CN109465006A - A kind of preparation method and application of titanium Modified Activated Carbon based low-temperature denitration catalyst - Google Patents

A kind of preparation method and application of titanium Modified Activated Carbon based low-temperature denitration catalyst Download PDF

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Publication number
CN109465006A
CN109465006A CN201811312650.4A CN201811312650A CN109465006A CN 109465006 A CN109465006 A CN 109465006A CN 201811312650 A CN201811312650 A CN 201811312650A CN 109465006 A CN109465006 A CN 109465006A
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activated carbon
tio
catalyst
modified activated
solution
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黄张根
侯亚芹
李昱琳
李巧艳
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Shanxi Institute of Coal Chemistry of CAS
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Shanxi Institute of Coal Chemistry of CAS
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/20Vanadium, niobium or tantalum
    • B01J23/22Vanadium
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation 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
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/74General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86Catalytic processes
    • B01D53/8621Removing nitrogen compounds
    • B01D53/8625Nitrogen oxides
    • B01D53/8628Processes characterised by a specific catalyst

Abstract

A kind of titanium Modified Activated Carbon based low-temperature denitration catalyst is by TiO2Modified activated carbon fibre is as complex carrier, and load active component CeO on it2Or V2O5Or the mixture of two kinds of active components, the weight percent of each component are as follows: complex carrier 90.0-99.0%, wherein TiO2Weight percent content is 5.0%-10.0%;Remaining is active component.The present invention prepares catalyst denitrification rate >=80% under low temperature (80-200 DEG C) in denitrification process, can stable operation 90h, there is good commercial application potentiality.

Description

A kind of preparation method and application of titanium Modified Activated Carbon based low-temperature denitration catalyst
Technical field
The invention belongs to technical field of waste gas treatment, it is related to a kind of titanium Modified Activated Carbon based low-temperature denitration catalyst and preparation method And application.
Background technique
Clearly propose that China in 2018 will start steel for steel industry pollutant control, in the government work report in this year Iron industry minimum discharge transformation, ecological, environmental protective portion has issued that " iron and steel enterprise's minimum discharge retrofit work scheme (consults in the recent period Original text) ", specify the small hourly value concentration of emission of flue gas of sintering machine head, pellet roasting flue gas particles, sulfur dioxide, nitrogen oxides not Higher than 10,35,50mg/m3.Steel industry Air Pollution Control mention mark transformation it is extremely urgent, in this context, develop novel height It is imperative to imitate steel sintering catalyst for denitrating flue gas.
Carbon based material (active carbon, activated coke, activated carbon fibre etc.) is the low-temperature dry sintering flue gas of most application potential Denitrating catalyst or carrier.Country's Taiyuan steel enterprise Introduced from Japan technology is to 450m at present2With 6002Sintering machine is using activity Charcoal comprehensive treatment flue gas, the equipment desulfurization degree are 95%, and denitrification rate 40%, dust removal efficiency is 80% or more.Although Taiyuan Iron and Steel Co. uses Active carbon is realized sintering flue gas and is removed, but national requirements for environmental protection is much not achieved also about only 40% in its denitrification rate.It is based on The above problem, the low-temperature denitration activity for improving carbon base catalyst is the key point solved the problems, such as.
Summary of the invention
For the low disadvantage of current commercial catalysts low temperature active, the present invention provides a kind of titanium Modified Activated Carbon that low temperature active is high Based low-temperature denitration catalyst and preparation method and application.
Innovative proposition of the invention prepares composite carrier for sintering flue gas low temperature using organic and inorganic materials coupling Remove nitrogen oxides.Wherein, inorganic matter selects TiO2, one side TiO2It is a kind of oxide with reducibility, was restoring Cheng Zhongke is partially reduced to form Lacking oxygen, improves the oxidisability of catalyst surface, and then is conducive to the absorption of reactant molecule With activation;On the other hand, TiO2As a kind of acidulous material, catalyst surface acidity can be improved to improve urging for catalyst Change activity.
Technical solution provided by the invention is as follows:
A kind of titanium Modified Activated Carbon based low-temperature denitration catalyst, by TiO2Modified activated carbon fibre as complex carrier, and Load active component CeO on it2Or V2O5Or the mixture of both the above active component, the weight percent of each component Are as follows: complex carrier 90.0-99.0%, wherein TiO2Weight percent content is 5.0%-10.0%;Remaining is active component.
If two kinds of active components mixed component when, CeO2: V2O5Molar ratio is 0.5-1.0.
Preparation method of the invention, comprising the following steps:
(1) active carbon fiber fabrics are cut into the round that diameter is 8-12mm, cut and boils processing 1- in boiling water 3h obtains activated carbon fibre carrier;
(2) butyl titanate is taken to be dissolved in dehydrated alcohol, it is 0.04- that mixed solution, which is added dropwise to concentration, It in the nitric acid solution of 0.08mol/l, at the uniform velocity stirs at room temperature, obtains transparent nano-TiO2Solution, wherein butyl titanate: nothing Water-ethanol: nitric acid solution volume ratio=5-15:20-30:150-200;
(3) complex carrier is prepared using excessive infusion process, the activated carbon fibre carrier that step (1) is handled well is placed in step (2) configured TiO210-12h is adsorbed in solution, at 60-80 DEG C, revolving speed is 10-100r/min magnetic agitation, filters off water Divide, 100-120 DEG C of drying 3-5h, obtains complex carrier (TiO2-ACF);
(4) equi-volume impregnating is used, the complex carrier (TiO for taking step (3) to prepare2- ACF) to be impregnated in cerous nitrate water-soluble Liquid or ammonium metavanadate/oxalic acid solution are placed at room temperature for 2-5h, dry 3-10h at 50-80 DEG C, dry 2- at 100-120 DEG C Then 8h successively calcines 2-8h under 300-500 DEG C of argon atmosphere, 2-5h is calcined in 200-250 DEG C of air to get catalyst.
The application of catalyst of the present invention, includes the following steps:
Catalyst is fitted into fixed bed reactors, and reaction temperature is controlled at 80~200 DEG C, and reaction pressure is normal pressure, reaction Air speed is controlled in 1000h-1~10000h-1, processing gas is nitrogen-containing oxide discharge gas, and gas concentration range is 500- 1000ppm。
The present invention has the advantage that
1. in view of the unique physicochemical properties of ACF (big specific surface area and micro content abundant), present invention preparation Titanium Modified Activated Carbon based composite catalyst have have a wide range of application, vapour lock is small, NOx and catalyst surface time of contact are long and low temperature is living The excellent advantage of property.
2. the catalyst that the method for the invention is prepared, in denitrification process denitrification rate under low temperature (80-200 DEG C) >= 80%, can stable operation 90h, have good commercial application potentiality.
3. passing through TiO2Modified catalyst, so that the acidity and oxidisability of catalyst surface increase, to be conducive to The absorption and oxidation of NO.
4. catalyst of the present invention has apparent advantage: catalytic activity is high, vapour lock is small, stability is strong, preparation method is simple The features such as.When reaction temperature is 200 degree, exit NOx concentration meets minimum discharge requirement close to 25ppm.
In short, charcoal based composite catalyst prepared by the present invention, reduces reaction vapour lock, the diffusion for increasing reaction gas is passed It passs.The operation temperature of removing NOx has been widened, higher denitration activity can have been reached under (80-200 DEG C) at a lower temperature, thus Substantially increase the application range of catalyst.
Specific embodiment
Embodiment 1
Active carbon fiber fabrics carrier is cut into the shape that diameter is 8mm, and 1h drying is boiled in boiling water.5ml titanium is taken under room temperature Sour four butyl esters are dissolved in 20ml dehydrated alcohol, are added dropwise to the 150ml nitric acid solution that concentration is 0.04mol/l after mixing In, form transparent nano-TiO2Solution.Take that a certain amount of (those skilled in the art can voluntarily select practical use according to actual needs Amount) ACF that handles well is excessively impregnated in the nano-TiO prepared2In solution, stirring impregnates 10h, then 110 DEG C of drying 3h, Obtain the modified activated carbon fibre (ACF-TiO of titanium2), wherein TiO2Content is 5wt%.Take the above-mentioned complex carrier dipping of 0.5g In the cerous nitrate aqueous solution of the 0.0009g/ml of 15ml, it is placed at room temperature for 3h, 50 DEG C of dry 5h, then 110 DEG C of dry 5h exist 8h is calcined under 300 DEG C of argon atmospheres to get being 6%CeO to mass percent2/ACF-TiO2Catalyst.The catalyst is packed into solid In fixed bed reactor, reaction temperature controls simulated flue gas 500ppm NO, the 500ppm NH being passed through under normal pressure at 120 DEG C3, 5%O2, Balance Air N2, reaction velocity control is in 1000h-1.The conversion ratio of NO is 82% when stable state, and selectivity is 90%.
Embodiment 2
Activated carbon fibre carrier is cut into the shape that diameter is 10mm, and 2h drying is boiled in boiling water.10ml titanium is taken under room temperature Sour four butyl esters are dissolved in 25ml dehydrated alcohol, are added dropwise to the 150ml nitric acid solution that concentration is 0.05mol/l after mixing In, form transparent nano-TiO2Solution.Take that a certain amount of (those skilled in the art can voluntarily select practical use according to actual needs Amount) ACF that handles well is excessively impregnated in the nano-TiO prepared2In solution, stirring impregnates 10h, then 110 DEG C of drying 4h, Obtain the modified activated carbon fibre (ACF-TiO of titanium2), wherein TiO2Content is 7wt%.Take the above-mentioned complex carrier dipping of 0.5g In the cerous nitrate aqueous solution of the 0.0009g/ml of 15ml, 3h, 50 DEG C of dry 5h, 110 DEG C of dry 5h are then placed at room temperature for, so 8h is calcined under 300 DEG C of argon atmospheres afterwards to get being 6%CeO to mass percent2/ACF-TiO2Catalyst.Catalyst dress Enter in fixed bed reactors, reaction temperature is controlled at 200 DEG C, the simulated flue gas 500ppm NO, 500ppm that are passed through under normal pressure NH3, 5%O2, Balance Air N2, reaction velocity control is in 4000h-1.The conversion ratio of NO is 91% when stable state, and selectivity is 93%.
Embodiment 3
Activated carbon fibre carrier is cut into the shape that diameter is 10mm, and 2h drying is boiled in boiling water.10ml titanium is taken under room temperature Sour four butyl esters are dissolved in 25ml dehydrated alcohol, are added dropwise to the 150ml nitric acid solution that concentration is 0.06mol/l after mixing In, form transparent nano-TiO2Solution.Take that a certain amount of (those skilled in the art can voluntarily select practical use according to actual needs Amount) ACF that handles well is excessively impregnated in the nano-TiO prepared2In solution, stirring impregnates 10h, then 110 DEG C of drying 4h, Obtain the modified activated carbon fibre (ACF-TiO of titanium2), wherein TiO2Content is 7wt%.Take the above-mentioned complex carrier dipping of 0.5g In ammonium metavanadate/oxalic acid solution of the 0.0788g/ml of 20ml, it is then placed at room temperature for 2h, 50 DEG C of dry 3h, 110 DEG C of dryings 5h, then successively calcining under 500 DEG C of argon atmospheres in 8h and 250 DEG C of air and calcining 5h to get mass percent is 2%V2O5/ ACF-TiO2Catalyst.The catalyst is fitted into fixed bed reactors, and reaction temperature control is at 180 DEG C, the mould being passed through under normal pressure Quasi- flue gas 500ppm NO, 500ppm NH3, 5%O2, Balance Air N2, reaction velocity control is in 5000h-1.The conversion of NO when stable state Rate is 87%, and selectivity is 92%.
Embodiment 4
Activated carbon fibre carrier is cut into the shape that diameter is 12mm, and 3h drying is boiled in boiling water.10ml titanium is taken under room temperature Sour four butyl esters are dissolved in 20ml dehydrated alcohol, are added dropwise to the 150ml nitric acid solution that concentration is 0.06mol/l after mixing In, form transparent nano-TiO2Solution.Take that a certain amount of (those skilled in the art can voluntarily select practical use according to actual needs Amount) ACF that handles well is excessively impregnated in the nano-TiO prepared2In solution, stirring impregnates 10h, then 110 DEG C of drying 3h, Obtain the modified activated carbon fibre (ACF-TiO of titanium2), wherein TiO2Content is 5wt%.Take the above-mentioned complex carrier dipping of 0.5g In ammonium metavanadate/oxalic acid solution of the 0.0788g/ml of 20ml, it is then placed at room temperature for 2h, 50 DEG C of dry 3h, 110 DEG C of dryings 5h, then successively calcining under 500 DEG C of argon atmospheres in 8h and 250 DEG C of air and calcining 5h to get mass percent is 2%V2O5/ ACF-TiO2Catalyst.Weigh 0.4g2%V2O5/ACF-TiO2Catalyst is immersed in the cerous nitrate water of the 0.0004g/ml of 17ml In solution, be then placed at room temperature for 3h, 50 DEG C of dry 5h, 110 DEG C of dry 5h, then under 300 DEG C of argon atmospheres calcine 8h to get It is 3%CeO to mass percent2- 2%V2O5/ACF-TiO2Catalyst.The catalyst is fitted into fixed bed reactors, reaction temperature Degree controls simulated flue gas 500ppm NO, the 500ppm NH being passed through under normal pressure at 120 DEG C3, 5%O2, Balance Air N2, reaction sky Speed control is in 6000h-1.The conversion ratio of NO is 85% when stable state.Selectivity is 92%.
Embodiment 5
Activated carbon fibre carrier is cut into the shape that diameter is 10mm, and 1h drying is boiled in boiling water.10ml titanium is taken under room temperature Sour four butyl esters are dissolved in 30ml dehydrated alcohol, are added dropwise to the 200ml nitric acid solution that concentration is 0.08mol/l after mixing In, form transparent nano-TiO2Solution.Take that a certain amount of (those skilled in the art can voluntarily select practical use according to actual needs Amount) ACF that handles well is excessively impregnated in the nano-TiO prepared2In solution, stirring impregnates 10h, then 110 DEG C of drying 3h, Obtain the modified activated carbon fibre (ACF-TiO of titanium2), wherein TiO2Content is 5wt%.Take the above-mentioned complex carrier dipping of 0.5g In ammonium metavanadate/oxalic acid solution of the 0.0788g/ml of 20ml, it is then placed at room temperature for 2h, 50 DEG C of dry 3h, 110 DEG C of dryings 5h, then successively calcining under 500 DEG C of argon atmospheres in 8h and 250 DEG C of air and calcining 5h to get mass percent is 2%V2O5/ ACF-TiO2Catalyst.Weigh 0.4g2%V2O5/ACF-TiO2Catalyst is immersed in the cerous nitrate water of the 0.0004g/ml of 17ml In solution, be then placed at room temperature for 3h, 50 DEG C of dry 5h, 110 DEG C of dry 5h, then under 300 DEG C of argon atmospheres calcine 8h to get It is 3%CeO to mass percent2- 2%V2O5/ACF-TiO2Catalyst.The catalyst is fitted into fixed bed reactors, reaction temperature Degree controls simulated flue gas 500ppm NO, the 500ppm NH being passed through under normal pressure at 200 DEG C3, 5%O2, Balance Air N2, reaction sky Speed control is in 9500h-1.The conversion ratio of NO is 83% when stable state.Selectivity is 95%.
Embodiment 6
Activated carbon fibre carrier is cut into the shape that diameter is 12mm, and 1h drying is boiled in boiling water.15ml titanium is taken under room temperature Sour four butyl esters are dissolved in 30ml dehydrated alcohol, are added dropwise to the 200ml nitric acid solution that concentration is 0.06mol/l after mixing In, form transparent nano-TiO2Solution.Take that a certain amount of (those skilled in the art can voluntarily select practical use according to actual needs Amount) ACF that handles well is excessively impregnated in the nano-TiO prepared2In solution, stirring impregnates 12h, then 110 DEG C of drying 5h, Obtain the modified activated carbon fibre (ACF-TiO of titanium2), wherein TiO2Content is 10wt%.Take the above-mentioned complex carrier dipping of 0.5g In ammonium metavanadate/oxalic acid solution of the 0.0788g/ml of 20ml, it is then placed at room temperature for 2h, 50 DEG C of dry 3h, 110 DEG C of dryings 5h, then successively calcining under 500 DEG C of argon atmospheres in 8h and 250 DEG C of air and calcining 5h to get mass percent is 2%V2O5/ ACF-TiO2Catalyst.Weigh 0.4g2%V2O5/ACF-TiO2Catalyst is immersed in the cerous nitrate water of the 0.0004g/ml of 17ml In solution, be then placed at room temperature for 3h, 50 DEG C of dry 5h, 110 DEG C of dry 5h, then under 300 DEG C of argon atmospheres calcine 8h to get It is 3%CeO to mass percent2- 2%V2O5/ACF-TiO2Catalyst.The catalyst is fitted into fixed bed reactors, reaction temperature Degree controls simulated flue gas 500ppm NO, the 500ppm NH being passed through under normal pressure at 200 DEG C3, 5%O2, Balance Air N2, reaction sky Speed control is in 4000h-1.NO conversion ratio is 94% when stable state, and long period 100h does not observe the obvious deactivation phenomenom of catalyst, 90% or more NO conversion ratio holding, it is with good stability.

Claims (4)

1. a kind of titanium Modified Activated Carbon based low-temperature denitration catalyst, it is characterised in that catalyst is by TiO2Modified activated carbon fibre is made For complex carrier, and load active component CeO on it2Or V2O5Or the mixture of two kinds of active components, each component Weight percent are as follows: complex carrier 90.0-99.0%, wherein TiO2Weight percent content is 5.0%-10.0%;Remaining is work Property component.
2. a kind of titanium Modified Activated Carbon based low-temperature denitration catalyst as described in claim 1, it is characterised in that two kinds of active components CeO in mixture2: V2O5Molar ratio is 0.5-1.0.
3. a kind of preparation method of titanium Modified Activated Carbon based low-temperature denitration catalyst as described in claim or 1 or 2, it is characterised in that The following steps are included:
(1) active carbon fiber fabrics are cut into the round that diameter is 8-12mm, cut and boil processing 1-3h in boiling water, obtains To activated carbon fibre carrier;
(2) butyl titanate is taken to be dissolved in dehydrated alcohol, it is 0.04-0.08mol/l's that mixed solution, which is added dropwise to concentration, It in nitric acid solution, at the uniform velocity stirs at room temperature, obtains transparent nano-TiO2Solution, wherein butyl titanate: dehydrated alcohol: nitric acid Liquor capacity ratio=5-15:20-30:150-200;
(3) complex carrier is prepared using excessive infusion process, the activated carbon fibre carrier that step (1) is handled well is placed in step (2) Configured TiO210-12h is adsorbed in solution, at 60-80 DEG C, revolving speed is 10-100r/min magnetic agitation, filter off moisture, 100-120 DEG C of drying 3-5h, obtains complex carrier;
(4) equi-volume impregnating is used, the complex carrier for taking step (3) to prepare is impregnated in cerous nitrate aqueous solution or metavanadic acid Ammonium/oxalic acid solution is placed at room temperature for 2-5h, drying 3-10 h at 50-80 DEG C, dry 2-8 h at 100-120 DEG C, then successively 2-8 h is calcined under 300-500 DEG C of argon atmosphere, and 2-5 h is calcined in 200-250 DEG C of air to get catalyst.
4. a kind of application of titanium Modified Activated Carbon based low-temperature denitration catalyst as described in claim or 1 or 2, it is characterised in that including Following steps:
Catalyst is fitted into fixed bed reactors, and reaction temperature is controlled at 80~200 DEG C, and reaction pressure is normal pressure, reaction velocity Control is in 1000h-1~10000 h-1, processing gas is nitrogen-containing oxide discharge gas, and gas concentration range is 500- 1000ppm。
CN201811312650.4A 2018-11-06 2018-11-06 A kind of preparation method and application of titanium Modified Activated Carbon based low-temperature denitration catalyst Pending CN109465006A (en)

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