CN116920590A - Denitration material and method for denitration of cement kiln tail gas by using methanol as reducing agent - Google Patents
Denitration material and method for denitration of cement kiln tail gas by using methanol as reducing agent Download PDFInfo
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 99
- 239000004568 cement Substances 0.000 title claims abstract description 40
- 239000003638 chemical reducing agent Substances 0.000 title claims abstract description 28
- 239000000463 material Substances 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 title claims abstract description 21
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 128
- 239000002245 particle Substances 0.000 claims abstract description 39
- 239000003054 catalyst Substances 0.000 claims abstract description 34
- 239000002893 slag Substances 0.000 claims abstract description 28
- 239000000843 powder Substances 0.000 claims abstract description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 20
- 235000013162 Cocos nucifera Nutrition 0.000 claims abstract description 20
- 244000060011 Cocos nucifera Species 0.000 claims abstract description 20
- 238000000227 grinding Methods 0.000 claims abstract description 20
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000002699 waste material Substances 0.000 claims abstract description 15
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 13
- WMOHXRDWCVHXGS-UHFFFAOYSA-N [La].[Ce] Chemical compound [La].[Ce] WMOHXRDWCVHXGS-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000011572 manganese Substances 0.000 claims abstract description 12
- 239000006104 solid solution Substances 0.000 claims abstract description 12
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 11
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 11
- PNVJTZOFSHSLTO-UHFFFAOYSA-N Fenthion Chemical compound COP(=S)(OC)OC1=CC=C(SC)C(C)=C1 PNVJTZOFSHSLTO-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002131 composite material Substances 0.000 claims abstract description 10
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 10
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910000428 cobalt oxide Inorganic materials 0.000 claims abstract description 8
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims abstract description 8
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000004519 manufacturing process Methods 0.000 claims abstract description 7
- 239000007789 gas Substances 0.000 claims description 19
- 239000002994 raw material Substances 0.000 claims description 15
- 238000002360 preparation method Methods 0.000 claims description 13
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 11
- 239000003546 flue gas Substances 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 9
- 239000002817 coal dust Substances 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- 239000007921 spray Substances 0.000 claims description 3
- 230000000694 effects Effects 0.000 abstract description 7
- 230000008569 process Effects 0.000 abstract description 4
- 231100000989 no adverse effect Toxicity 0.000 abstract description 2
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 30
- 238000006243 chemical reaction Methods 0.000 description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 description 5
- 238000006722 reduction reaction Methods 0.000 description 5
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 5
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000013543 active substance Substances 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229910052596 spinel Inorganic materials 0.000 description 3
- 239000011029 spinel Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 239000002910 solid waste Substances 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- 229910002482 Cu–Ni Inorganic materials 0.000 description 1
- 229910017827 Cu—Fe Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 239000001120 potassium sulphate Substances 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
Classifications
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Environmental & Geological Engineering (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a denitration material and a method for denitration of cement kiln tail gas by using methanol as a reducing agent, wherein the denitration material comprises a denitration agent A, a denitration agent B and a denitration agent C which are independently packaged; uniformly mixing lanthanum cerium solid solution, waste vanadium-based denitration catalyst and perovskite type composite metal oxide, and grinding to form a denitration agent A; crushing coconut shell carbon into small particles, and uniformly mixing the small particles with carbide slag powder to form a denitration agent B; and (3) uniformly mixing OMS-2 with one or more of zirconia, cobalt oxide and ferroferric oxide, then adding electrolytic manganese slag, uniformly mixing, and grinding to a certain particle size to form the denitration agent C. The cement kiln denitration agent is added into the cement production process in different adding modes respectively to cooperatively play a denitration role, so that the cement kiln denitration effect is realized. By the invention, NO is realized by using methanol as a reducing agent x The method has the advantages of removal and ultralow emission, no secondary pollution in the whole process and no adverse effect on the performance of cement clinker.
Description
Technical Field
The invention belongs to the technical field of environmental engineering, and particularly relates to a denitration material and a denitration method for denitration of cement kiln tail gas by using methanol as a reducing agent.
Background
The cement industry is one of the main emission sources of nitrogen oxides, polluting the environment and endangering human health. In recent years, ecological environmentA series of policies and documenting limits on the concentration and total emissions of nitrogen oxides are promulgated by the department. The comprehensive working scheme of energy conservation and emission reduction proposes that the total emission amount of the nitrogen oxides is reduced by more than 10 percent than 2020. The performance of cement enterprises is classified in technical guidelines for making emergency emission reduction measures in heavy pollution weather major industries, and the emission limit of nitrogen oxides of cement enterprises with A-level performance level is required to be 50mg/Nm 3 Ammonia slip < 5mg/Nm 3 。
To achieve the above emission index, SCR technology is one of the most mature and reliable denitration technologies. Currently, in the cement industry, technologies mainly applied include high-temperature high-dust SCR technology and medium-temperature medium-dust SCR technology. Because the escaping ammonia of the SNCR system is used as the reducing agent, a certain amount of ammonium sulfate salt can be generated, equipment corrosion and pipeline blockage are caused, and meanwhile, the problem of secondary pollution exists. Therefore, the development of SCR denitration with non-ammonia reducing agent is a better choice, and a plurality of patents disclose the use of CO as a reducing agent for denitration reaction
Patent CN 113275008 discloses a CO-SCR catalyst, a preparation method and application thereof, and mentions that the catalyst can be used for flue gas denitration in the cement industry. SiO is adopted 2 The ball load Ir and K are used for CO-SCR denitration reaction, noble metal is adopted as a main active component, and the cement industry has large smoke amount and large catalyst dosage, and is not suitable for noble metal catalysts with high price. The invention adopts a fixed bed catalyst, combines the existing cement production process, needs to arrange a reactor at the outlet position of a preheater, and can be influenced by sulfides in flue gas in the temperature range of 225-350 ℃, especially the auxiliary agent and SO 2 O and O 2 The reaction takes place to form potassium sulphate and at this temperature the reaction is irreversible, thus resulting in deactivation of the catalyst.
Patent CN 112138665A discloses a CO-SCR low-temperature Gao Xiaofei noble metal oxide catalyst and a preparation method thereof, which adopts a transition metal oxide CuCoAlO x Is a catalyst; CN 113908842A discloses a denitration catalyst for CO-SCR flue gas denitration and a preparation method thereof, and a Cu-Ce-Al/mullite catalyst is prepared, wherein O is not introduced in the test process of the two patents 2 While CO-SCR reaction is opposite to O 2 Extremely sensitive to concentration, let in O 2 The post-denitration efficiency is greatly reduced.
CN 112371126A discloses a low-temperature CO-SCR denitration Cu-Fe/AC catalyst, a preparation method and application thereof, CN 114682294A discloses a CO-SCR denitration catalyst, a preparation method and application thereof, and a Y-type molecular sieve and TiO are adopted 2 And magnesia is used as a carrier, and oxides of La, ce and Sr are used as auxiliary agents; CN112316946 discloses a low-temperature CO-SCR denitration Cu-Ni/AC catalyst and a preparation method thereof; CN111229212 discloses a CO-SCR denitration catalyst, a preparation method and application, wherein one or more of Cu, fe, ce, co and Ni oxide are used as active components, transition metal or rare earth metal oxide is used as active components, and a fixed bed is used for CO-SCR denitration, because of SO 2 Is easily oxidized into SO by a catalyst 3 And then reacts with oxides to generate metal sulfate, so that sulfur poisoning can occur in the practical application of cement flue gas denitration, and the service life of the catalyst is influenced.
In summary, the existing denitration technology in the cement industry has the following problems:
(1) Ammonia is adopted as a reducing agent for SCR denitration reaction, a certain amount of ammonium sulfate or ammonium nitrate is generated at the rear end and deposited on the surface of a catalyst or in equipment and pipelines, so that the catalyst is deactivated, the equipment is corroded or a pipeline is blocked;
(2) Denitration using a fixed bed reactor with CO as the reducing agent, because the reaction is specific to O 2 The denitration efficiency of the cement kiln at the rear end of the preheater is greatly affected due to the extremely sensitive property;
(3) By adopting the fixed bed CO-SCR denitration, the catalyst is deactivated rapidly, so that the waste denitration catalyst can be generated, and the environmental protection cost is greatly improved if the waste denitration catalyst is identified as dangerous waste.
Disclosure of Invention
Aiming at the problems existing in the prior art, one of the purposes of the invention is to provide a denitration material and a method for denitration of cement kiln tail gas by using methanol as a reducing agent, wherein A, B, C denitration agent is adopted as an active component, and the denitration material and the method are respectively added into a cement kiln through different adding modesIn the cement production process, the denitration effect is synergistically exerted, and the denitration effect of the cement kiln is realized. By the invention, NO is realized by using methanol as a reducing agent x The method has the advantages of removal and ultralow emission, no secondary pollution in the whole process and no adverse effect on the performance of cement clinker.
In order to solve the technical problems, the invention adopts the following technical scheme: a denitration material for denitration of cement kiln tail gas by using methanol as a reducing agent comprises a denitration agent A, a denitration agent B and a denitration agent C which are independently packaged;
the preparation of the denitration agent A comprises the steps of uniformly mixing a lanthanum-cerium solid solution, a waste vanadium-based denitration catalyst and a perovskite type composite metal oxide according to a certain mass, and grinding to form the denitration agent A;
the preparation of the denitration agent B comprises the steps of crushing a certain amount of coconut shell carbon into small particles with a certain size, and uniformly mixing the small particles with carbide slag powder to form the denitration agent B;
and (3) preparing the denitration agent C, uniformly mixing a certain mass of OMS-2 with one or more of zirconia, cobalt oxide and ferroferric oxide, then adding electrolytic manganese slag, uniformly mixing, and grinding to a certain particle size to form the denitration agent C.
The particle size of the mixture of the denitration agent A after grinding is less than or equal to 80 mu m, and the screen residue is less than 14%.
According to the mass parts, the waste vanadium-based denitration catalyst accounts for 3-5 parts; 8-10 parts of perovskite type oxide; 2-5 parts of lanthanum-cerium solid solution.
The perovskite type composite metal oxide A site is one or a combination of more than one of La and Ce, bi, sm, gd, ca, be, ba, sr, and the B site is one or a combination of more than one of Cu, ni and Ti, V, cr, mn, fe, co, wherein La accounts for more than 20% of the A site, cu accounts for more than 20% of the B site, and Ni accounts for more than 30% of the B site.
According to the parts by weight, the particle size of the crushed coconut shell carbon is 0.01-1 mm, the particle size of the carbide slag powder is less than or equal to 80 mu m, the screen residue is less than 14%, the coconut shell carbon particles account for 3-5 parts, and the carbide slag powder accounts for 1-2 parts.
According to the mass portion, the size of the powder of the denitrating agent C is less than or equal to 40 mu m, the screen residue is less than 8%, wherein OMS-2 accounts for 1-2 portions, zirconia accounts for 0-1 portion, cobalt oxide accounts for 0-1 portion, ferroferric oxide accounts for 0-1 portion, and electrolytic manganese slag accounts for 1-2 portions.
The method for denitration of cement kiln tail gas by using methanol as a reducing agent adopts the denitration materials to realize denitration by using methanol in flue gas as the reducing agent, and comprises the following steps:
(1) Uniformly mixing the denitration agent C with coal dust, and adding the mixture into a cement production system from a decomposing furnace;
(2) Adding a denitration agent B into the rear end of the outlet of the decomposing furnace;
(3) Mixing the denitration agent A with the raw material, grinding, and adding the mixed raw material from a connecting air pipe of a kiln tail C1 and a C2 cyclone;
the total denitration material accounts for 0.1 per mill to 0.5 percent of the mass of the raw material, wherein the total denitration material comprises 2 to 3 parts by mass of denitration agent A, 3 to 5 parts by mass of denitration agent B and 1 to 2 parts by mass of denitration agent C.
The methanol is sprayed in a spray gun of the original SNCR system.
The beneficial effects of the invention are as follows:
1) The invention can realize the removal of NOx in the tail gas of the cement kiln without adding NH 3 And subsequent pipeline blockage and equipment corrosion are avoided.
2) The temperature in the decomposing furnace is high and can reach more than 900 ℃, at the temperature, solid waste components in the denitration agent C can be effectively decomposed into active catalytic components, and other components in the denitration agent C are combined to form a three-functional catalyst in a synergistic way, so that on one hand, the coal dust can be catalyzed to be fully combusted, the ignition point is reduced, the burnout degree is improved, and meanwhile, the active components move to the adding position of the denitration agent B along with the flue gas; the denitration agent B is added at the rear end of the decomposing furnace, the coconut shell carbon in the denitration agent B is crushed into particles, so that the coconut shell carbon is prevented from being taken away too quickly by flue gas, partial catalyst is added by utilizing the catalysis effect, the oxidation efficiency of the coconut shell carbon is improved, and the oxygen content in the system is further reduced.
3) The denitration agent B is added at the rear end of the decomposing furnace, the temperature is higher and can reach more than 800 ℃, which is favorable for exerting CH of active components 3 OH-SCR denitration and is subjected to SO 2 Influence relative toSmaller.
4) The perovskite component in the denitration agent A can promote denitration and methanol oxidation, avoid exceeding the standard of methanol emission, has lower sulfur-resistant temperature, and can realize the generation of active components and the catalysis of NO at 550 DEG C x Deep reduction and removal, the lanthanum-cerium solid solution plays a role in synergistic denitration, improves denitration efficiency and eliminates part of SO (sulfur oxide) 2 Is a function of (a) and (b).
5) According to the invention, solid waste can be treated while catalytic denitration is performed, and resource recycling is performed, so that environmental protection value is created.
6) The denitration method of the invention does not generate dust and waste liquid additionally, has simple operation in the process, and does not increase equipment and occupied area newly.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention; it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments, and that all other embodiments obtained by persons of ordinary skill in the art without making creative efforts based on the embodiments in the present invention are within the protection scope of the present invention.
The invention relates to a denitration material for denitration of cement kiln tail gas by using methanol as a reducing agent, which comprises a denitration agent A, a denitration agent B and a denitration agent C which are independently packaged;
the preparation of the denitration agent A comprises the steps of uniformly mixing a lanthanum-cerium solid solution, a waste vanadium-based denitration catalyst and a perovskite type composite metal oxide according to a certain mass, and grinding to form the denitration agent A;
the preparation of the denitration agent B comprises the steps of crushing a certain amount of coconut shell carbon into small particles with a certain size, and uniformly mixing the small particles with carbide slag powder to form the denitration agent B;
and (3) preparing the denitration agent C, uniformly mixing a certain mass of OMS-2 with one or more of zirconia, cobalt oxide and ferroferric oxide, then adding electrolytic manganese slag, uniformly mixing, and grinding to a certain particle size to form the denitration agent C.
The particle size of the mixture of the denitration agent A after grinding is less than or equal to 80 mu m, and the screen residue is less than 14%.
According to the mass parts, the waste vanadium-based denitration catalyst accounts for 3-5 parts; 8-10 parts of perovskite type oxide; 2-5 parts of lanthanum-cerium solid solution.
The perovskite type composite metal oxide A site is one or a combination of more than one of La and Ce, bi, sm, gd, ca, be, ba, sr, and the B site is one or a combination of more than one of Cu, ni and Ti, V, cr, mn, fe, co, wherein La accounts for more than 20% of the A site, cu accounts for more than 20% of the B site, and Ni accounts for more than 30% of the B site.
According to the parts by weight, the particle size of the crushed coconut shell carbon is 0.01-1 mm, the particle size of the carbide slag powder is less than or equal to 80 mu m, the screen residue is less than 14%, the coconut shell carbon particles account for 3-5 parts, and the carbide slag powder accounts for 1-2 parts.
According to the mass portion, the size of the powder of the denitrating agent C is less than or equal to 40 mu m, the screen residue is less than 8%, wherein OMS-2 accounts for 1-2 portions, zirconia accounts for 0-1 portion, cobalt oxide accounts for 0-1 portion, ferroferric oxide accounts for 0-1 portion, and electrolytic manganese slag accounts for 1-2 portions.
The method for denitration of cement kiln tail gas by using methanol as a reducing agent adopts the denitration materials to realize denitration by using methanol in flue gas as the reducing agent, and comprises the following steps:
(1) Uniformly mixing the denitration agent C with coal dust, and adding the mixture into a cement production system from a decomposing furnace;
(2) Adding a denitration agent B into the rear end of the outlet of the decomposing furnace;
(3) Mixing the denitration agent A with the raw material, grinding, and adding the mixed raw material from a connecting air pipe of a kiln tail C1 and a C2 cyclone;
the total denitration material accounts for 0.1 per mill to 0.5 percent of the mass of the raw material, wherein the total denitration material comprises 2 to 3 parts by mass of denitration agent A, 3 to 5 parts by mass of denitration agent B and 1 to 2 parts by mass of denitration agent C.
Since the invention does not use NH 3 As a reducing agent, methanol can be injected at a spray gun of the original SNCR system;
the denitration agent A, B, C is used in combination to realize the effect of adopting methanol in flue gas to carry out denitration;
mixing the denitration agent C with pulverized coalUniformly, adding a cement production system from a decomposing furnace, and moving the denitration agent C along with flue gas to the kiln tail preheater after decomposing and reacting with each other in the decomposing furnace due to smaller powder particle size; the temperature of the adding position of the denitration agent C is higher, wherein the electrolytic manganese slag component is decomposed to generate active substances, the active substances and other active components move to the adding position of the denitration agent B to cooperatively play the denitration effect, and the active substances are not easy to react with SO in the temperature section 2 The combination is favorable for the denitration agent C to exert better catalytic function.
Adding the denitration agent B into the rear end of the outlet of the decomposing furnace at the position O 2 The concentration is low and can reach 1%, which is favorable for CH 3 The occurrence of an OH-SCR reaction; coconut shell carbon small particles and O in denitration agent B 2 The reaction can further reduce O 2 The concentration, the powder moves to the adding position of the denitrating agent B after the denitrating agent C is reacted and decomposed, and the medium active component catalyzes the reduction reaction of methanol and NOx to generate H in the temperature range of 550-800 DEG C 2 O、CO 2 And N 2 Because the active component in the denitration agent C is a transition metal coupled rare earth metal element, part of sulfur dioxide can be fixed by carbide slag powder in the denitration agent B, and the effect of protecting the active component is achieved;
the denitration agent A and the raw material are mixed and then ground, the mixed raw material is added from a connecting air pipe of a kiln tail C1 and a C2 cyclone, and perovskite active components in the raw material A have two functions, and the element valence state of the perovskite active components can be changed between +2 and +3, so that the perovskite active components have excellent catalytic performance, can further promote methanol-SCR reaction at a higher temperature of 400-550 ℃, and can promote the catalytic oxidation of residual methanol to CO at a lower temperature of 330-400 DEG simultaneously 2 And H 2 O, avoid polluting the environment. Meanwhile, the sulfur-resistant temperature of the waste denitration catalyst in the denitration agent A is low, the generation of active components and the catalytic NOx deep reduction removal can be realized at 550 ℃, the lanthanum-cerium solid solution plays a role in synergistic denitration, and part of SO is eliminated while the denitration efficiency is improved 2 Is a function of (1);
the parts in the examples below are parts by weight.
Example 1
(1) Preparing a denitration agent A: uniformly mixing 3 parts of waste vanadium-based denitration catalyst, 2 parts of lanthanum cerium solid solution and 10 parts of perovskite type composite metal oxide, and grinding to obtain particles with the size less than or equal to 80 mu m (the screen residue is less than 14 percent) to form a denitration agent A; wherein the spinel composition is La 0.6 Ce 0.4 Cu 0.2 Ni 0.3 Co 0.7 O 4 ；
(2) Preparing a denitration agent B: crushing 3 parts of coconut shell carbon into small particles with a certain size, and uniformly mixing with 1 part of carbide slag powder to form a denitration agent B; the particle size of the crushed coconut shell carbon is 0.01-0.1 mm, and the particle size of the carbide slag powder is less than or equal to 80 mu m (the screen residue is less than 14 percent);
(3) Preparing a denitration agent C: uniformly mixing 1 part of OMS-2 and 1 part of ferroferric oxide, then adding 1 part of electrolytic manganese slag, uniformly mixing, and grinding until the size is less than or equal to 40 mu m (the screen residue is less than 8 percent) to form a denitration agent C;
the mass parts of the denitration agent A, the denitration agent B and the denitration agent C are 2 parts of the denitration agent A, 3 parts of the denitration agent B and 1 part of the denitration agent C. The mass sum of the denitration agent A, the denitration agent B and the denitration agent C accounts for 0.3% of the mass of the raw material; the injection amount of methanol is 200L/h;
the background emission concentration of the nitrogen oxide at the C1 outlet is 300mg/Nm 3 After A, B and the denitration agent C are added according to the adding method in the specification, the nitrogen oxide in the tail gas is reduced to 45mg/Nm 3 。
Example 2
(1) Preparing a denitration agent A: uniformly mixing 4 parts of waste vanadium-based denitration catalyst, 3 parts of lanthanum cerium solid solution and 9 parts of perovskite type composite metal oxide, and grinding to obtain particles with the size less than or equal to 80 mu m (the screen residue is less than 14 percent) to form a denitration agent A; wherein the spinel composition is La 0.9 Bi 0.1 Cu 0.33 Ni 0.3 Fe 0.4 O 4 ；
(2) Preparing a denitration agent B: crushing 4 parts of coconut shell carbon into small particles with a certain size, and uniformly mixing with 1 part of carbide slag powder to form a denitration agent B; the particle size of the crushed coconut shell carbon is 0.01-0.1 mm, and the particle size of the carbide slag powder is less than or equal to 80 mu m (the screen residue is less than 14 percent);
(3) Preparing a denitration agent C: uniformly mixing 2 parts of OMS-2 and 1 part of zirconia, then adding 1 part of electrolytic manganese slag, uniformly mixing, and grinding until the size is less than or equal to 40 mu m (the screen residue is less than 8 percent) to form a denitration agent C;
the mass parts of the denitration agent A, the denitration agent B and the denitration agent C are 3 parts of the denitration agent A, 3 parts of the denitration agent B and 2 parts of the denitration agent C. The mass sum of the denitration agent A, the denitration agent B and the denitration agent C accounts for 0.5% of the mass of the raw material; the injection amount of methanol is 260L/h;
the background emission concentration of the nitrogen oxide at the C1 outlet is 300mg/Nm 3 After A, B and the denitration agent C are added according to the adding method in the specification, the nitrogen oxide in the tail gas is reduced to 30mg/Nm 3 。
Example 3
(1) Preparing a denitration agent A: uniformly mixing 3 parts of waste vanadium-based denitration catalyst, 2 parts of lanthanum cerium solid solution and 8 parts of perovskite type composite metal oxide, and grinding to obtain particles with the size less than or equal to 80 mu m (the screen residue is less than 14 percent) to form a denitration agent A; wherein the spinel composition is La 0.7 Bi 0.3 Cu 0.55 Ni 0.3 Mn 0.2 O 4 ；
(2) Preparing a denitration agent B: crushing 3 parts of coconut shell carbon into small particles with a certain size, and uniformly mixing with 1 part of carbide slag powder to form a denitration agent B; the particle size of the crushed coconut shell carbon is 0.01-0.1 mm, and the particle size of the carbide slag powder is less than or equal to 80 mu m (the screen residue is less than 14 percent);
(3) Preparing a denitration agent C: uniformly mixing 1 part of OMS-2, 1 part of zirconia and 1 part of cobalt oxide, then adding 1 part of electrolytic manganese slag, uniformly mixing, and grinding until the size is less than or equal to 40 mu m (the screen residue is less than 8 percent) to form a denitration agent C;
the mass parts of the denitration agent A, the denitration agent B and the denitration agent C are 3 parts of the denitration agent A, 3 parts of the denitration agent B and 1 part of the denitration agent C. The mass sum of the denitration agent A, the denitration agent B and the denitration agent C accounts for 0.1% of the mass of the raw material; the injection amount of methanol is 200L/h;
the background emission concentration of the nitrogen oxide at the C1 outlet is 300mg/Nm 3 After A, B and the denitration agent C are added according to the adding method in the specification, the nitrogen oxide in the tail gas is reduced to 50mg/Nm 3 。
The above-described embodiments are only for illustrating the technical spirit and features of the present invention, and it is intended that those skilled in the art can understand the content of the present invention and implement it accordingly, and the scope of the present invention is not limited to the embodiments, i.e., equivalent changes or modifications to the spirit of the present invention are included in the scope of the present invention.
Claims (8)
1. A denitration material for denitration of cement kiln tail gas by using methanol as a reducing agent is characterized by comprising a denitration agent A, a denitration agent B and a denitration agent C which are independently packaged;
the preparation of the denitration agent A comprises the steps of uniformly mixing a lanthanum-cerium solid solution, a waste vanadium-based denitration catalyst and a perovskite type composite metal oxide according to a certain mass, and grinding to form the denitration agent A;
the preparation of the denitration agent B comprises the steps of crushing a certain amount of coconut shell carbon into small particles with a certain size, and uniformly mixing the small particles with carbide slag powder to form the denitration agent B;
and (3) preparing the denitration agent C, uniformly mixing a certain mass of OMS-2 with one or more of zirconia, cobalt oxide and ferroferric oxide, then adding electrolytic manganese slag, uniformly mixing, and grinding to a certain particle size to form the denitration agent C.
2. The denitration material for denitration of cement kiln tail gas by using methanol as a reducing agent according to claim 1, wherein the particle size of the mixture of the denitration agent A after grinding is less than or equal to 80 mu m, and the screen residue is less than 14%.
3. The denitration material for denitration of cement kiln tail gas by using methanol as a reducing agent according to claim 1, wherein the waste vanadium-based denitration catalyst accounts for 3-5 parts by mass; 8-10 parts of perovskite type oxide; 2-5 parts of lanthanum-cerium solid solution.
4. The denitration material for denitration of cement kiln exhaust gas by using methanol as a reducing agent according to claim 1, wherein the perovskite type composite metal oxide has an A site of one or more of La and Ce, bi, sm, gd, ca, be, ba, sr, and a B site of one or more of Cu, ni and Ti, V, cr, mn, fe, co, wherein La accounts for more than 20% of the A site, cu accounts for more than 20% of the B site, and Ni accounts for more than 30% of the B site.
5. The denitration material for denitration of cement kiln tail gas by using methanol as a reducing agent according to claim 1, wherein the size of the crushed coconut shell carbon particles is 0.01-1 mm, the size of the carbide slag powder particles is less than or equal to 80 mu m, the screen residue is less than 14%, the coconut shell carbon particles account for 3-5 parts, and the carbide slag powder accounts for 1-2 parts.
6. The denitration material for denitration of cement kiln tail gas by using methanol as a reducing agent according to claim 1, wherein the size of the denitration agent C powder is less than or equal to 40 mu m, the screen residue is less than 8%, wherein OMS-2 accounts for 1-2 parts, zirconia accounts for 0-1 part, cobalt oxide accounts for 0-1 part, ferroferric oxide accounts for 0-1 part, and electrolytic manganese slag accounts for 1-2 parts.
7. A method for denitration of cement kiln tail gas by using methanol as a reducing agent, which is characterized in that denitration materials in any one of claims 1-6 are used in combination to realize denitration by using methanol in flue gas as the reducing agent, and the method comprises the following steps:
(1) Uniformly mixing the denitration agent C with coal dust, and adding the mixture into a cement production system from a decomposing furnace;
(2) Adding a denitration agent B into the rear end of the outlet of the decomposing furnace;
(3) Mixing the denitration agent A with the raw material, grinding, and adding the mixed raw material from a connecting air pipe of a kiln tail C1 and a C2 cyclone;
the total denitration material accounts for 0.1 per mill to 0.5 percent of the mass of the raw material, wherein the total denitration material comprises 2 to 3 parts by mass of denitration agent A, 3 to 5 parts by mass of denitration agent B and 1 to 2 parts by mass of denitration agent C.
8. The method for denitration of cement kiln tail gas by using methanol as a reducing agent according to claim 7, wherein the methanol is injected at a spray gun of an original SNCR system.
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