag collected by the dust collector is sent to the preheater unit 1 through the conveying system 8, and then enters the rotary kiln to be calcined to obtain clinker. In this example, the desulfurizing slag is fed at the raw material feed port of the preheater unit 1.
Example 2
Referring to fig. 1, the embodiment provides a low-temperature denitration and sulfur fixation method based on a cement clinker production line, which includes self-denitration of a decomposing furnace, SNCR denitration, on-line desulfurization, self-desulfurization, low-temperature denitration and sulfur fixation, waste gas dehydration and desulfurized slag transportation.
Self-denitration of a decomposing furnace: the temperature of the flue gas discharged from the rotary kiln 10 is generally 900-1150 ℃, and NO in the flue gas x The concentration is generally 800 to 1500 ppm. The smoke discharged from the rotary kiln 10 enters a decomposing furnace 1-1 through a kiln tail smoke chamber 9, and NO in the smoke discharged from the kiln is removed through reaction with reducing gas generated by fuel combustion in the decomposing furnace 1-1 x . The decomposing furnace 1-1 is a gradient combustion self-denitration decomposing furnace with self-denitration efficiency>60 percent of NO in flue gas discharged from the decomposing furnace x The concentration is 500-800 ppm.
SNCR denitration: an SNCR spray gun is arranged on an air pipe between the outlet of the decomposing furnace 1-1 and the inlet of the final stage cyclone 1-2, and ammonia water is sprayed into the SNCR spray gun, so that the concentration of nitrogen oxides in flue gas can be reduced to less than 200 ppm. The number of SNCR spray guns is determined according to NO in the flue gas discharged from the decomposing furnace x And (4) determining the concentration. The ammonia water consumption of the SNCR system needs to ensure the ammonia escape amount<10ppm。
Online desulfurizer taking: the cement raw meal a is subjected to heat exchange with hot flue gas in a preheater unit 1 to obtain active heat raw meal. Active heat raw materials are extracted from a discharging pipe of a last stage cyclone 1-2 of a preheater unit 1, the amount of the extracted active heat raw materials accounts for 0.1-5% of the total amount of the raw materials, the ignition loss of the extracted active heat raw materials is less than 5%, the content of calcium oxide is more than 50%, and the temperature of the active heat raw materials at a material extracting point is 800-950 ℃. The taken active hot raw material is divided into two parts by a material dividing valve 4-2, wherein one part enters a cooling system 5 through a hot raw material pipeline I4-1 and is cooled to below 150 ℃ by air cooling through the cooling system 5.
Self-desulfurization: the flue gas out of the primary cyclone 1-3 of the preheater unit 1 contains NO x 、SO 2 And the temperature of the flue gas is 250-350 ℃, and the water content is 5-10 percent. Under the action of the high-temperature fan 3, the flue gas enters the reactor 6 through the high-temperature fan 3 after heat exchange through the heat exchange system 2, simultaneously, the cooled active raw material enters the reactor 6, and the active ingredient CaO in the active raw material reacts with the water in the flue gas to generate Ca (OH) with higher desulfurization activity 2 ,Ca(OH) 2 Then with SO 2 The reaction produces a desulphurization by-product calcium sulfite. The reaction formula for the self-desulfurization process is as follows:
CaO+H 2 O→Ca(OH) 2
Ca(OH) 2 +SO 2 →CaSO 3 +H 2 O
the heat exchange system 2 is a waste heat power generation system or a heat exchanger, and recovers the enthalpy in the flue gas of the primary cyclone 1-3. The temperature of the flue gas discharged from the heat exchange system 2 is 120-200 ℃ and the water content is 5-10%. When the water content of the flue gas discharged from the outlet of the preheater unit 1 is not enough, a small amount of water can be sprayed into the pipeline discharged from the cooling system 5, so that the effective generation amount of the active calcium hydroxide is ensured.
The air speed of the flue gas out of the high-temperature fan 3 and entering the channel at the bottom of the reactor 6 is 20-50 m/s, so that material collapse is avoided.
Low-temperature denitration and sulfur fixation: the calcium sulfite enters an air pipe connected with the outlet of the reactor 6 along with the desulfurized flue gas after exiting the reactor 6, and a sodium chlorite solution b is sprayed into the air pipe close to the outlet of the reactor 6. The sodium chlorite solution b is fully contacted with the flue gas out of the reactor 6, and respectively reacts with nitrogen oxides and calcium sulfite for denitrification and sulfur fixation, so that the concentration of NOx in the flue gas is reduced, and the calcium sulfite is oxidized into calcium sulfate. The concentration of NOx in the flue gas after low-temperature denitration is 20-50 ppm.
The reaction formula of the low-temperature denitration process is as follows:
(5-2x)NaClO 2 +4NO x +2H 2 O→4HNO 3 +(5-2x)NaCl
4HNO 3 +Ca(OH) 2 →Ca(NO 3 ) 2 +H 2 O
the reaction formula of the low-temperature sulfur fixation process is as follows:
NaClO 2 +2CaSO 3 =2CaSO 4 +NaCl
the mass fraction of sodium chlorite in the sodium chlorite solution is 3-10 percent. The sodium chlorite solution is fully atomized by spray guns and then sprayed into an air duct, and the number of the spray guns is 1 to 4.
The dosage of the sodium chlorite solution is determined by NO in the flue gas x And SO 2 Concentration adjustment, the concrete adjustment mode is:
in the formula, V is the volume of spraying sodium chlorite solution into the air duct, and the unit is L; omega is the mass fraction of the sodium chlorite solution; rho is the density of the sodium chlorite solution and is expressed in kg/m 3 ;[NO x ] i 、[SO 2 ] i Respectively NO in the flue gas of the high-temperature fan x And SO 2 In ppm; [ NO ] x ] j NO to meet emission requirements x Concentration; k is a radical of 1 Is NO x Concentration correction coefficient is 1 x-1.5 x, wherein x is NO x The number of middle O; k is a radical of 2 Is SO 2 And (5) correcting the coefficient of concentration by taking 1.5-2.5.
Waste gas dehydration: after denitration, the flue gas continuously moves to the inlet of the dust collector, and the other strand of hot raw material is sprayed into an air pipe close to the inlet of the dust collector 7 through a hot raw material pipeline II 4-4 to absorb the water increased by spraying the sodium chlorite solution b into the air pipe.
The dehydration is carried out by using the hot raw material decomposed by the preheater unit 1, so that the problems of reduced dust removal efficiency and equipment blockage caused by increased moisture in the waste gas due to the spraying of the sodium chlorite solution a are solved, and the temperature of the flue gas is controlled to be more than 80 ℃ before entering the dust collector by using the high temperature of the hot raw material and the heat released by the dehydration reaction, so that the water vapor in the flue gas is prevented from becoming dew, and the influence on the dust collector 7 and the conveying system 8 equipment is prevented.
Conveying the desulfurized slag: the desulfurized slag enters a dust collector 7 along with the denitrated flue gas, the dedusted flue gas is discharged, and the collected desulfurized slag is fed into a raw material feeding port of a preheater unit 1 through a conveying system 8 and enters a rotary kiln 10 to be calcined to obtain clinker. The desulfurization slag comprises desulfurization product calcium sulfate, denitration product calcium nitrate and dehydration product calcium hydroxide. Calcium sulfate is more stable than calcium sulfite, can not be decomposed at high temperature, and avoids secondary generation of SO 2 。
In summary, the invention utilizes the characteristic that the hot raw meal decomposed by the preheater unit has high desulfurization activity, and adopts the cement kiln to self-heat the raw meal and SO in the flue gas 2 The reaction solves the problem of the emission of sulfur dioxide in flue gas, realizes the self-sufficiency of the desulfurizer and saves the cost of outsourcing the desulfurizer. The sodium chlorite solution is adopted to realize low-temperature deep denitration, and the system combines the decomposing furnace self-denitration technology and the SNCR denitration technology, so that the NO can be effectively controlled at the source, the process and the tail end of the production line x The emission concentration can realize the degree of depth denitration on the one hand, satisfies more rigorous environmental protection requirement, and on the other hand can the at utmost reduce the use amount of denitrifier aqueous ammonia, reduces excessive, guarantees production safety. The sodium chlorite solution is adopted, low-temperature sulfur fixation can be realized, calcium sulfite is oxidized into calcium sulfate, the calcium sulfate is fed into a preheater unit and then enters a kiln to be calcined to obtain clinker, the resource utilization of the desulfurized slag is realized, and the problem that SO is easily decomposed in a high-temperature environment to cause the calcium sulfite is solved 2 The problem of secondary escape.
According to the invention, the sodium chlorite solution is adopted to realize low-temperature deep denitration and sulfur fixation, so that the production of a normal production line is not influenced, the system is simple, the operation is convenient, the denitration efficiency is high, and the recycling of calcium sulfite is effectively realized.
It should be noted that the sodium chlorite solution of the present invention can be replaced by other oxidants, such as sodium hypochlorite, potassium chlorite, ozone, chlorine dioxide, etc.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. A low-temperature denitration and sulfur fixation method based on a cement clinker production line comprises the steps of self-denitration of a decomposing furnace and SNCR denitration; wherein, the decomposing furnace is self-denitrating: the smoke discharged from the rotary kiln enters a decomposing furnace through a kiln tail smoke chamber, and NO in the smoke discharged from the rotary kiln is removed through reaction with reducing gas generated by fuel combustion in the decomposing furnace x (ii) a The SNCR denitration comprises the following steps: spraying ammonia water on an outlet air pipe of the decomposing furnace to reduce the concentration of nitrogen oxides in the flue gas; the method is characterized in that:
the method also comprises the steps of online desulfurizer taking, self-desulfurization, low-temperature denitration and sulfur fixation, waste gas dehydration and desulfurization slag conveying; wherein,
and the online desulfurizer taking: extracting active thermal raw meal from a preheater unit, dividing the extracted active thermal raw meal into two streams, wherein one stream of active thermal raw meal is cooled to below 150 ℃;
the self-desulfurization: the flue gas out of the preheater unit enters the reactor through the high-temperature fan after heat exchange under the action of the high-temperature fan, and is subjected to desulfurization reaction with the active raw material which enters the reactor after cooling, wherein the desulfurization byproduct is calcium sulfite;
and (3) low-temperature denitration and sulfur fixation: calcium sulfite enters an air pipe connected with an outlet of the reactor along with the desulfurized flue gas out of the reactor, and a sodium chlorite solution is sprayed into the air pipe close to the outlet of the reactor, is fully contacted with the flue gas out of the reactor, and carries out denitration and sulfur fixation reaction to oxidize the calcium sulfite into calcium sulfate, wherein the concentration of NOx in the flue gas after low-temperature denitration is 20-50 ppm;
dehydrating the waste gas: after denitration, the flue gas continuously moves to the inlet of the dust collector, and the other active hot raw material is sprayed into an air pipe close to the inlet of the dust collector to absorb water and then enters the dust collector;
conveying the desulfurization slag: and the desulfurized slag collected by the dust collector is fed into a preheater unit through a conveying system, and then enters a rotary kiln to be calcined to obtain clinker, and the flue gas after dust removal is discharged.
2. The low-temperature denitration sulfur-fixing method based on the cement clinker production line as claimed in claim 1, wherein in the on-line desulfurizer taking process, the amount of the extracted active heat raw meal accounts for 0.1-5% of the total amount of the raw meal, the loss on ignition of the taken active heat raw meal is less than 5%, the content of calcium oxide is more than 50%, and the temperature of the active heat raw meal at the material taking point is 800-950 ℃; the cooling method of the active thermal raw material is air cooling.
3. The low-temperature denitration and sulfur fixation method based on the cement clinker production line as recited in claim 1, wherein in the self-desulfurization process, the moisture content of the flue gas exiting the preheater unit is 5% -10%; the speed of the flue gas entering the bottom of the reactor is 20-50 m/s.
4. The method for low-temperature denitration and sulfur fixation based on the cement clinker production line as claimed in claim 1, wherein in the low-temperature denitration and sulfur fixation process, the mass fraction of sodium chlorite in the sodium chlorite solution is 3% -10%; the sodium chlorite solution is fully atomized by a spray gun and then sprayed into an air duct.
5. The method for low-temperature denitration and sulfur fixation based on cement clinker production line as claimed in claim 1, wherein the amount of the sodium chlorite solution is determined according to NO in flue gas x And SO 2 Concentration adjustment, the concrete adjustment mode is:
in the formula, V is the volume of spraying sodium chlorite solution into the air duct, and the unit is L; omega is the mass of the sodium chlorite solutionA score; rho is the density of the sodium chlorite solution and is expressed in kg/m 3 ;[NO x ] i 、[SO 2 ] i Respectively NO in the flue gas of the high-temperature fan x And SO 2 In ppm; [ NO ] x ] j NO to meet emission requirements x Concentration; k is a radical of 1 Is NO x Concentration correction coefficient is 1 x-1.5 x, wherein x is NO x The number of middle O; k is a radical of 2 Is SO 2 And (5) correcting the coefficient of concentration by taking 1.5-2.5.
6. The method for low-temperature denitration and sulfur fixation on the basis of the cement clinker production line as claimed in claim 1, wherein the flue gas dehydration process controls the temperature of the flue gas to be more than 80 ℃ before entering the dust collector, and prevents water vapor in the flue gas from becoming dew, so that the dust collector and conveying system equipment are prevented from being influenced.
7. The method for low-temperature denitration and sulfur fixation on the basis of the cement clinker production line as recited in claim 1, wherein the desulfurization slag comprises desulfurization product calcium sulfate, denitration product calcium nitrate and dehydration product calcium hydroxide.
8. The method for low-temperature denitration and sulfur fixation based on the cement clinker production line as recited in claim 1, wherein the decomposition furnace is a gradient combustion self-denitration decomposition furnace, the self-denitration efficiency is > 60%, and the concentration of NOx in the flue gas discharged from the decomposition furnace is 500-800 ppm.
9. The method for low-temperature denitration and sulfur fixation on the basis of the cement clinker production line as recited in claim 1, wherein the SNCR denitration is carried out by using the amount of ammonia water to control the ammonia escape amount to be less than 10 ppm.
10. The system for low-temperature denitration and sulfur fixation based on the cement clinker production line comprises a preheater unit, a heat exchange system and a high-temperature fan, wherein the preheater unit comprises a cyclone and a decomposing furnace which are arranged in a multi-stage manner, and the heat exchange system and the high-temperature fan are sequentially arranged on an outlet air pipe of a primary cyclone of the preheater unit; the method is characterized in that:
the system comprises a preheater unit, a cooling system, a reactor, a dust collector and a conveying system, wherein the preheater unit comprises a last-stage cyclone cylinder, a feed pipe, a thermal raw material pipeline I and a thermal raw material pipeline II;
the first hot raw material pipeline is connected with an inlet of a cooling system, the cooling system is used for cooling active hot raw materials in the first hot raw material pipeline to be below 150 ℃, an outlet of the cooling system is connected with a material inlet at the bottom of the reactor, and a flue gas inlet at the bottom of the reactor is connected with an outlet of a high-temperature fan;
an outlet at the top of the reactor is connected with a dust collector through an air pipe, a sodium chlorite solution spraying port is arranged on the air pipe close to the outlet of the reactor, and an outlet of the hot raw material pipeline II is connected with the air pipe close to the inlet of the dust collector, so that the temperature of flue gas at the inlet of the dust collector is higher than 80 ℃ before entering the dust collector; and a discharge port of the dust collector is connected with the preheater unit through a conveying system.
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