CN102744095B - Preparation method of catalyst with zeolite-activated carbon-attapulgite composite carrier for flue gas denitrification - Google Patents
Preparation method of catalyst with zeolite-activated carbon-attapulgite composite carrier for flue gas denitrification Download PDFInfo
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- CN102744095B CN102744095B CN201210238273.0A CN201210238273A CN102744095B CN 102744095 B CN102744095 B CN 102744095B CN 201210238273 A CN201210238273 A CN 201210238273A CN 102744095 B CN102744095 B CN 102744095B
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Abstract
The invention discloses a preparation method of a catalyst with a zeolite-activated carbon-attapulgite composite carrier for flue gas denitrification, which comprises the steps of: grinding and charring rice husks, adding alkali and aluminum source solution to synthesize zeolite-activated carbon; then mixing the zeolite-activated carbon, water and attapulgite, stirring, filtering, extruding into strips, drying, calcining for formation, and impregnating the mixture into acetic acid solution of copper nitrate; and finally calcining the mixture at high temperature under nitrogen protection to prepare the catalyst with the zeolite-activated carbon-attapulgite composite carrier for denitrification. The carrier is prepared with inexpensive attapulgite and rice husks as raw materials, the cost is low, and the attapulgite is used as a bonding agent and simultaneously a catalyst carrier; the zeolite-activated carbon prepared with the rice husks has a large specific surface area, the composite carrier of the catalyst is prepared by adding into the attapulgite, the air permeability of the attapulgite can be improved, and the adsorption and denitration rate of the catalyst on gas can be increased.
Description
Technical field
The present invention relates to a kind of preparation method of the catalyst for denitrating flue gas take zeolite-active carbon-attapulgite composite material as carrier, specifically one is prepared zeolite-active carbon take rice husk as raw material, adds subsequently recessed soil and slaine and prepares the method that zeolite-active carbon-attapulgite composite material is the catalyst for denitrating flue gas of carrier.
Background technology
Nitrogen oxide (NO
x) be one of Air Pollutant Discharge, can cause serious harm to human health and environment, it is mainly derived from vehicle exhaust and burning of coal, and therefore denitrating flue gas is to control NO
xthe important channel of polluting.In current method of denitration with NH
3for selective reduction (SCR) the denitration method of reducing agent is the most effective, also economical, in the method, crucial core technology is to select suitable catalyst.The SCR catalyst of existing business application is with TiO
2for carrier, supported V
2o
5active component and WO
3, there is price, the higher shortcoming of reaction flue-gas temperature in auxiliary agent preparation (ZL200910030398.2, CN102274723A).Therefore, for reducing costs, many cheap carriers are prepared denitrating catalyst as cordierite (ZL 200710062007.6), active carbon (ZL03145680.4), kaolin (ZLCN102389791A), bentonite (ZL200610028191.8) and flyash (ZL200310100420.9) etc. are used to the metal oxides such as load Fe, Cu, V and Cr.
Attapulgite clay (hereinafter to be referred as recessed soil) also can be used for preparing denitrating catalyst as carrier supported metal oxide, as direct load (ZL200910145015.6) or with flyash compound (CN102000564A) load MnO
x, load TiO
2and active component (CN101862648A).In these denitrating catalysts, because recessed native viscosity is large and specific area is limited, gas absorption and penetrating needing are improved.
Summary of the invention
The object of the invention is: the preparation method that a kind of zeolite-active carbon-recessed native composite carrier flue gas denitrating catalyst is provided, take rice husk as raw material, prepare zeolite-active carbon by charing, interpolation alkali and aluminium source, add subsequently recessed soil and slaine, calcining preparation SCR denitrating catalyst under nitrogen, preparation technology is simple, and production cost is low.
Technical solution of the present invention is that this preparation method comprises the following steps: first, after rice husk adopts pulverizer to pulverize in special atmosphere oven high temperature carbonization under nitrogen protection; Then, add alkali lye and aluminium source solution, hydrothermal crystallizing, washing, dry to obtain zeolite-active carbon; Finally, zeolite-active carbon is distributed in water, adds recessed soil, stir, and filtration, extrusion, oven dry, calcining, incipient impregnation slaine, under nitrogen, high-temperature calcination obtains SCR denitrating catalyst.
The preparation method of catalyst for denitrating flue gas of the present invention comprises following concrete steps:
Step 1, rice husk adopt pulverizer to pulverize, and are placed in special atmosphere oven, pass into nitrogen, are warmed up to 600～800 ℃ with 5 ℃/min, and insulation 1～3h, is cooled to room temperature, obtains rice hull active carbon;
Step 2, according to solid-liquid mass volume ratio 1:4, rice hull active carbon is joined in 200g/L NaOH solution, stir 30min, add subsequently the isopyknic 40～128g/LNaAlO of alkali lye
2solution, stirs 30min, transfers in the stainless steel cauldron with polytetrafluoroethylliner liner, in 80～90 ℃ of crystallization 5～10h, takes out reactor, cool to room temperature, and suction filtration, washing, obtain zeolite-active carbon;
Step 3, according to solid-liquid mass volume ratio 1:20, zeolite-active carbon is transferred in water, and adding subsequently quality is the recessed soil of 2～4 times of zeolite-active carbons, stirs 5～10h, suction filtration, banded extruder extrusion, 110 ℃ of oven dry, 250 ℃ of calcining 3h, then adding solid-liquid mass volume ratio is the copper nitrate acetic acid solution of 1:1, mixture is in 40 ℃ of oven dry, then transfers in special atmosphere oven 500 ℃ of charing 2h under nitrogen protection, obtains zeolite-active carbon-recessed native complex carrier denitrating catalyst; Wherein, copper nitrate quality is solid carrier 15～36%, and acetic acid content is 10%, and all the other are water.
Denitrating catalyst application process of the present invention is as follows: 0.5g denitrating catalyst is joined in fixed bed reactors, and inlet gas consists of 1000 × 10
6nO, 1200 × 10
6nH
3, 10% O
2and Balance Air N
2, overall flow rate is 200 mL/min, and corresponding air speed is 8000 L/ (kgh), and reaction temperature is 220～280 ℃.Flue gas analyzer on-line monitoring outlet NO concentration, uses the residual NH of phosphoric acid wash-out before NO test
3, denitration rate is 83～92%.
Compared with prior art, adopting cheap recessed soil and rice husk is that raw material is prepared carrier in the present invention, and cost is lower, and recessed soil is the carrier of binding agent and catalyst simultaneously; Zeolite-active carbon prepared by rice husk has larger specific area, is also the carrier of denitrating catalyst, adds in recessed soil, contributes to improve the gas permeability of recessed soil, improves absorption and the denitration rate of catalyst to gas.
The specific embodiment
Below in conjunction with specific embodiment, the present invention is described in further detail; Should be understood that these embodiment are technical solution in order to demonstrate the invention, but not limit the scope of the invention by any way.
Embodiment 1:
20g rice husk, after pulverizer is pulverized, is placed in special atmosphere oven, under nitrogen, calcines, and 600 ℃ of insulation 3h, cooling, obtain rice hull active carbon; Take 5g rice hull active carbon, join in 20mL200g/LNaOH solution, stir 30min, then add 20mL40g/LNaAlO
2solution, stirs 30min, transfers in the stainless steel cauldron of polytetrafluoroethylliner liner, in 80 ℃ of crystallization 10h, cooling, suction filtration, and washing, obtains X-type zeolite-active carbon; Finally, 5gX type zeolite-active carbon is transferred in 100mL water, added the recessed soil of 20g, stir 10h, suction filtration, use banded extruder extrusion, in 110 ℃ of oven dry, 250 ℃ of calcining 3h, add 25mL copper nitrate acetic acid solution, mixture is in 40 ℃ of oven dry, and in special atmosphere oven, 500 ℃ of calcining 2h under nitrogen protection, obtain CuO-X type zeolite-active carbon-recessed native denitrating catalyst; Wherein, copper nitrate is 3.80g, and acetic acid is 2.5mL.At 220 ℃, carry out denitration reaction, denitration rate is 83%.
Embodiment 2:
20g rice husk, after pulverizer is pulverized, is placed in special atmosphere oven, under nitrogen, calcines, and 700 ℃ of insulation 2h, cooling, obtain rice hull active carbon; Take 5g rice hull active carbon, join in 20mL200g/LNaOH solution, stir 30min, then add 20mL70g/LNaAlO
2solution, stirs 30min, transfers in the stainless steel cauldron of polytetrafluoroethylliner liner, in 85 ℃ of crystallization 8h, cooling, suction filtration, washing, preparation A+X type zeolite-active carbon; Finally, 5gA+X type zeolite-active carbon is transferred in 100mL water, added the recessed soil of 15g, stir 8h, suction filtration, use banded extruder extrusion, in 110 ℃ of oven dry, 250 ℃ of calcining 3h, add 20mL copper nitrate acetic acid solution, mixture is in 40 ℃ of oven dry, and in special atmosphere oven, 500 ℃ of calcining 2h under nitrogen protection, obtain CuO-A+X type zeolite-active carbon-recessed native denitrating catalyst; Wherein, copper nitrate is 4.86g, and acetic acid is 2 mL.At 250 ℃, carry out denitration reaction, denitration rate is 87 %.
Embodiment 3:
20g rice husk, after pulverizer is pulverized, is placed in special atmosphere oven, under nitrogen, calcines, and 800 ℃ of insulation 1h, cooling, obtain rice hull active carbon; Take 5g rice hull active carbon, join in 20mL200g/LNaOH solution, stir 30min, then add 20mL128g/LNaAlO
2solution, stirs 30min, transfers in the stainless steel cauldron of polytetrafluoroethylliner liner, in 90 ℃ of crystallization 5h, cooling, suction filtration, washing, preparation A type zeolite-active carbon; Finally, 5gA type zeolite-active carbon is transferred in 100mL water, added the recessed soil of 10g, stir 5h, suction filtration, use banded extruder extrusion, in 110 ℃ of oven dry, 250 ℃ of calcining 3h, add 15mL copper nitrate acetic acid solution, mixture is in 40 ℃ of oven dry, and in special atmosphere oven, 500 ℃ of calcining 2h under nitrogen protection, obtain CuO-A type zeolite-active carbon-recessed native denitrating catalyst; Wherein, copper nitrate is 5.46g, and acetic acid is 1.5mL.Carry out denitration reaction at 280 ℃, denitration rate is 92%.
Claims (1)
1. the preparation method of zeolite-active carbon-recessed native composite carrier flue gas denitrating catalyst, this preparation method comprises the following steps: first, rice husk, through pulverizing, charing, adds alkali and aluminium source solution synthetic zeolite-active carbon; Subsequently, stirring after zeolite-active carbon, water mix with recessed soil, suction filtration, extrusion, oven dry, calcining moulding, then flood copper nitrate acetic acid solution; Finally, zeolite-active carbon-recessed native composite carrier flue gas denitrating catalyst is prepared in mixture high-temperature calcination under nitrogen protection; It is characterized in that comprising the steps:
Step 1, rice husk adopt pulverizer to pulverize, and are placed in special atmosphere oven, pass into nitrogen, are warmed up to 600～800 ℃ with 5 ℃/min, and insulation 1～3h, is cooled to room temperature, obtains rice hull active carbon;
Step 2, according to solid-liquid mass volume ratio 1:4, rice hull active carbon is joined in 200g/L NaOH solution, stir 30min, add subsequently the isopyknic 40～128g/LNaAlO of alkali lye
2solution, stirs 30min, transfers in the stainless steel cauldron with polytetrafluoroethylliner liner, in 80～90 ℃ of crystallization 5～10h, takes out reactor, cool to room temperature, and suction filtration, washing, obtain zeolite-active carbon;
Step 3, according to solid-liquid mass volume ratio 1:20, zeolite-active carbon is transferred in water, adding subsequently quality is the recessed soil of 2～4 times of zeolite-active carbons, stir 5～10h, suction filtration, banded extruder extrusion, 110 ℃ of oven dry, 250 ℃ of calcining 3h, then adding solid-liquid mass volume ratio is the copper nitrate acetic acid solution of 1:1, and wherein, copper nitrate quality is solid carrier 15～36%, acetic acid content is 10%, and all the other are water; Mixture is in 40 ℃ of oven dry, then transfers in special atmosphere oven 500 ℃ of charing 2h under nitrogen protection, obtains zeolite-active carbon-recessed native composite carrier flue gas denitrating catalyst.
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| CN103447079B (en) * | 2013-08-23 | 2014-12-24 | 淮阴工学院 | Preparation method of Cu-Fe-ZSM-5-attapulgite compound flue gas denitrification catalyst |
| CN103447072B (en) * | 2013-08-23 | 2014-12-03 | 淮阴工学院 | Preparation method of Fe-NaY-C-attapulgite compound flue gas denitrification catalyst |
| CN103495434B (en) * | 2013-09-13 | 2015-02-18 | 北京矿迪科技有限公司 | Desulphurization and denitration agent based on waste biomass and preparation method thereof |
| CN115920618B (en) * | 2023-01-06 | 2024-06-14 | 广州绿华环保科技股份有限公司 | Composite denitration agent and waste gas denitration method |
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