CN114345317A - V/Fe bimetallic desulfurization and denitrification catalyst and preparation method and application thereof - Google Patents
V/Fe bimetallic desulfurization and denitrification catalyst and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 89
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 42
- 230000023556 desulfurization Effects 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 70
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 10
- 238000010521 absorption reaction Methods 0.000 claims abstract description 9
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims abstract description 7
- 230000000694 effects Effects 0.000 claims abstract description 5
- 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 46
- 238000001035 drying Methods 0.000 claims description 28
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 24
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 23
- 238000007598 dipping method Methods 0.000 claims description 23
- 238000005406 washing Methods 0.000 claims description 22
- 238000010438 heat treatment Methods 0.000 claims description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 238000002791 soaking Methods 0.000 claims description 10
- 239000013543 active substance Substances 0.000 claims description 9
- 239000012456 homogeneous solution Substances 0.000 claims description 9
- 235000006408 oxalic acid Nutrition 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 238000005303 weighing Methods 0.000 claims description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 2
- 238000012216 screening Methods 0.000 claims description 2
- 239000011149 active material Substances 0.000 claims 1
- 238000005470 impregnation Methods 0.000 claims 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 5
- 239000003546 flue gas Substances 0.000 abstract description 5
- 229910000831 Steel Inorganic materials 0.000 abstract description 4
- 239000010959 steel Substances 0.000 abstract description 4
- 238000007670 refining Methods 0.000 abstract description 2
- 229910002651 NO3 Inorganic materials 0.000 abstract 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 abstract 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract 1
- 239000002253 acid Substances 0.000 abstract 1
- 239000003513 alkali Substances 0.000 abstract 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 abstract 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 abstract 1
- 229910052717 sulfur Inorganic materials 0.000 abstract 1
- 239000011593 sulfur Substances 0.000 abstract 1
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 18
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 14
- 238000001816 cooling Methods 0.000 description 12
- 238000011156 evaluation Methods 0.000 description 8
- 239000012153 distilled water Substances 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 229910002091 carbon monoxide Inorganic materials 0.000 description 6
- 238000004090 dissolution Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 238000003916 acid precipitation Methods 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- 150000003568 thioethers Chemical class 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000010531 catalytic reduction reaction Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000002802 bituminous coal Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000003009 desulfurizing effect Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- GNMQOUGYKPVJRR-UHFFFAOYSA-N nickel(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Ni+3].[Ni+3] GNMQOUGYKPVJRR-UHFFFAOYSA-N 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- PZFKDUMHDHEBLD-UHFFFAOYSA-N oxo(oxonickeliooxy)nickel Chemical compound O=[Ni]O[Ni]=O PZFKDUMHDHEBLD-UHFFFAOYSA-N 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 210000002345 respiratory system Anatomy 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
- 239000008117 stearic acid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
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Abstract
The invention discloses a V/Fe bimetallic desulfurization and denitrification catalyst, a preparation method and application thereof, wherein the catalyst prepared by the method comprises active components of vanadium pentoxide and ferric oxide with the mass percentage of 2-3.5% and 3-4.5%, and an active carbon carrier with the mass percentage of 92-95%. The carrier is active carbon modified by acid or alkali pretreatment, and the water absorption of the active carbon is not less than 20%. The catalyst has good effects on desulfurization and denitration, can remove more than 80% of nitrate and sulfur in the flue gas, and can be widely applied to the desulfurization and denitration of the catalyst in large-scale flue gas emission enterprises such as steel enterprises, refining enterprises, metallurgical industries and the like.
Description
Technical Field
The invention relates to the technical field of chemical industry, in particular to the field of industrial catalysis of refining, steel enterprises and the like, and relates to a catalyst for simultaneously removing sulfur dioxide and nitrogen oxide in tail gas.
Background
Along with the rapid development of economy in China, the demand for coal is increasing day by day. The consumption and utilization of coal resources, the discharge amount of sulfur dioxide and nitrogen oxides is increased, and the discharged sulfides and nitrogen oxides seriously damage an ecological system. Statistics shows that sulfur dioxide and nitrogen oxides generated by coal combustion are one of main sources of air pollution in China. In which the SO is discharged2Is easily dissolved in water and can form H2SO3Usually in a catalyst such as NO2In the presence of H2SO3Will be further oxidized into H2SO4And thus acid rain is formed. Acid rain seriously damages the ecological environment, harms human health, and seriously corrodes building steel and the like, thereby causing huge economic loss. Nitrogen oxides are extremely damaging to the human respiratory system. NO and NO2Predominantly NOxIs an important cause of photochemical smog and acid rain.
At present, the more mature coal-fired flue gas desulfurization and denitration technology studied at home and abroad adopts limestone-gypsum desulfurization and NH3The selective catalytic reduction denitration (SCR) technology is characterized in that sulfides and nitrides are respectively treated, the selective catalytic reduction denitration technology has the problems of large occupied area, complex equipment, high investment and operation cost, secondary pollution and the like, and the increasingly strict environmental protection requirements are difficult to meet.
Invention patent CN103691476AA catalyst for synchronously desulfurizing and denitrifying flue gas at low temperature is prepared through mixing mesoporous SBA-15, nano-titanium dioxide (anatase type), multiple metal oxides (Mn, V, Cr, Ce, W and Mo), ammonia water and deionized water to prepare a catalyst precursor, mixing the reinforcing agent glass fiber, cross-linking agent methacrylic acid-2-hydroxyethyl ester, surfactant stearic acid and heat stabilizer to form a secondary mixture, and calcining to obtain the porous catalyst. The invention patent CN105643239A discloses a catalyst for simultaneous desulfurization and denitrification without reducing gas and a preparation method thereof, wherein a carrier ZSM-5 molecular sieve and active components CuO and K are adopted2O、CoO、Ni2O3、V2O5And WO3The catalyst is obtained by adopting a one-time or multi-time dipping method, evaporating to dryness and roasting.
Disclosure of Invention
In view of the complex preparation process of the catalyst, the invention aims to provide the catalyst which has the advantages of easily available raw materials, simple process, low price, high desulfurization and denitrification efficiency, regeneration and cyclic utilization and no secondary pollution.
The invention provides the following technical scheme: a V/Fe bimetallic desulfurization and denitrification catalyst takes active carbon as a carrier and V2O5、Fe2O3Is active component, the mass content of the active carbon is 92-95%, and the mass of the active component is 2-3.5% and 3-4.5% respectively.
Generally, the particle size of the activated carbon particles is between 0.5 and 1cm, and the water absorption rate is not lower than 20%.
The active carbon is the active carbon after the dipping treatment of nitric acid or sodium hydroxide.
The invention provides a preparation process of the catalyst carrier, which comprises the following steps:
(1) crushing and screening the active carbon into particles with the particle size of 0.5-1 cm;
(2) soaking the screened active carbon in a nitric acid or sodium hydroxide solution with the concentration of 2-4mol/L for 4-6 hours;
(3) and (3) washing the soaked activated carbon until the pH =7, and drying in an oven to obtain the catalyst carrier.
The preparation process of the active component of the catalyst comprises the steps of weighing ammonium metavanadate and ferric nitrate according to the mass percentage of a carrier, dissolving the ammonium metavanadate and the ferric nitrate by adopting oxalic acid distilled water, and uniformly stirring to form a uniform solution.
The catalyst forming process comprises the steps of dipping the treated carrier in a uniform solution of ferric nitrate and ammonium metavanadate, and dipping the carrier for 4-6 hours in twice equal volumes to dip active substances; after dipping, washing until the PH =7, and drying in an oven for 8-10 hours at 110 ℃; in N2Under the protection of atmosphere, the temperature rise rate is 150 ℃/h, the temperature rises to 450-temperature-plus-500 ℃, and the catalyst is roasted for 4-6 hours to obtain the desulfurization and denitrification catalyst.
The finished catalyst is activated for 2 hours at 500 ℃ before the raw material gas is introduced; the reaction temperature is 300--1The gas component is NO: 500-700ppm SO2: 500-750ppm, CO: 1-3% by volume, O2: 1-3% and the balance of N2The gas is balanced, the removal rate of nitrogen oxides is up to 80 percent and the removal rate of sulfides is over 95 percent under normal pressure.
In the process of the desulfurization and denitrification catalyst, after the activity is reduced, the catalyst is heated to 450-500 ℃ under the condition of air normal pressure, and the catalyst can be activated again after being heated for 4-5 hours.
The catalyst can be widely applied to large-scale flue gas emission desulfurization and denitrification enterprises such as bituminous coal power plants, metallurgical enterprises and steel enterprises.
Detailed Description
For further illustration of the present invention, the following will describe the "a V/Fe bimetallic desulfurization and denitrification catalyst" in detail with reference to the examples, but the present invention is not limited thereto.
Example 1
1.2g of ammonium metavanadate and 2.4g of oxalic acid were weighed into a 100ml beaker, dissolved with distilled water (about 20ml), and after complete dissolution, 1.8g of ferric nitrate was added, and heated with stirring until a homogeneous solution was formed.
50g of activated carbon with the diameter of 0.5-1cm and the water absorption of 20 percent is weighed, and 2mol/LHNO is adopted3The solution was soaked for 4 hours. Washing the soaked activated carbon ionized water to PH =7, and drying in an oven to obtain the catalystAn agent carrier. Dipping the pretreated carrier in a uniform solution of ferric nitrate and ammonium metavanadate, and dipping for 4 hours in an equal volume to dip active substances; after dipping, washing until the pH is =7, drying in a drying oven at 110 ℃ for 8 hours; roasting the impregnated and dried catalyst in a muffle furnace; in N2Under the protection of atmosphere, heating up to 450 ℃ at the heating rate of 150 ℃/h, roasting for 4 hours, naturally cooling, secondarily soaking the uniform solution of ferric nitrate and ammonium metavanadate, washing, drying and roasting to obtain the desulfurization and denitrification catalyst.
Weighing 40g of finished catalyst, adding the catalyst into a fixed bed reactor with the diameter of 1cm and the height of 30cm, heating the fixed bed to 500 ℃ to activate the catalyst for 2 hours, and naturally cooling to 350 ℃. According to the airspeed of 1500 h-1NO500ppm and SO were introduced2500ppm, 1% CO by volume and the balance N2And (4) balancing the qi. The evaluation results are shown in Table I.
Watch 1
The desulfurization and denitrification rate is calculated according to the following formula:
desulfurization rate = [ (SO)2)Raw materials-(SO2)An outlet]/(SO2)Raw materials
Denitration rate = [ (NO)Raw materials-(NO)An outlet]/(NO)Raw materials。
As can be seen from Table I, 2mol/LHNO3Solution-treated activated carbon, SO loaded with active component2The average desulfurization rate was 97.4%, and the average denitrification rate was 88.3%.
Example 2
1.2g of ammonium metavanadate and 2.4g of oxalic acid were weighed into a 100ml beaker, dissolved with distilled water (about 20ml), and after complete dissolution, 1.8g of ferric nitrate was added, and heated with stirring until a homogeneous solution was formed.
50g of activated carbon with the diameter of 0.5-1cm and the water absorption of 20 percent is weighed and soaked for 4 hours by adopting a solution with the concentration of 2 mol/LNaOH. And (3) washing the soaked activated carbon ionized water to PH =7, and drying in an oven to obtain the catalyst carrier. Dipping the pretreated carrier in ferric nitrate,Soaking the ammonium metavanadate homogeneous solution for 4 hours in an equal volume to soak the active substances; after dipping, washing until the pH is =7, drying in a drying oven at 110 ℃ for 8 hours; roasting the impregnated and dried catalyst in a muffle furnace; in N2Under the protection of atmosphere, heating up to 500 ℃ at the heating rate of 150 ℃/h, roasting for 4 hours, naturally cooling, secondarily soaking the uniform solution of ferric nitrate and ammonium metavanadate, washing, drying and roasting to obtain the desulfurization and denitrification catalyst.
Weighing 40g of finished catalyst, adding the catalyst into a fixed bed reactor with the diameter of 1cm and the height of 30cm, heating the fixed bed to 500 ℃ to activate the catalyst for 2 hours, and naturally cooling to 350 ℃. According to the airspeed of 1500 h-1NO500ppm and SO were introduced2500ppm, 1% CO by volume and the balance N2And (4) balancing the qi. The evaluation results are shown in Table II.
Watch two
As shown in Table two, the SO of the activated carbon loaded with the active component after the activated carbon is treated with 2mol/LNaOH solution2The average desulfurization rate was 97%, and the average denitrification rate was 88.3%.
Example 3
2.1 g of ammonium metavanadate and 4.2g of oxalic acid were weighed into a 100ml beaker, dissolved with distilled water (about 20ml), and after complete dissolution, 2.7g of ferric nitrate was added, and heated with stirring until a homogeneous solution was formed.
50g of activated carbon with the diameter of 0.5-1cm and the water absorption of 20 percent is weighed, and the activated carbon with the concentration of 4mol/LHNO is adopted3The solution was soaked for 6 hours. And (3) washing the soaked activated carbon ionized water to PH =7, and drying in an oven to obtain the catalyst carrier. Dipping the pretreated carrier in a uniform solution of ferric nitrate and ammonium metavanadate, and dipping for 6 hours in an equal volume to dip active substances; after dipping, washing until the pH is =7, drying in a drying oven at 110 ℃ for 8 hours; roasting the impregnated and dried catalyst in a muffle furnace; in N2Heating to 450 ℃ at the heating rate of 150 ℃/h under the atmosphere protection, roasting for 6 hours, naturally cooling, secondarily soaking the uniform solution of ferric nitrate and ammonium metavanadate, washing, drying and roasting to obtain the desulfurization and denitrificationA catalyst.
Weighing 40g of finished catalyst, adding the catalyst into a fixed bed reactor with the diameter of 1cm and the height of 30cm, heating the fixed bed to 500 ℃ to activate the catalyst for 2 hours, and naturally cooling to 350 ℃. At a space velocity of 3000h-1NO500ppm and SO were introduced2500ppm, 1% CO by volume and the balance N2And (4) balancing the qi. The evaluation results are shown in Table three.
Watch III
From Table III, it can be seen that the ratio of 4mol/LHNO3Solution-treated activated carbon, SO loaded with active component2The average desulfurization rate was 96.6% and the average denitrification rate was 87.4%.
Example 4
2.1 g of ammonium metavanadate and 4.2g of oxalic acid were weighed into a 100ml beaker, dissolved with distilled water (about 20ml), and after complete dissolution, 2.7g of ferric nitrate was added, and heated with stirring until a homogeneous solution was formed.
50g of activated carbon with the diameter of 0.5-1cm and the water absorption of 20 percent is weighed, and the activated carbon with the concentration of 4mol/LHNO is adopted3The solution was soaked for 6 hours. And (3) washing the soaked activated carbon ionized water to PH =7, and drying in an oven to obtain the catalyst carrier. Dipping the pretreated carrier in a uniform solution of ferric nitrate and ammonium metavanadate, and dipping for 6 hours in an equal volume to dip active substances; after dipping, washing until the pH is =7, drying in a drying oven at 110 ℃ for 8 hours; roasting the impregnated and dried catalyst in a muffle furnace; in N2Under the protection of atmosphere, heating up to 450 ℃ at the heating rate of 150 ℃/h, roasting for 6 hours, naturally cooling, secondarily soaking the uniform solution of ferric nitrate and ammonium metavanadate, washing, drying and roasting to obtain the desulfurization and denitrification catalyst.
Weighing 40g of finished catalyst, adding the catalyst into a fixed bed reactor with the diameter of 1cm and the height of 30cm, heating the fixed bed to 500 ℃ to activate the catalyst for 2 hours, and naturally cooling to 350 ℃. According to the airspeed of 1500 h-1Introducing SO2750ppm, NO700ppm, 3% CO by volume, and the balance N2And (4) balancing the qi. The evaluation results are shown in Table four.
Watch four
As can be seen from Table IV, the ratio of LHNO is 4mol/LHNO3Solution-treated activated carbon, SO loaded with active component2The average desulfurization rate was 96.5% and the average denitrification rate was 86.4%.
Example 5
2.1 g of ammonium metavanadate and 4.2g of oxalic acid were weighed into a 100ml beaker, dissolved with distilled water (about 20ml), and after complete dissolution, 2.7g of ferric nitrate was added, and heated with stirring until a homogeneous solution was formed.
50g of activated carbon with the diameter of 0.5-1cm and the water absorption of 20 percent is weighed, and the activated carbon with the concentration of 4mol/LHNO is adopted3The solution was soaked for 6 hours. And (3) washing the soaked activated carbon ionized water to PH =7, and drying in an oven to obtain the catalyst carrier. Dipping the pretreated carrier in a uniform solution of ferric nitrate and ammonium metavanadate, and dipping for 6 hours in an equal volume to dip active substances; after dipping, washing until the pH is =7, drying in a drying oven at 110 ℃ for 8 hours; roasting the impregnated and dried catalyst in a muffle furnace; in N2Under the protection of atmosphere, heating up to 500 ℃ at the heating rate of 150 ℃/h, roasting for 6 hours, naturally cooling, secondarily soaking the uniform solution of ferric nitrate and ammonium metavanadate, washing, drying and roasting to obtain the desulfurization and denitrification catalyst.
Weighing 40g of finished catalyst, adding the catalyst into a fixed bed reactor with the diameter of 1cm and the height of 30cm, heating the fixed bed to 500 ℃ to activate the catalyst for 2 hours, and naturally cooling to 350 ℃. At a space velocity of 3000h-1Introducing SO2750ppm, NO700ppm, 3% CO by volume, and the balance N2And (4) balancing the qi. The evaluation results are shown in Table five.
Watch five
As can be seen from Table five, the molecular weight distribution was 4mol/LHNO3Solution-treated activated carbon, SO loaded with active component2Average desulfurization rate95.7%, and the average denitration rate was 85.3%.
Example 6
2.1 g of ammonium metavanadate and 4.2g of oxalic acid were weighed into a 100ml beaker, dissolved with distilled water (about 20ml), and after complete dissolution, 2.7g of ferric nitrate was added, and heated with stirring until a homogeneous solution was formed.
50g of activated carbon with the diameter of 0.5-1cm and the water absorption of 20 percent is weighed and soaked in 4mol/LNaOH solution for 6 hours. And (3) washing the soaked activated carbon ionized water to PH =7, and drying in an oven to obtain the catalyst carrier. Dipping the pretreated carrier in a uniform solution of ferric nitrate and ammonium metavanadate, and dipping for 6 hours in an equal volume to dip active substances; after dipping, washing until the pH is =7, drying in a drying oven at 110 ℃ for 8 hours; roasting the impregnated and dried catalyst in a muffle furnace; in N2Under the protection of atmosphere, heating up to 500 ℃ at the heating rate of 150 ℃/h, roasting for 6 hours, naturally cooling, secondarily soaking the uniform solution of ferric nitrate and ammonium metavanadate, washing, drying and roasting to obtain the desulfurization and denitrification catalyst.
Weighing 40g of finished catalyst, adding the catalyst into a fixed bed reactor with the diameter of 1cm and the height of 30cm, heating the fixed bed to 500 ℃ to activate the catalyst for 2 hours, and naturally cooling to 350 ℃. At a space velocity of 3000h-1Introducing SO2750ppm, NO700ppm, 3% CO by volume, and the balance N2And (4) balancing the qi. The evaluation results are shown in Table six.
Watch six
As can be seen from Table six, the molecular weight distribution was 4mol/LHNO3Solution-treated activated carbon, SO loaded with active component2The average desulfurization rate was 95.8%, and the average denitrification rate was 84.8%.
Example 7
The catalysts of example 1, example 3 and example 5 were recovered, and each was charged into a quartz tube, heated to 450 ℃ under air conditions for 4 hours, cooled naturally, and charged into a furnace. The catalyst was activated at 500 ℃ for 2 hours and allowed to cool naturally to 350 ℃. The raw material gas is introduced according to the process conditions of example 1, example 3 and example 5. The evaluation results are shown in Table seven.
Watch seven
As can be seen from Table VII, the catalytic desulfurization and denitration efficiency after regeneration still exceeds 95% and 80%, and the catalyst recovery effect is good.
Example 8
The catalysts of example 2, example 4 and example 6 were recovered, and each was charged into a quartz tube, heated to 500 ℃ under air for 5 hours, cooled naturally, and charged into a furnace. The catalyst was activated at 500 ℃ for 2 hours and allowed to cool naturally to 350 ℃. The raw material gas is introduced according to the process conditions of the embodiment 2, the embodiment 4 and the embodiment 6. The evaluation results are shown in Table eight.
Table eight
As can be seen from the table VIII, the catalytic desulfurization and denitration efficiency after regeneration still exceeds 95% and 80%, and the catalyst recovery effect is good.
Claims (10)
1. A V/Fe bimetallic desulfurization and denitrification catalyst is characterized in that the catalyst takes active carbon as a carrier and V2O5、Fe2O3Is active component, the mass content of the active carbon is 92-95%, and the mass of the active component is 2-3.5% and 3-4.5% respectively.
2. The desulfurization and denitrification catalyst according to claim 1, wherein the activated carbon particles have a particle size of 0.5-1cm and a water absorption of not less than 20%.
3. The desulfurization and denitrification catalyst according to claim 1 or 2, wherein the activated carbon is activated carbon impregnated with nitric acid or sodium hydroxide.
4. The method for preparing a desulfurization and denitrification catalyst according to claim 1, wherein the catalyst carrier is prepared by the steps of:
(1) crushing and screening the active carbon into particles with the particle size of 0.5-1 cm;
(2) soaking the screened activated carbon in a nitric acid or sodium hydroxide solution with the concentration of 2-4mol/L for 4-6 h;
(3) and washing the activated carbon subjected to the soaking pretreatment to the pH =7, and drying to obtain the catalyst carrier.
5. The method for preparing a desulfurization and denitrification catalyst according to claim 1, wherein the preparation of the active components of the catalyst comprises the following steps: weighing ammonium metavanadate and ferric nitrate according to the mass percentage of the carrier, dissolving the ammonium metavanadate and then dissolving the ferric nitrate by using an oxalic acid solution, and uniformly stirring to form a uniform solution.
6. The method for preparing the desulfurization and denitrification catalyst according to claim 4 or 5, wherein the carrier is impregnated in a homogeneous solution, active substances are impregnated twice in equal volumes, and the impregnated active substances are dried and roasted to obtain the desulfurization and denitrification catalyst.
7. The method for preparing a desulfurization and denitrification catalyst according to claim 4 or 5, wherein the carrier is impregnated in a homogeneous solution, and active materials are impregnated by twice equal-volume impregnation for 4-6 hours; after dipping, washing until the pH is =7, and drying in an oven for 8-10 hours at 110 ℃; in N2Under the protection of atmosphere, the temperature rise rate is 150 ℃/h, the temperature rises to 450-temperature-plus-500 ℃, and the catalyst is roasted for 4-6 hours to obtain the desulfurization and denitrification catalyst.
8. The application of the desulfurization and denitrification catalyst according to claim 1, wherein the catalyst is activated at 500 ℃ for 2 hours before being introduced into the feed gas.
9. The use of the desulfurization and denitrification catalyst as recited in claim 8, wherein the catalyst is heated to 450 ℃ and 500 ℃ under atmospheric conditions and atmospheric pressure after the activity of the catalyst is reduced, and the catalyst is reactivated by heating for 4-5 hours.
10. The application of the desulfurization and denitrification catalyst as claimed in claim 1, wherein the reaction temperature is 300--1The gas component is NO: 500-700ppm SO2: 500-750ppm, CO: 1-3% by volume, O2: 1-3% and the balance of N2And (4) balancing the qi.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1792455A (en) * | 2005-12-27 | 2006-06-28 | 中国科学院山西煤炭化学研究所 | Cellular activated-carbon catalyst used for denitrification of flue-gas, prepn. method and application thereof |
| 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 | Nano V205/activated coke denitration catalyst and preparation method of catalyst |
| CN103769114A (en) * | 2014-02-14 | 2014-05-07 | 中国科学院生态环境研究中心 | Vanadium-modified iron-based activated carbon catalyst, preparation method and application thereof |
| CN103861439A (en) * | 2014-03-25 | 2014-06-18 | 云南亚太环境工程设计研究有限公司 | Method for simultaneously desulfurizing, denitrating and purifying flue gas |
| 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 |
| CN110961114A (en) * | 2018-09-30 | 2020-04-07 | 中国石油化工股份有限公司 | Desulfurization and denitrification catalyst and preparation method thereof |
-
2020
- 2020-10-13 CN CN202011090684.0A patent/CN114345317A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1792455A (en) * | 2005-12-27 | 2006-06-28 | 中国科学院山西煤炭化学研究所 | Cellular activated-carbon catalyst used for denitrification of flue-gas, prepn. method and application thereof |
| 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 | Nano V205/activated coke denitration catalyst and preparation method of catalyst |
| CN103769114A (en) * | 2014-02-14 | 2014-05-07 | 中国科学院生态环境研究中心 | Vanadium-modified iron-based activated carbon catalyst, preparation method and application thereof |
| CN103861439A (en) * | 2014-03-25 | 2014-06-18 | 云南亚太环境工程设计研究有限公司 | Method for simultaneously desulfurizing, denitrating and purifying flue gas |
| 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 |
| CN110961114A (en) * | 2018-09-30 | 2020-04-07 | 中国石油化工股份有限公司 | Desulfurization and denitrification catalyst and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| WEIWEI YANG ET AL.: ""Effect of V2O5 Additive on the SO2 Resistance of a Fe2O3/AC Catalyst for NH3‑SCR of NOx at Low Temperatures"", 《INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH》, vol. 55, pages 2677 - 2685 * |
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