CN102513095B - Medium temperature denitration catalyst with carbon-based material loaded with cerium tungsten and preparation method of medium temperature denitration catalyst - Google Patents
Medium temperature denitration catalyst with carbon-based material loaded with cerium tungsten and preparation method of medium temperature denitration catalyst Download PDFInfo
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- CN102513095B CN102513095B CN 201110375073 CN201110375073A CN102513095B CN 102513095 B CN102513095 B CN 102513095B CN 201110375073 CN201110375073 CN 201110375073 CN 201110375073 A CN201110375073 A CN 201110375073A CN 102513095 B CN102513095 B CN 102513095B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 66
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- IADRPEYPEFONML-UHFFFAOYSA-N [Ce].[W] Chemical compound [Ce].[W] IADRPEYPEFONML-UHFFFAOYSA-N 0.000 title claims 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 34
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 12
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 12
- 239000013543 active substance Substances 0.000 claims abstract description 6
- 229910000420 cerium oxide Inorganic materials 0.000 claims abstract description 5
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000003426 co-catalyst Substances 0.000 claims abstract description 4
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 claims abstract 4
- 239000002041 carbon nanotube Substances 0.000 claims abstract 3
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract 3
- 238000005470 impregnation Methods 0.000 claims abstract 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 23
- 239000000243 solution Substances 0.000 claims description 22
- 229910001868 water Inorganic materials 0.000 claims description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 229910052684 Cerium Inorganic materials 0.000 claims description 13
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical class [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 13
- 229910052721 tungsten Inorganic materials 0.000 claims description 13
- 239000010937 tungsten Substances 0.000 claims description 13
- 239000002994 raw material Substances 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 239000003245 coal Substances 0.000 claims description 4
- 238000000746 purification Methods 0.000 claims description 4
- 235000013399 edible fruits Nutrition 0.000 claims description 3
- 235000013162 Cocos nucifera Nutrition 0.000 claims description 2
- 244000060011 Cocos nucifera Species 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 239000002109 single walled nanotube Substances 0.000 claims description 2
- 239000002023 wood Substances 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims 5
- 230000004913 activation Effects 0.000 claims 2
- 229920000049 Carbon (fiber) Polymers 0.000 claims 1
- 239000002048 multi walled nanotube Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 15
- 230000009467 reduction Effects 0.000 abstract description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract 1
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 23
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 17
- 239000003546 flue gas Substances 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 16
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 14
- 229910052799 carbon Inorganic materials 0.000 description 13
- 238000003756 stirring Methods 0.000 description 13
- 238000001354 calcination Methods 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 10
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 10
- 238000010306 acid treatment Methods 0.000 description 8
- 235000013842 nitrous oxide Nutrition 0.000 description 8
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical class OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 7
- 239000010453 quartz Substances 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 229910010413 TiO 2 Inorganic materials 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 4
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 4
- 238000005229 chemical vapour deposition Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 3
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 3
- 239000011149 active material Substances 0.000 description 2
- 229910003481 amorphous carbon Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000010531 catalytic reduction reaction Methods 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 229910001200 Ferrotitanium Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 238000001994 activation Methods 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen 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
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明公开了一种具有良好活性和选择性的中温选择性还原脱硝催化剂，以载体为炭基材料，铈的氧化物为活性物质，三氧化钨为助催化剂，所述的炭基材料为活性炭、活性炭纤维或碳纳米管中的一种。本发明还公开了该类催化剂的制备工艺，即先用浓硝酸对炭基材料进行纯化处理和表面活化处理，然后采用浸渍法负载活性物质和助催化剂。本发明的催化剂在230～420℃范围内具有良好的脱硝活性和选择性，是一种很好的中温脱硝催化剂，具有较好的应用前景。The invention discloses a medium-temperature selective reduction denitrification catalyst with good activity and selectivity. The carrier is a carbon-based material, cerium oxide is an active substance, tungsten trioxide is a cocatalyst, and the carbon-based material is activated carbon. , activated carbon fiber or carbon nanotube. The invention also discloses a preparation process of the catalyst, that is, the carbon-based material is purified and surface-activated with concentrated nitric acid, and then the impregnation method is used to load active substances and co-catalysts. The catalyst of the invention has good denitrification activity and selectivity in the range of 230-420° C., is a good medium-temperature denitrification catalyst, and has good application prospects.
Description
Technical field
The present invention relates to the air pollution control technique field, be specifically related to a kind of denitrifying catalyst with selective catalytic reduction and preparation technology thereof, be applicable to flue-gas temperature and be the denitrating flue gas of 230～420 ℃.
Background technology
Sulfur dioxide and nitrogen oxide are the main gas pollutants that causes acid rain, and wherein nitrogen oxide also can cause the generation of photochemical fog.Along with generally applying of flue gas desulfurization technique, the discharge capacity of sulfur dioxide is effectively controlled, but the discharge capacity of nitrogen oxide but is not effectively controlled.For satisfying the needs of sustainable development and environmental protection, China had carried forward vigorously control and the improvement of nitrogen oxide in recent years, and new discharged nitrous oxides standard is also ready to appear.
Nitrogen oxide can be divided into moving source and stationary source according to the source, and stationary source is take various discharged from coal-fired boiler as main, and the denitration technology of its main flow is SCR (SCR) denitration technology.The SCR denitration technology is applied in developed countries such as Europe, the United States, days at present, is gas denitrifying technology most widely used in world wide, that occupation rate of market is the highest, operation is the most reliable and the most stable.That most SCR denitrification apparatus adopts is V
2O
5-WO
3/ TiO
2Or V
2O
5-MoO
3/ TiO
2Catalyst, this class catalytic component based on vanadium active temperature windows focuses mostly at 300～450 ℃.
The SCR denitration technology can be divided into the SCR of the high grey SCR that arranges, the low grey SCR that arranges and end layout according to the position difference.The SCR device that high ash is arranged is between economizer and air preheater, and flue-gas temperature is many at 300～400 ℃, so V
2O
5-WO
3/ TiO
2And V
2O
5-MoO
3/ TiO
2Catalyst is very applicable; After the SCR device that end is arranged was positioned at dust arrester and desulfurizer, its flue-gas temperature was too low, and the SCR device that early stage Europe and Japanese end are arranged all needs flue gas is carried out heat again, and this arrangement can cause cost to increase; After the SCR device that low ash is arranged was positioned at dust arrester, arrangement can effectively be alleviated arsenic in ash content, alkali and alkaline earth metal ions etc. to the murder by poisoning of catalyst like this, but flue-gas temperature has decline before than dedusting, and in most of situation, flue-gas temperature is not at V
2O
5-WO
3/ TiO
2And V
2O
5-MoO
3/ TiO
2In the optimum working temperature scope of catalyst, cause denitration efficiency as one wishes not to the utmost.Therefore in the situation that not to flue gas reheat, if select the catalyst (middle temperature denitrating catalyst) of optimum working temperature in the SCR device flue-gas temperature scope that low ash is arranged, effective life-span of extending catalyst, and then reduction denitration cost.
Less about the patent of middle temperature denitrating catalyst both at home and abroad at present, application number is that 200710121422.4 Chinese invention patent discloses the ferrotitanium composite oxides thing catalyst that is used for ammine selectivity catalytic reduction nitrous oxides, and this catalyst can be used for the SCR denitrification apparatus that low ash is arranged.In document, (Catalysis Communications 12 (2011) 394-398) have reported that cerium oxide loads on that to have good low-temperature denitration on NACF active.Disclosed by the invention is a kind of catalyst of carbon based material cerium-carrying tungsten, this catalyst has higher activity and selectivity between 250～400 ℃, therefore be highly suitable for the SCR denitrification apparatus that low ash is arranged, these catalyst raw material wide material sources, preparation technology are simple, are a kind of good middle temperature catalysts.
Summary of the invention
The invention provides a kind of have excellent activity and optionally in warm denitrating catalyst and preparation technology thereof, described middle temperature denitrating catalyst take carbon based material as carrier, the oxide of cerium is co-catalyst as active material, tungstic acid.
The raw material of described middle temperature denitrating catalyst consists of the soluble-salt of carbon based material, water, cerium and the soluble-salt of tungsten, and the mol ratio between each raw material is:
Carbon based material: 1
Water: 10～1000
The soluble-salt of cerium: 0.0001～0.1
The soluble-salt of tungsten: 0.0001～0.2
Described carbon based material is a kind of in active carbon, NACF or CNT.Described active carbon is a kind of in cocoanut active charcoal, active fruit shell carbon, coal mass active carbon or wood powder shaped activated carbon, and described CNT is single-walled nanotube or many walls nanotube.
The preparation technology of above-mentioned catalyst comprises the following steps:
(1) purification process of carbon based material and surface activation process: be that 60%～90% red fuming nitric acid (RFNA) soaks carbon based material with mass fraction, and stirred in the water bath with thermostatic control of 70～90 ℃ 2～10 hours, then be 6～7 with deionized water rinsing to pH, oven dry under 60～150 ℃ at last;
(2) infusion process carrying active substance and co-catalyst: first the soluble-salt of cerium and the soluble-salt decibel of tungsten are configured to cerium solution and tungsten solution; then the carrier carbon based material that step (1) is obtained joins in the mixed solution of cerium solution and tungsten solution and stirred 2～20 hours; then oven dry under 60～150 ℃; under last nitrogen protection, calcination is 2～10 hours, and calcination temperature is 300～700 ℃.
A lot of carbon based materials contain many impurity, and Fe, Co, Ni such as containing a small amount of amorphous carbon and trace in coal mass active carbon contain a small amount of amorphous carbon in CNT, and the nitric acid purification process can be got rid of these impurity to the impact of catalyst.Simultaneously the carbon based material surface after nitric acid treatment has been introduced into a large amount of oxy radicals and nitrogen-containing group, and this is conducive to the Uniform Dispersion of active component.
Cerium oxide because of environmental friendliness, have the characteristic such as oxygen storage capacity, in recent years by extensively with and catalytic field.In the catalyst take cerium oxide as active material, cerous existence has important function to the activity of catalyst, manages to improve cerous content and often can effectively improve the activity of catalyst.In the present invention, the oxide of cerium and tungstic acid all form in the calcination process, strong reciprocation can occur between both, finally cause more trivalent cerium to generate.In addition, the interpolation of tungstic acid has increased catalyst surface can be for the adsorption potential of reacting gas absorption, and this is conducive to the carrying out of catalytic reaction.Therefore, the interpolation of tungsten can effectively improve the activity of catalyst.
Catalyst preparation process disclosed by the invention is simple and practical, the denitrating catalyst of preparation has good denitration activity, selective and stable, be that 230～420 ℃, air speed are that the denitration efficiency of catalyst under the condition of 100000h-1 can be kept more than 80% in reaction temperature, substantially can't detect the generation of laughing gas, in 250～400 ℃, reaction temperature interval, denitration efficiency is stabilized in more than 90%.This catalyst be a kind of well in warm denitrating catalyst, have application prospect preferably.
The specific embodiment
Embodiment 1:
Catalyst raw material mol ratio is CNT, water, cerium nitrate and ammonium tungstate.CNT makes with chemical vapour deposition technique, first soaks CNT with 68% red fuming nitric acid (RFNA), and stirs 2 hours in the water bath with thermostatic control of 80 ℃, is then 6.5 with deionized water rinsing to pH, oven dry under 80 ℃ at last.Get the CNT that 2 gram nitric acid treatment are crossed, toward wherein adding 0.2 gram Ce (NO
3)
36H
2O (with appropriate water-soluble solution) and 0.5 gram ammonium tungstate (with appropriate saturated oxalic acid solution dissolving), the rear 80 ℃ of oven dry that stir, then 350 ℃ of calcinations namely got the catalyst finished product in 3 hours under nitrogen protection.
The catalyst of preparation is put into the fixed bed quartz tube reactor carry out activity and selectivity test, reaction temperature is that 230～420 ℃, air speed are 100000h
-1Condition under, denitration efficiency is stabilized in more than 85%, substantially can't detect the generation of laughing gas, in 250～400 ℃, reaction temperature interval, denitration efficiency is stabilized in more than 95%.Simulated flue gas is by N
2, O
2, NO, NH
3And SO
2Form NO 600ppm wherein, NH
3600ppm, SO
21000ppm, O
25%.
Embodiment 2:
Catalyst raw material mol ratio is active carbon, water, cerium nitrate and ammonium tungstate.Active carbon is coal mass active carbon, first soaks active carbon with 68% red fuming nitric acid (RFNA), and stirs 4 hours in the water bath with thermostatic control of 80 ℃, is then 6 with deionized water rinsing to pH, oven dry under 100 ℃ at last.Get the active carbon that 2 gram nitric acid treatment are crossed, toward wherein adding 0.05 gram Ce (NO
3)
36H
2O (with appropriate water-soluble solution) and 0.08 gram ammonium tungstate (with appropriate saturated oxalic acid solution dissolving), the rear 80 ℃ of oven dry that stir, then 450 ℃ of calcinations namely got the catalyst finished product in 3 hours under nitrogen protection.
The catalyst of preparation is put into the fixed bed quartz tube reactor carry out activity and selectivity test, reaction temperature is that 230～420 ℃, air speed are 100000h
-1Condition under, denitration efficiency is stabilized in more than 80%, substantially can't detect the generation of laughing gas, in 250～400 ℃, reaction temperature interval, denitration efficiency is stabilized in more than 90%.Simulated flue gas is by N
2, O
2, NO, NH
3And SO
2Form NO 600ppm wherein, NH
3600ppm, SO
21000ppm, O
25%.
Embodiment 3:
Catalyst raw material mol ratio is NACF, water, cerium nitrate and ammonium tungstate.First soaking NACF with 68% red fuming nitric acid (RFNA), and stirred 4 hours in the water bath with thermostatic control of 80 ℃, is then 6.5 with deionized water rinsing to pH, oven dry under 80 ℃ at last.Get the NACF that 2 gram nitric acid treatment are crossed, toward wherein adding 1 gram Ce (NO
3)
36H
2O (with appropriate water-soluble solution) and 1.2 gram ammonium tungstates (with appropriate saturated oxalic acid solution dissolving), the rear 60 ℃ of oven dry that stir, then 550 ℃ of calcinations namely got the catalyst finished product in 3 hours under nitrogen protection.
The catalyst of preparation is put into the fixed bed quartz tube reactor carry out activity and selectivity test, reaction temperature is that 230～420 ℃, air speed are 100000h
-1Condition under, denitration efficiency is stabilized in more than 80%, substantially can't detect the generation of laughing gas, in 250～400 ℃, reaction temperature interval, denitration efficiency is stabilized in more than 90%.Simulated flue gas is by N
2, O
2, NO, NH
3And SO
2Form NO 600ppm wherein, NH
3600ppm, SO
21000ppm, O
25%.
Embodiment 4:
Catalyst raw material mol ratio is active carbon, water, cerium nitrate and ammonium tungstate.Active carbon is active fruit shell carbon, first soaks active carbon with 68% red fuming nitric acid (RFNA), and stirs 5 hours in the water bath with thermostatic control of 80 ℃, is then 6.5 with deionized water rinsing to pH, oven dry under 100 ℃ at last.Get the active carbon that 2 gram nitric acid treatment are crossed, toward wherein adding 1.5 gram Ce (NO
3)
36H
2O (with appropriate water-soluble solution) and 2 gram ammonium tungstates (with appropriate saturated oxalic acid solution dissolving), the rear 80 ℃ of oven dry that stir, then 650 ℃ of calcinations namely got the catalyst finished product in 4 hours under nitrogen protection.
The catalyst of preparation is put into the fixed bed quartz tube reactor carry out activity and selectivity test, reaction temperature is that 230～420 ℃, air speed are 100000h
-1Condition under, denitration efficiency is stabilized in more than 80%, substantially can't detect the generation of laughing gas, in 250～400 ℃, reaction temperature interval, denitration efficiency is stabilized in more than 90%.Simulated flue gas is by N
2, O
2, NO, NH
3And SO
2Form NO 600ppm wherein, NH
3600ppm, SO
21000ppm, O
25%.
Embodiment 5:
Catalyst raw material mol ratio is CNT, water, cerium nitrate and ammonium tungstate.CNT makes with chemical vapour deposition technique, first soaks CNT with 68% red fuming nitric acid (RFNA), and stirs 4 hours in the water bath with thermostatic control of 80 ℃, is then 6.5 with deionized water rinsing to pH, oven dry under 150 ℃ at last.Get the CNT that 2 gram nitric acid treatment are crossed, toward wherein adding 0.2 gram Ce (NO
3)
36H
2O (with appropriate water-soluble solution) and 0.2 gram ammonium tungstate (with appropriate saturated oxalic acid solution dissolving), the rear 80 ℃ of oven dry that stir, then 300 ℃ of calcinations namely got the catalyst finished product in 3 hours under nitrogen protection.
The catalyst of preparation is put into the fixed bed quartz tube reactor carry out activity and selectivity test, reaction temperature is that 230～420 ℃, air speed are 100000h
-1Condition under, denitration efficiency is stabilized in more than 85%, substantially can't detect the generation of laughing gas, in 250～400 ℃, reaction temperature interval, denitration efficiency is stabilized in more than 95%.Simulated flue gas is by N
2, O
2, NO, NH
3And SO
2Form NO 600ppm wherein, NH
3600ppm, SO
21000ppm, O
25%.
Embodiment 6:
Catalyst raw material mol ratio is CNT, water, cerium nitrate and ammonium tungstate.CNT makes with chemical vapour deposition technique, first soaks CNT with 68% red fuming nitric acid (RFNA), and stirs 4 hours in the water bath with thermostatic control of 80 ℃, is then 6.5 with deionized water rinsing to pH, oven dry under 80 ℃ at last.Get the CNT that 2 gram nitric acid treatment are crossed, toward wherein adding 3 gram Ce (NO
3)
36H
2O (with appropriate water-soluble solution) and 2 gram ammonium tungstates (with appropriate saturated oxalic acid solution dissolving), the rear 80 ℃ of oven dry that stir, then 350 ℃ of calcinations namely got the catalyst finished product in 3 hours under nitrogen protection.
The catalyst of preparation is put into the fixed bed quartz tube reactor carry out activity and selectivity test, reaction temperature is that 230～420 ℃, air speed are 100000h
-1Condition under, denitration efficiency is stabilized in more than 85%, substantially can't detect the generation of laughing gas, in 250～400 ℃, reaction temperature interval, denitration efficiency is stabilized in more than 95%.Simulated flue gas is by N
2, O
2, NO, NH
3And SO
2Form NO 600ppm wherein, NH
3600ppm, SO
21000ppm, O2 5%.
Embodiment 7:
Catalyst raw material mol ratio is CNT, water, cerium nitrate and ammonium tungstate.CNT makes with chemical vapour deposition technique, first soaks CNT with 68% red fuming nitric acid (RFNA), and stirs 10 hours in the water bath with thermostatic control of 60 ℃, is then 6.5 with deionized water rinsing to pH, oven dry under 80 ℃ at last.Get the CNT that 2 gram nitric acid treatment are crossed, toward wherein adding 5 gram Ce (NO
3)
36H
2O (with appropriate water-soluble solution) and 3 gram ammonium tungstates (with appropriate saturated oxalic acid solution dissolving), the rear 80 ℃ of oven dry that stir, then 700 ℃ of calcinations namely got the catalyst finished product in 3 hours under nitrogen protection.
The catalyst of preparation is put into the fixed bed quartz tube reactor carry out activity and selectivity test, reaction temperature is that 230～420 ℃, air speed are 100000h
-1Condition under, denitration efficiency is stabilized in more than 85%, substantially can't detect the generation of laughing gas, in 250～400 ℃, reaction temperature interval, denitration efficiency is stabilized in more than 95%.Simulated flue gas is by N
2, O
2, NO, NH
3And SO
2Form NO 600ppm wherein, NH
3600ppm, SO
21000ppm, O
25%.
Above-described embodiment is several typical specific embodiments of the present invention, and those skilled in the art can make various modifications within the scope of the appended claims.
Claims (5)
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| CN102861579A (en) * | 2012-09-22 | 2013-01-09 | 台州学院 | Copper-based nano denitration catalyst and preparation method thereof |
| CN103785374B (en) * | 2014-02-20 | 2015-10-14 | 重庆大学 | A kind of C nano pipe demercuration catalyst and preparation method thereof |
| CN104148055B (en) * | 2014-08-22 | 2016-03-02 | 北京中南亚太环境科技发展有限公司 | A kind of denitrating catalyst |
| CN105921181B (en) * | 2016-04-29 | 2019-02-22 | 苏州科博思环保科技有限公司 | A kind of high-quality desulphurization denitration catalyst and its preparation method and application |
| CN106345453A (en) * | 2016-08-26 | 2017-01-25 | 成都国化环保科技有限公司 | Carbon-based material low-temperature denitrification catalyst and preparation method thereof |
| CN112823884A (en) * | 2019-11-21 | 2021-05-21 | 中冶京诚工程技术有限公司 | Active carbon carrier iron-based NH3-SCR catalyst, preparation method and application |
| CN111686716B (en) * | 2020-07-29 | 2022-06-14 | 江西省生态环境科学研究与规划院 | WOxLow-temperature SCR (selective catalytic reduction) flue gas denitration catalyst with modified carbon nano tube loaded with metal oxide, and preparation method and application thereof |
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| CN101234345A (en) * | 2008-03-06 | 2008-08-06 | 南京工业大学 | A monolithic catalyst for flue gas denitration using aluminum-based ceramics as a carrier and its preparation method |
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