CN112169808A - Desulfurization and denitrification catalyst and preparation method thereof - Google Patents
Desulfurization and denitrification catalyst and preparation method thereof Download PDFInfo
- Publication number
- CN112169808A CN112169808A CN201910591422.3A CN201910591422A CN112169808A CN 112169808 A CN112169808 A CN 112169808A CN 201910591422 A CN201910591422 A CN 201910591422A CN 112169808 A CN112169808 A CN 112169808A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- active coke
- desulfurization
- soaking
- nitrate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 53
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 40
- 230000023556 desulfurization Effects 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 239000000571 coke Substances 0.000 claims abstract description 51
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000003607 modifier Substances 0.000 claims abstract description 7
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 54
- 238000005303 weighing Methods 0.000 claims description 31
- 238000002791 soaking Methods 0.000 claims description 30
- 238000001035 drying Methods 0.000 claims description 26
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 26
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 22
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 18
- 235000006408 oxalic acid Nutrition 0.000 claims description 18
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 13
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 13
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 13
- 235000010333 potassium nitrate Nutrition 0.000 claims description 13
- 239000004323 potassium nitrate Substances 0.000 claims description 13
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 238000001914 filtration Methods 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 11
- 230000007935 neutral effect Effects 0.000 claims description 11
- 229910017604 nitric acid Inorganic materials 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- 238000005470 impregnation Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 2
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 claims description 2
- 230000008901 benefit Effects 0.000 abstract description 6
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 abstract 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 abstract 1
- 239000005751 Copper oxide Substances 0.000 abstract 1
- 229910000428 cobalt oxide Inorganic materials 0.000 abstract 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 abstract 1
- 239000000306 component Substances 0.000 abstract 1
- 229910000431 copper oxide Inorganic materials 0.000 abstract 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 abstract 1
- 229910001950 potassium oxide Inorganic materials 0.000 abstract 1
- 230000000087 stabilizing effect Effects 0.000 abstract 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 13
- 239000003546 flue gas Substances 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- RAHZWNYVWXNFOC-UHFFFAOYSA-N sulfur dioxide Inorganic materials O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 7
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000000746 purification Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 2
- 230000020477 pH reduction Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 108010054147 Hemoglobins Proteins 0.000 description 1
- 102000001554 Hemoglobins Human genes 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 108010061951 Methemoglobin Proteins 0.000 description 1
- 206010035664 Pneumonia Diseases 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 206010006451 bronchitis Diseases 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 210000000795 conjunctiva Anatomy 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 208000032839 leukemia Diseases 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 230000005180 public health Effects 0.000 description 1
- 230000000241 respiratory effect Effects 0.000 description 1
- 210000001533 respiratory mucosa Anatomy 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/847—Vanadium, niobium or tantalum or polonium
- B01J23/8472—Vanadium
-
- 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
- B01D53/86—Catalytic processes
- B01D53/8637—Simultaneously removing sulfur oxides and nitrogen oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Environmental & Geological Engineering (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to the technical field of catalysts, and relates to a modified desulfurization and denitrification catalyst and a preparation method thereof. The catalyst is loaded on an active coke carrier by taking vanadium pentoxide as an active component and copper oxide, iron oxide, potassium oxide and cobalt oxide as modifiers, wherein the vanadium pentoxide is measured by mass percentage, and V2O51‑5%、CuO2‑5%、Fe3O42‑5%、K2O1-1.5%, CoO1-1.5%, and the balance active coke carrier. The modified catalyst can realize simultaneous desulfurization and denitrification in one furnace, the desulfurization efficiency reaches 100 percent, the denitrification efficiency reaches 85 percent, and the modified catalyst has the advantages of reducing equipment, saving space, reducing investment, stabilizing operation and the like.
Description
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to a modified desulfurization and denitrification catalyst and a preparation method thereof.
Background
Coal is one of the main energy sources for industrial development and is developed and utilized rapidly, and SO is contained in flue gas discharged by coal-fired boilers and thermal power plants2、NOxAnd dust and other harmful substances, which causes the environment to worsen and seriously threatens the ecological environment and public health.
Therefore, effective control and reduction of sulfur oxide and nitrogen oxide emissions has become a very urgent task at present.
The flue gas type pollution is a main pollution source of atmospheric pollution at present stage of China, and is particularly expressed as SO2And NOxAcid rain and photochemical smog are caused by the emission of (a). The smoke pollution can not only cause soil acidification, slow growth of animals and plants, water body acidification, building corrosion and the like, but also harm human health to a great extent, such as NOxThe harm to human body is shown in that NO is combined with hemoglobin in blood to cause methemoglobin leukemia and the like; SO in atmosphere2Has strong irritation to upper respiratory mucosa and conjunctiva, and is easy to cause diseases of respiratory organs, such as pneumonia and bronchitis.
SO2And NOxAt the same time in the discharged flue gas, SO2And NOxThe chemical properties are different, the difference of the removing mechanism is large, and if the removing method is adopted, the problems of large occupied area, more equipment, complex operation, poor economic benefit and the like are caused. Since both gases are acidic oxides, a simultaneous removal process can be designed.
At present, the integration of flue gas desulfurization and denitration mainly comprises several processes of wet desulfurization and denitration, dry desulfurization and denitration and semi-dry desulfurization and denitration. Wherein, the wet-method removal effect is better, but the problems of serious pollution of waste liquid after removal and the like exist; the dry removal has the defects of high operating equipment cost and the like; the semidry method has the advantages of the dry method and the wet method, but has the problems of unstable operation and the like.
The dry purification integrated desulfurization and denitrification technology realizes simultaneous desulfurization and denitrification processes on the same set of device, and has the advantages of less equipment, space saving, investment reduction, stable operation and the like.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to realize a dry purification integrated desulfurization and denitrification technology by modifying a prepared desulfurization and denitrification catalyst, and solve the problems of serious waste liquid pollution, high operating equipment cost, unstable operation and the like in the conventional desulfurization and denitrification processes.
The technical scheme is as follows: the purpose of the invention is realized by the following technical scheme.
The invention provides a modified desulfurization and denitrification catalyst, which takes active coke as a carrier and V2O5CuO and Fe are used as active components3O4、K2O, CoO is a modifier.
The catalyst component is calculated by mass percent, V2O51-5%、CuO2-5%、Fe3O42-5%、K2O1-1.5%, CoO1-1.5%, and the balance of carrier.
The specific surface area of the active coke carrier is 280-400 m2/g。
The active component V2O5Is prepared from ammonium metavanadate and modifier chosen from copper nitrate, iron nitrate, potassium nitrate and cobalt nitrate.
The invention also provides a preparation method of the catalyst, which comprises the following steps: firstly, soaking an active coke carrier in a nitric acid solution, filtering, washing to be neutral, and drying for later use; secondly, weighing ammonium metavanadate according to the mass percentage, and preparing a solution by the ammonium metavanadate and oxalic acid; soaking active coke carrier by an isovolumetric soaking method, drying, and N2Roasting under the protection condition to obtain V2O5Active coke is used; weighing copper nitrate, ferric nitrate, potassium nitrate and cobalt nitrate according to mass percentage, adding deionized water, heating and stirring until the mixture is completely dissolved; fourthly, the roasted V2O5Adding active coke into the solution, soaking in the same volume, drying, and roasting to obtain the catalyst.
Preferably, the catalyst preparation method of the present invention comprises the following steps:
(1) soaking the active coke carrier in a nitric acid solution with the concentration of 0.4mol/L for 3-5h, filtering and washing to be neutral, and drying in a 120 ℃ oven for 5-6h for later use;
(2) weighing ammonium metavanadate according to mass percent, weighing oxalic acid according to a molar ratio of 1:2, and preparing a solution; soaking active coke carrier by isovolumetric soaking method, oven drying at 120 deg.C for 5-6h, and muffle furnace N at 500 deg.C2Roasting for 5 hours under the protection condition to obtain V2O5Active coke is used;
(3) weighing copper nitrate, ferric nitrate, potassium nitrate and cobalt nitrate according to the mass percentage, adding deionized water, heating and stirring until the mixture is completely dissolved;
(4) the roasted V is2O5Adding active coke into the solution III, soaking for 6h in the same volume, drying in a 120 ℃ oven for 5-6h, and roasting in a 500 ℃ muffle furnace for 5-6h to obtain the catalyst.
The invention also provides an application of the catalyst, and the catalyst is used for desulfurization and denitrification reactions.
Preferably, the catalyst is activated for 2-3h at 500 ℃ before being used in desulfurization and denitrification reactions.
Preferably, the conditions of the catalyst for desulfurization and denitrification reaction are as follows: the reaction temperature is 280 plus 350 ℃ and the space velocity is 1000 plus 5000h-1The gas component is NO: 500-700ppm SO2:500-750ppm、NH3：600-800ppm、O2The total volume content is 8 percent, and the rest is N2The reaction is carried out at normal pressure.
The invention has the advantages of
(1) By adopting the catalyst, the removal rate of nitrogen oxide measured by the reaction at the flue gas outlet reaches more than 85 percent, and the removal rate of sulfur dioxide can reach 100 percent;
(2) by adopting the catalyst, the integrated desulfurization and denitrification technology of dry purification is realized, namely, the simultaneous desulfurization and denitrification process is realized on the same set of device, and the catalyst has the advantages of less equipment, space saving, investment reduction, stable operation and the like.
Detailed Description
The present invention will be further described with reference to specific embodiments.
Example 1
Weighing 50g of active coke, adding the active coke into 0.4mol/L dilute nitric acid, soaking for 3h, filtering, washing to be neutral, and drying for 5h in an oven at 120 ℃ to obtain the active coke for later use. Weighing 5.15g of ammonium metavanadate and 11.0g of oxalic acid, dissolving in deionized water to prepare a solution, heating until the ammonium metavanadate and the oxalic acid are completely dissolved, adding active coke for equal-volume impregnation, fully impregnating for 5 hours, drying in a 120 ℃ oven for 5 hours; placing in a muffle furnace at 500 ℃ and N2Roasting for 5 hours for standby under the atmosphere condition. Weighing 5.28g, 5.39g, 2.17g and 4.65g of copper nitrate, ferric nitrate, potassium nitrate and cobalt nitrate respectively, completely dissolving in deionized water, soaking the modified components in the same volume for 6 hours, baking in a 120 ℃ oven for 5 hours, placing in a muffle furnace, and roasting at 500 ℃ for 5 hours to obtain the desulfurization and denitrification catalyst.
Example 2
Weighing 50g of active coke, adding the active coke into 0.4mol/L dilute nitric acid, soaking for 3h, filtering, washing to be neutral, and drying for 5h in a muffle furnace at 120 ℃ to obtain the active coke for standby. Weighing 10.3g of ammonium metavanadate and 22.0g of oxalic acid, dissolving in deionized water to prepare a solution, heating until the ammonium metavanadate and the oxalic acid are completely dissolved, adding active coke for equal-volume impregnation, fully impregnating for 5 hours, drying in a 120 ℃ oven for 5 hours; placing in a muffle furnace at 500 ℃ and N2Roasting for 5 hours for standby under the atmosphere condition. Weighing 5.28g, 5.39g, 2.17g and 4.65g of copper nitrate, ferric nitrate, potassium nitrate and cobalt nitrate respectively, completely dissolving in deionized water, soaking the modified components in the same volume for 6 hours, baking in a 120 ℃ oven for 5 hours, placing in a muffle furnace, and roasting at 500 ℃ for 5 hours to obtain the desulfurization and denitrification catalyst.
Example 3
Weighing 50g of active coke, adding the active coke into 0.4mol/L dilute nitric acid, soaking for 3h, filtering, washing to be neutral, and drying for 5h in a muffle furnace at 120 ℃ to obtain the active coke for standby. Weighing 10.3g of ammonium metavanadate and 22.0g of oxalic acid, dissolving in deionized water to prepare a solution, heating until the ammonium metavanadate and the oxalic acid are completely dissolved, adding active coke for equal-volume impregnation, fully impregnating for 5 hours, drying in a 120 ℃ oven for 5 hours; placing in a muffle furnace at 500 ℃ and N2Roasting for 5 hours for standby under the atmosphere condition. Weighing 6.24g, 6.54g, 3.06g and 4.82g of copper nitrate, ferric nitrate, potassium nitrate and cobalt nitrate respectively, completely dissolving in deionized water, soaking the modified components in the same volume for 6 hours, baking in a 120 ℃ oven for 5 hours, placing in a muffle furnace, and roasting at 500 ℃ for 5 hours to obtain the desulfurization and denitrification catalyst.
Example 4
Weighing 50g of active coke, adding the active coke into 0.4mol/L dilute nitric acid, soaking for 5 hours, filtering, washing to be neutral, and drying for 5 hours in a muffle furnace at the temperature of 120 ℃ to obtain the active coke for standby. Weighing 10.3g of ammonium metavanadate and 22.0g of oxalic acid, dissolving in deionized water to prepare a solution, heating until the ammonium metavanadate and the oxalic acid are completely dissolved, adding active coke for equal-volume impregnation, fully impregnating for 5 hours, drying in a 120 ℃ oven for 5 hours; placing in a muffle furnace at 500 ℃ and N2Roasting for 5 hours for standby under the atmosphere condition. Weighing 8.64g, 8.74g, 4.22g and 6.04g of copper nitrate, ferric nitrate, potassium nitrate and cobalt nitrate respectively, completely dissolving in deionized water, soaking the modified components in the same volume for 6 hours, baking in a 120 ℃ oven for 5 hours, placing in a muffle furnace, and roasting at 500 ℃ for 5 hours to obtain the desulfurization and denitrification catalyst.
Example 5
Weighing 50g of active coke, adding the active coke into 0.4mol/L dilute nitric acid, soaking for 4 hours, filtering, washing to be neutral, and drying for 6 hours in a muffle furnace at the temperature of 120 ℃ to obtain the active coke for standby. Weighing 5.15g of ammonium metavanadate and 11.0g of oxalic acid, dissolving in deionized water to prepare a solution, heating until the ammonium metavanadate and the oxalic acid are completely dissolved, adding active coke for equal-volume impregnation, fully impregnating for 5 hours, drying in a 120 ℃ oven for 6 hours; placing in a muffle furnace at 500 ℃ and N2Roasting for 5 hours for standby under the atmosphere condition. Weighing 8.64g, 8.74g, 4.22g and 6.04g of copper nitrate, ferric nitrate, potassium nitrate and cobalt nitrate respectively, completely dissolving in deionized water, soaking the modified components in the same volume for 6 hours, baking in a 120 ℃ oven for 6 hours, placing in a muffle furnace, and roasting at 500 ℃ for 6 hours to obtain the desulfurization and denitrification catalyst.
Example 6
Weighing 50g of active coke, adding the active coke into 0.4mol/L dilute nitric acid, soaking for 5 hours, filtering, washing to be neutral, and drying for 5 hours in a muffle furnace at the temperature of 120 ℃ to obtain the active coke for later useSexual intercourse. Weighing 7.21g of ammonium metavanadate and 15.4g of oxalic acid, dissolving in deionized water to prepare a solution, heating until the ammonium metavanadate and the oxalic acid are completely dissolved, adding active coke for equal-volume impregnation, fully impregnating for 5 hours, drying in a 120 ℃ oven for 5 hours; placing in a muffle furnace at 500 ℃ and N2Roasting for 5 hours for standby under the atmosphere condition. Weighing 8.64g, 8.74g, 4.22g and 6.04g of copper nitrate, ferric nitrate, potassium nitrate and cobalt nitrate respectively, completely dissolving in deionized water, soaking the modified components in the same volume for 6 hours, baking in a 120 ℃ oven for 5 hours, placing in a muffle furnace, and roasting at 500 ℃ for 6 hours to obtain the desulfurization and denitrification catalyst.
Example 7
Weighing 50g of active coke, adding the active coke into 0.4mol/L dilute nitric acid, soaking for 5 hours, filtering, washing to be neutral, and drying for 5 hours in a muffle furnace at the temperature of 120 ℃ to obtain the active coke for standby. Weighing 7.21g of ammonium metavanadate and 15.4g of oxalic acid, dissolving in deionized water to prepare a solution, heating until the ammonium metavanadate and the oxalic acid are completely dissolved, adding active coke for equal-volume impregnation, fully impregnating for 5 hours, drying in a 120 ℃ oven for 5 hours; placing in a muffle furnace at 500 ℃ and N2Roasting for 5 hours for standby under the atmosphere condition. Weighing 5.28g, 5.39g, 2.17g and 4.65g of copper nitrate, ferric nitrate, potassium nitrate and cobalt nitrate respectively, completely dissolving in deionized water, soaking the modified components in the same volume for 6 hours, baking in a 120 ℃ oven for 5 hours, placing in a muffle furnace, and roasting at 500 ℃ for 6 hours to obtain the desulfurization and denitrification catalyst.
Example 8
The desulfurization and denitrification catalyst prepared in the example 1 is loaded on a fixed bed, the temperature of the bed layer is raised to 500 ℃, the catalyst is activated for 2 hours, then the temperature is lowered to 280 ℃, and flue gas is introduced, wherein the flue gas components are as follows: SO (SO)2 600ppm、NO 500ppm、NH3 600ppm、O2Volume is 8 percent, nitrogen is balance gas, and airspeed is 1000h-1. The test result shows that the desulfurization efficiency is 100 percent and the denitration efficiency is 88.6 percent.
Example 9
The desulfurization and denitrification catalyst prepared in the example 1 is loaded on a fixed bed, the temperature of the bed layer is raised to 500 ℃, after the catalyst is activated for 3 hours, the temperature is lowered to 300 ℃, and flue gas is introduced, wherein the flue gas comprises the following components: SO (SO)2500ppm、NO 500ppm、NH3 700ppm、O2The volume of the mixture is 8 percent,the nitrogen is balance gas, and the space velocity is 2000h-1. The test result shows that the desulfurization efficiency is 100 percent and the denitration efficiency is 85.9 percent.
Example 10
The desulfurization and denitrification catalyst prepared in the embodiment 2-4 is placed on a fixed bed, the temperature of the bed layer is raised to 500 ℃, the catalyst is activated for 3 hours, then the temperature is lowered to 320 ℃, and flue gas is introduced, wherein the flue gas comprises the following components: SO (SO)2 750ppm、NO 600ppm、NH3 800ppm、O2Volume is 8 percent, nitrogen is balance gas, and space velocity is 3000h-1. The test result shows that the desulfurization efficiency is 100 percent and the denitration efficiency is 85.2 percent.
Example 11
The catalyst prepared in examples 5 to 7 and used for simultaneous desulfurization and denitrification is placed on a fixed bed, the temperature of the bed layer is raised to 500 ℃, the catalyst is activated for 3 hours, then the temperature is lowered to 350 ℃, and flue gas is introduced, wherein the flue gas comprises the following components: SO (SO)2 750ppm、NO 700ppm、NH3 800ppm、O2Volume is 8 percent, nitrogen is balance gas, and airspeed is 5000h-1. The test result shows that the desulfurization efficiency is 100 percent and the denitration efficiency is 86.4 percent.
Claims (10)
1. A desulfurization and denitrification catalyst is characterized in that: the catalyst uses active coke as carrier and V2O5CuO and Fe are used as active components3O4、K2O, CoO is a modifier.
2. The catalyst according to claim 1, characterized in that the catalyst employs an active coke specific surface area of 280-400 m2/g。
3. The catalyst according to claim 1, characterized in that the catalyst active component V2O5Is prepared from ammonium metavanadate and modifier chosen from copper nitrate, iron nitrate, potassium nitrate and cobalt nitrate.
4. The catalyst of claim 1, wherein the active component and the modifier are respectively V in percentage by mass2O5 1-5%、CuO 2-5%、Fe3O4 2-5%、K2O 1-1.5%、Co1 to 1.5 percent of O and the balance of active coke carrier.
5. The method for preparing the catalyst according to claim 1, wherein the catalyst is loaded with the active component and the modifier by a step impregnation method.
6. The method according to claim 5, characterized by comprising the steps of: firstly, soaking an active coke carrier in a nitric acid solution, filtering, washing to be neutral, and drying for later use; secondly, weighing ammonium metavanadate according to the mass percentage, and preparing a solution by the ammonium metavanadate and oxalic acid; soaking active coke carrier by an isovolumetric soaking method, drying, and N2Roasting under the protection condition to obtain V2O5Active coke is used; weighing copper nitrate, ferric nitrate, potassium nitrate and cobalt nitrate according to mass percentage, adding deionized water, heating and stirring until the mixture is completely dissolved; fourthly, the roasted V2O5Adding active coke into the solution, soaking in the same volume, drying, and roasting to obtain the catalyst.
7. The method according to claim 6, characterized by comprising the steps of: firstly, soaking an active coke carrier for 3-5h by using a nitric acid solution with the concentration of 0.4mol/L, filtering and washing to be neutral, and drying in an oven for 5-6h at 120 ℃ for later use; secondly, weighing ammonium metavanadate according to mass percentage, weighing oxalic acid according to a molar ratio of 1:2, and preparing a solution; soaking active coke carrier for 5h by adopting an isovolumetric soaking method, drying in a 120 ℃ oven for 5-6h, and then drying in a 500 ℃ muffle furnace N2Roasting for 5 hours under the protection condition to obtain V2O5Active coke is used; weighing copper nitrate, ferric nitrate, potassium nitrate and cobalt nitrate according to mass percentage, adding deionized water, heating and stirring until the mixture is completely dissolved; fourthly, the roasted V2O5Adding active coke into the solution III, soaking for 6h in the same volume, drying in a 120 ℃ oven for 5-6h, and roasting in a 500 ℃ muffle furnace for 5-6h to obtain the catalyst.
8. The use of the catalyst according to claim 1, wherein the catalyst is used for desulfurization and denitrification reactions.
9. The use of claim 8, wherein the catalyst is activated at 500 ℃ for 2-3h before use in desulfurization and denitrification reactions.
10. The use of claim 8, wherein the catalyst is used in desulfurization and denitrification reactions under the following conditions: the reaction temperature is 280 plus 350 ℃, and the space velocity is 1000 plus 5000h-1The gas component is NO: 500-700ppm SO2:500-750ppm、NH3：600-800ppm、O2The total volume content is 8 percent, and the rest is N2The reaction is carried out at normal pressure.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910591422.3A CN112169808A (en) | 2019-07-02 | 2019-07-02 | Desulfurization and denitrification catalyst and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910591422.3A CN112169808A (en) | 2019-07-02 | 2019-07-02 | Desulfurization and denitrification catalyst and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112169808A true CN112169808A (en) | 2021-01-05 |
Family
ID=73914873
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910591422.3A Pending CN112169808A (en) | 2019-07-02 | 2019-07-02 | Desulfurization and denitrification catalyst and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112169808A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113522299A (en) * | 2021-05-25 | 2021-10-22 | 宁夏亘峰嘉能能源科技股份有限公司 | Desulfurization, denitrification and mercury removal catalyst and preparation method thereof |
| CN116139898A (en) * | 2022-12-02 | 2023-05-23 | 佛山市国燊科技有限公司 | Gas catalyst for desulfurization and denitrification and having energy-saving effect |
| CN116272334A (en) * | 2022-12-26 | 2023-06-23 | 杭州尚善若水环保科技有限公司 | Coupling desulfurization and denitrification medicament, preparation method and use method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102489307A (en) * | 2011-12-10 | 2012-06-13 | 山西潞安矿业(集团)有限责任公司 | Catalyst for removing sulfur and saltpeter in smoke and preparing method thereof and application thereof |
| CN102764657A (en) * | 2012-08-10 | 2012-11-07 | 武汉科技大学 | A kind of nano V2O5/activated coke denitration catalyst and its preparation method |
| CN104525116A (en) * | 2014-12-31 | 2015-04-22 | 上海克硫环保科技股份有限公司 | Desulfurization and denitrification modified active coke and preparation method thereof |
-
2019
- 2019-07-02 CN CN201910591422.3A patent/CN112169808A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102489307A (en) * | 2011-12-10 | 2012-06-13 | 山西潞安矿业(集团)有限责任公司 | Catalyst for removing sulfur and saltpeter in smoke and preparing method thereof and application thereof |
| CN102764657A (en) * | 2012-08-10 | 2012-11-07 | 武汉科技大学 | A kind of nano V2O5/activated coke denitration catalyst and its preparation method |
| CN104525116A (en) * | 2014-12-31 | 2015-04-22 | 上海克硫环保科技股份有限公司 | Desulfurization and denitrification modified active coke and preparation method thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113522299A (en) * | 2021-05-25 | 2021-10-22 | 宁夏亘峰嘉能能源科技股份有限公司 | Desulfurization, denitrification and mercury removal catalyst and preparation method thereof |
| CN116139898A (en) * | 2022-12-02 | 2023-05-23 | 佛山市国燊科技有限公司 | Gas catalyst for desulfurization and denitrification and having energy-saving effect |
| CN116272334A (en) * | 2022-12-26 | 2023-06-23 | 杭州尚善若水环保科技有限公司 | Coupling desulfurization and denitrification medicament, preparation method and use method thereof |
| CN116272334B (en) * | 2022-12-26 | 2023-08-15 | 杭州尚善若水环保科技有限公司 | Coupling desulfurization and denitrification medicament, preparation method and use method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US11331657B2 (en) | Method of preparing catalyst for low-temperature synergistic catalytic purification of NOx and HCN in flue gas, and use thereof | |
| CN102366722B (en) | Denitrition catalyst with mercury removal effect and its preparation method | |
| CN101352681B (en) | Low-temperature SCR catalyst using nitrogen-dopped activated carbon as carrier and preparation technique thereof | |
| CN104492424B (en) | Ozone Coupling MnO2/Al2O3 Catalytic Oxidation of SO2 in Flue Gas to Prepare Sulfuric Acid | |
| JP5598421B2 (en) | Method for desulfurization / denitration of exhaust gas from sintering furnace and method for producing carbon monoxide oxidation catalyst | |
| CN112892547B (en) | Catalyst for simultaneously removing nitrogen oxide and carbon monoxide and preparation method thereof | |
| CN112169808A (en) | Desulfurization and denitrification catalyst and preparation method thereof | |
| CN102553572A (en) | Selective catalytic reduction (SCR) catalyst of wide active temperature window and preparation method thereof | |
| CN101869833B (en) | Catalyst for SCR denitration of furnace middle temperature fume and preparation method thereof | |
| CN111097442B (en) | Flue gas synergistic denitration and demercuration catalyst and preparation method thereof | |
| CN104190432A (en) | Low-temperature denitration and synergetic desulfurization active carbon catalyst and preparation method thereof | |
| CN107008323B (en) | A kind of activated-carbon catalyst preparation method for flue gas desulfurization and denitrification | |
| CN108993476B (en) | Metal oxide-vanadate/TiO2Catalyst, preparation method and application thereof | |
| CN107185593A (en) | A kind of SCR denitration of resistant to potassium poisoning and preparation method thereof | |
| CN102764657A (en) | A kind of nano V2O5/activated coke denitration catalyst and its preparation method | |
| CN107261805B (en) | Hydrazine solution special for chimney flue gas desulfurization and denitrification and preparation method thereof | |
| CN101920211A (en) | A preparation method of semi-coke flue gas denitrification agent for low-temperature catalytic oxidation | |
| CN108236943A (en) | A kind of preparation method of vanadium oxide catalyst | |
| CN110961114A (en) | Desulfurization and denitrification catalyst and preparation method thereof | |
| CN103537273B (en) | Denitrating catalyst of a kind of collaborative demercuration and preparation method thereof | |
| CN110605092B (en) | An iron-based rare earth oxygen storage type composite solid solution adsorbent and its application in flue gas removal of arsenic and mercury | |
| CN106807390A (en) | A kind of W types flame boiler NOxThe method and its SCO of ultra-clean discharge remove ammonia catalyst | |
| CN111569873A (en) | High-load Ru-MnOXGraphene denitration catalyst | |
| CN109174097A (en) | A kind of catalyst and preparation method thereof for metallurgy sintering smoke desulphurization denitration | |
| CN114887475A (en) | Tail gas treatment method for lithium battery material production |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210105 |