CN106391040B - A kind of high efficient cryogenic denitration composite catalyst and preparation method thereof - Google Patents
A kind of high efficient cryogenic denitration composite catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of high efficient cryogenic denitration composite catalyst, which includes microporous carbon fiber carrier, V2O5Catalyst, Fe2O3And CeO2Auxiliary agent.V2O5、Fe2O3And CeO2Weight fraction be respectively 4 ~ 18wt%, 0.25 ~ 2wt%, 0.25 ~ 2wt%, surplus is microporous carbon fiber.The present invention provides a kind of high efficient cryogenic denitration composite catalyst and preparation method thereof, catalyst prepared by the present invention reduces the operation temperature of SCR, when denitrification rate reaches 80%, temperature range is 86 ~ 102 DEG C, at 120 DEG C, denitration efficiency is greater than 95%, has good SO2Anti- poisoning capability and wearability be strong, long service life.
Description
Technical field
The present invention relates to chemical fields, and in particular to a kind of high efficient cryogenic denitration composite catalyst and preparation method thereof.
Background technique
In view of the coal fire discharged NO in the current thermal power plant in Chinax、SO2Total amount is well beyond the self-purification ability of enviroment, causes
Serious environmental pollution, by Acid Rain Pollution, the desulphurization denitration for carrying out flue gas is extremely urgent on the territory of nearly one third.
Selective reduction (SCR) technology is as denitration method for flue gas best at present, due to its mature and reliable, nitric efficiency
Height, cost performance are high and are widely applied.Cardinal principle is reducing agent at certain temperature and catalyst action, there is selection
Ground is the NO in flue gasxIt is reduced to N2, while generating water.The actual desulphurization denitration program of power plant is at present: first with smoke outlet
(300 ~ 400 DEG C) progress denitrations of high temperature, are then dusted, finally carry out desulfurization.As it can be seen that a large amount of dust is to de- in flue gas
The denitrating catalyst of nitre link, which certainly will have, to be seriously affected.Commercial catalysts for SCR system mainly have noble metal catalyst,
The several types such as metal oxide catalyst, perovskite type catalyst, molecular sieve catalyst and carbon-supported catalysts.Catalyst
Activity is generally higher to temperature requirement, but smoke temperature is generally in middle low temperature range, and can currently obtain in middle cold stage higher
The catalyst of SCR denitration efficiency is seldom, and there are preparation processes it is complicated, at high cost, hydrothermal stability is poor the problems such as.Preferably
SCR denitration should have the following characteristics that high activity, anti-SO2Poisoning capability is strong；High mechanical strength, abrasion resistance properties are good；Have
Suitable operating temperature section (especially low-temperature range).The screening and group of excellent catalyst carrier and catalyst activity component
Proportion between point is the key that catalyst research.
With activated carbon supported V2O5The V of preparation2O5/ AC catalyst has good low temperature active (150 ~ 200 DEG C) and urges
Change efficiency and is widely used in simultaneous SO_2 and NO removal industry.(such as Ma Jianrong, Liu Zhenyu are removed in flue gas Ma Jianrong etc. simultaneously
The V of sulphur and nitre2O5/ AC catalyst research chemistry of fuel journal, 2005,33 (1): 6-11.) in fixed-bed micro-reactor
On studied by the catalyst used the desulphurization denitration in flue gas, discovery is by V2O5Load is obtained on activated carbon
V2O5/ AC catalyst can remove simultaneously the SO in flue gas at 200 DEG C2And NO.But SO in subtractive process2It easily adsorbs on the activated carbon
Sulfate is formed, the activity of catalyst is reduced.It is therefore prevented that the generation of sulfate, particle are grown up, regenerate catalyst
It is current key task to maintain higher catalytic activity.
For activated carbon fibre (ACF) compared with previous active carbon, the micropore of large specific surface area, rich content accounts for total pore volume
90% or so, pore-size distribution is narrow and uniform, and micropore size is mostly in 1 nm or so, and adsorption and desorption speed is fast, plasticity and again
Natural disposition is strong.Structure of Activated Carbon Fibers intensity is higher, can satisfy a variety of conditions of flue gas desulphurization denitration, can be processed into
Various shapes, improve the contact area of adsorption reaction, while reaching the Active pharmaceutical of desulphurization denitration.Activated carbon fibre desulphurization denitration
When rate compared with conventional carbon, hundred times of advantage can be reached, the adsorption capacity of desulphurization denitration not only can be improved, but also can
To promote the standard of purification.There are various functional groups on the surface ACF, has very well for metal ion, certain organic matters and certain gases
Selective absorption function, be used for nitrogen oxides in effluent catalytic purification research.Shirahama etc. (Shirahama N,
Mochida I, Korai Y, et al. Reaction of NO2 in air at room temperature with
urea supported on pitch based activated carbon fiber. Applied Catalysis B:
Environmental, 2004,52:173-179.) using ACF load urea purification NO2Effect is fine, and NO2It is easier to
It is reduced or is adsorbed agent absorption.But it is at a lower temperature, not satisfactory to the absorption of NO and reduction effect.Develop active carbon
It is that fiber can load, economically and technically the metal oxide catalyst under feasible low-temperature condition is nitrogen oxides control
The developing direction in field.
In conclusion research high activity, anti-SO2Poisoning capability is strong, and high mechanical strength, abrasion resistance properties are good, and there have to be suitable
The catalyst in operating temperature section (especially low-temperature range) improves SCR denitration process to denitration efficiency is improved, and reduction is produced into
This is particularly significant.
Summary of the invention
In view of the actual demand of analysis and desulphurization denitration above for existing result of study, existing catalyst is overcome to exist
Catalytic activity is low when lower temperature or denitration efficiency is low, easily generation SO2Poisoning and disadvantage easy to wear, the present invention provides one
Kind high efficient cryogenic denitration composite catalyst.Specific technical solution is as follows:
A kind of high efficient cryogenic denitration composite catalyst, the composite catalyst include carrier, catalyst and auxiliary agent；The carrier
It is V for microporous carbon fiber, the catalyst2O5, the auxiliary agent be Fe2O3And CeO2。
Preferably, the V2O5、Fe2O3And CeO2Weight fraction be respectively 4 ~ 18wt%, 0.25 ~ 2wt%, 0.25 ~ 2wt%,
Surplus is microporous carbon fiber carrier.
The present invention also provides a kind of preparation methods of above-mentioned high efficient cryogenic denitration composite catalyst, have following preparation step
It is rapid:
The preparation of microporous carbon fiber and Fe2O3The load of auxiliary agent: first by polyacrylonitrile and Fe organic precursor (such as second
Sour iron, ferric oxalate) it is dissolved in organic solvent (volatile non-toxic or low-toxic organic solvent, such as ethyl alcohol, tetrahydrofuran), into
Row electrostatic spinning prepares compounding fiber, then pre-oxidized at 200 ~ 250 DEG C, 600 ~ 800 DEG C be carbonized, obtain
Fe2O3The microporous carbon fiber of nanometer particle load.
V2O5Catalyst, CeO2The load of auxiliary agent: the nitrate of V, Ce are dissolved into wiring solution-forming first, pour into water heating kettle
In, then by Fe2O3The microporous carbon fiber of nanometer particle load is added, seals, in 180 DEG C of 2 h of heating.The sample of hydro-thermal process
It is roasted at 400 ~ 500 DEG C, obtains catalyst V2O5, auxiliary agent CeO2And Fe2O3The compound carbon fiber of nanometer particle load is catalyzed
Agent.
The present invention can improve the contact area of adsorption reaction using microporous carbon fiber as carrier, make to NOx adsorption capacity more
By force, fibre structure intensity is higher, can effectively extend the service life of catalyst.
Auxiliary agent Fe in the present invention2O3Nanoparticle in 20 nm or less, be uniformly dispersed, be embedded in inside carbon fiber, promote carbon
The local graphite of fiber makes carbon fiber have higher intensity and heating conduction, while Fe2O3Nanoparticle can significantly
The low-temperature SCR performance for improving catalyst enhances anti-poisoning capability (generation for preventing sulfate) and has catalyst well
Water resistant activity.
The present invention adds auxiliary agent CeO2Be since Ce is there are a variety of valence states, can be played in catalysis reaction transmitting electronics,
The effect of ion and storage oxygen, it can be used as auxiliary agent and NO promoted to be converted into NO2To improve the low-temperature SCR activity of catalyst.CeO2
The introducing of nanoparticle not only increases the low temperature active of catalyst, broadens reaction temperature window, and enhance catalyst
Wear-resisting property.
Since denitration reaction belongs to gas-solid out-phase reaction, the V that the present invention uses hydro-thermal method to be prepared2O5And CeO2Powder
Have the advantages that purity is high, grain component and form are controllable, gained diameter of particle is in 30 nm or less, evenly dispersed, with carrier knot
It closes stronger, can be further improved the activity of catalyst.
The present invention introduces V simultaneously on microporous carbon fiber2O5、Fe2O3And CeO2Component, the catalyst of preparation and existing catalysis
Agent is compared and is had the advantage that
High low temperature active: when temperature is 120 DEG C, NOx entirety removal efficiency is greater than 95%, when denitrification rate reaches 80%
Temperature range is 80 ~ 100 DEG C；
Good SO2Anti- poisoning capability and water resistant activity: catalyst is applied to SO during SCR denitration2Conversion ratio is lower than
2.5%；
Very strong mechanical strength, longer service life: catalyst abrasion amount is lower than 40 mg.
Specific embodiment
Below for preparing the 10 g composite catalyst, the present invention is described in detail:
Embodiment 1
A kind of high efficient cryogenic denitration composite catalyst, the composite catalyst include carrier microporous carbon fiber, catalyst V2O5、
Auxiliary agent Fe2O3And CeO2；V2O5、Fe2O3And CeO2Weight fraction be respectively 4wt%, 2wt%, 2wt%, surplus is microporous carbon fiber
Carrier.
A method of the catalyst is prepared, there is following preparation step:
The preparation of microporous carbon fiber and Fe2O3The load of auxiliary agent: first by 13.54 g polyacrylonitrile and 0.58 g acetic acid
Dissolved ferric iron in ethanol, carry out electrostatic spinning prepare compounding fiber, then 200 ~ 250 DEG C pre-oxidized, 600 ~ 800 DEG C
It is carbonized, finally obtains Fe2O3The microporous carbon fiber of nanometer particle load, wherein Fe2O3Nanoparticle average grain diameter is 15
Nm, it is uniformly dispersed, is embedded in inside carbon fiber；Microporous carbon fiber local graphite；
V2O5Catalyst and CeO2The load of auxiliary agent: first by 0.40 g V (NO3)5With 0.08 g Ce (NO3)3·6H2O
Wiring solution-forming is dissolved, is poured into water heating kettle, then by Fe2O3The microporous carbon fiber of nanometer particle load is added, seals, 180
DEG C heating 2 h.The sample of hydro-thermal process is roasted at 400 ~ 500 DEG C, obtains catalyst V2O5, auxiliary agent CeO2And Fe2O3Nanometer
The composite carbon fiber catalyst of particle load, catalyst V2O5, auxiliary agent CeO2Average grain diameter is 26 nm, evenly dispersed.
The catalyst is used for the SCR method denitration of flue gas, flue gas GHSV(gas space velocity per hour)=40000 h-1, wherein
NOX、NH3、O2、SO2Volume fraction be respectively 0.05%, 0.05%, 5%, 0.1%, N2For Balance Air, other compositions and practical flue gas
It forms almost the same.Experimental result: when temperature is 120 DEG C, NOXRemoval efficiency is 96%, SO2Conversion ratio is 1.2%, catalyst abrasion
Amount is 28 mg；Temperature is 95 DEG C when denitrification rate is up to 80%.
Embodiment 2
A kind of high efficient cryogenic denitration composite catalyst, the composite catalyst include carrier microporous carbon fiber, catalyst V2O5、
Auxiliary agent Fe2O3And CeO2；V2O5、Fe2O3And CeO2Weight fraction be respectively 18wt%, 0.25wt%, 0.25wt%, surplus is micropore
Carbon fibre carrier.
A method of the catalyst is prepared, there is following preparation step:
The preparation of microporous carbon fiber and Fe2O3The load of auxiliary agent: first by 12.0 g polyacrylonitrile and 3.64 g ferric acetates
Dissolution in ethanol, carry out electrostatic spinning prepare compounding fiber, then 200 ~ 250 DEG C pre-oxidized, 600 ~ 800 DEG C into
Row carbonization, finally obtains Fe2O3The microporous carbon fiber of nanometer particle load, wherein Fe2O3Nanoparticle average grain diameter be 16 nm,
It is uniformly dispersed, is embedded in inside carbon fiber；Microporous carbon fiber local graphite；
V2O5Catalyst and CeO2The load of auxiliary agent: first by 3.57 g V (NO3)5With 6.31 g Ce (NO3)3·6H2O
Wiring solution-forming is dissolved, is poured into water heating kettle, then by Fe2O3The microporous carbon fiber of nanometer particle load is added, seals, 180
DEG C heating 2 h.The sample of hydro-thermal process is roasted at 400 ~ 500 DEG C, obtains catalyst V2O5, auxiliary agent CeO2And Fe2O3Nanometer
The composite carbon fiber catalyst of particle load, catalyst V2O5, auxiliary agent CeO2Average grain diameter is 25 nm, evenly dispersed.
The catalyst is used for the SCR method denitration of flue gas, flue gas GHSV (gas space velocity per hour)=40000 h-1,
Middle NOX、NH3、O2、SO2Volume fraction be respectively 0.05%, 0.05%, 5%, 0.1%, N2For Balance Air, other compositions and practical cigarette
Gas composition is almost the same.Experimental result: when temperature is 120 DEG C, NOXRemoval efficiency is 98%, SO2Conversion ratio is 2.3%, catalyst mill
Damage amount is 35 mg；Temperature is 86 DEG C when denitrification rate is up to 80%.
Embodiment 3
A kind of high efficient cryogenic denitration composite catalyst, the composite catalyst include carrier microporous carbon fiber, catalyst V2O5、
Auxiliary agent Fe2O3And CeO2；V2O5、Fe2O3And CeO2Weight fraction be respectively 8wt%, 1wt%, 0.6wt%, surplus is micropore carbon fiber
Tie up carrier.
A method of the catalyst is prepared, there is following preparation step:
The preparation of microporous carbon fiber and Fe2O3The load of auxiliary agent: first by 13.31 g polyacrylonitrile and 0.29 g oxalic acid
Dissolved ferric iron in ethanol, carry out electrostatic spinning prepare compounding fiber, then 200 ~ 250 DEG C pre-oxidized, 600 ~ 800 DEG C
It is carbonized, finally obtains Fe2O3The microporous carbon fiber of nanometer particle load, wherein Fe2O3Nanoparticle average grain diameter is 16
Nm, it is uniformly dispersed, is embedded in inside carbon fiber；Microporous carbon fiber local graphite；
V2O5Catalyst and CeO2The load of auxiliary agent: first by 1.91 g V (NO3)5With 0.15 g Ce (NO3)3·6H2O
Wiring solution-forming is dissolved, is poured into water heating kettle, then by Fe2O3The microporous carbon fiber of nanometer particle load is added, seals, 180
DEG C heating 2 h.The sample of hydro-thermal process is roasted at 400 ~ 500 DEG C, obtains catalyst V2O5, auxiliary agent CeO2And Fe2O3Nanometer
The composite carbon fiber catalyst of particle load, catalyst V2O5, auxiliary agent CeO2Average grain diameter is 27 nm, evenly dispersed.
The catalyst is used for the SCR method denitration of flue gas, flue gas GHSV (gas space velocity per hour)=40000 h-1,
Middle NOX、NH3、O2、SO2Volume fraction be respectively 0.05%, 0.05%, 5%, 0.1%, N2For Balance Air, other compositions and practical cigarette
Gas composition is almost the same.Experimental result: when temperature is 120 DEG C, NOXRemoval efficiency is 98%, SO2Conversion ratio is 1.4%, catalyst mill
Damage amount is 36 mg；Temperature is 95 DEG C when denitrification rate is up to 80%.
Embodiment 4
A kind of high efficient cryogenic denitration composite catalyst, the composite catalyst include carrier microporous carbon fiber, catalyst V2O5、
Auxiliary agent Fe2O3And CeO2；V2O5、Fe2O3And CeO2Weight fraction be respectively 10%, 2wt%, 0.8wt%, surplus is microporous carbon fiber
Carrier.
A method of the catalyst is prepared, there is following preparation step:
The preparation of microporous carbon fiber and Fe2O3The load of auxiliary agent: first by 12.38 g polyacrylonitrile and 0.58 g oxalic acid
Dissolved ferric iron in tetrahydrofuran, carry out electrostatic spinning prepare compounding fiber, then 200 ~ 250 DEG C pre-oxidized, 600 ~
800 DEG C are carbonized, and finally obtain Fe2O3The microporous carbon fiber of nanometer particle load, wherein Fe2O3Nanoparticle average grain diameter
For 15 nm, it is uniformly dispersed, is embedded in inside carbon fiber；Microporous carbon fiber local graphite；
V2O5Catalyst and CeO2The load of auxiliary agent: first by 1.98 g V (NO3)5With 0.20 g Ce (NO3)3·6H2O
Wiring solution-forming is dissolved, is poured into water heating kettle, then by Fe2O3The microporous carbon fiber of nanometer particle load is added, seals, 180
DEG C heating 2 h.The sample of hydro-thermal process is roasted at 400 ~ 500 DEG C, obtains catalyst V2O5, auxiliary agent CeO2And Fe2O3Nanometer
The composite carbon fiber catalyst of particle load, catalyst V2O5, auxiliary agent CeO2Average grain diameter is 26 nm, evenly dispersed.
The catalyst is used for the SCR method denitration of flue gas, flue gas GHSV (gas space velocity per hour)=40000 h-1,
Middle NOX、NH3、O2、SO2Volume fraction be respectively 0.05%, 0.05%, 5%, 0.1%, N2For Balance Air, other compositions and practical cigarette
Gas composition is almost the same.Experimental result: when temperature is 120 DEG C, NOXRemoval efficiency is 97%, SO2Conversion ratio is 2.4%, catalyst mill
Damage amount is 28 mg；Temperature is 102 DEG C when denitrification rate is up to 80%.
Embodiment 5
A kind of high efficient cryogenic denitration composite catalyst, the composite catalyst include carrier microporous carbon fiber, catalyst V2O5、
Auxiliary agent Fe2O3And CeO2；V2O5、Fe2O3And CeO2Weight fraction be respectively 15wt%, 0.5wt%, 2wt%, surplus is micropore carbon fiber
Tie up carrier.
A method of the catalyst is prepared, there is following preparation step:
The preparation of microporous carbon fiber and Fe2O3The load of auxiliary agent: first by 12.15 g polyacrylonitrile and 0.15 g oxalic acid
Dissolved ferric iron in tetrahydrofuran, carry out electrostatic spinning prepare compounding fiber, then 200 ~ 250 DEG C pre-oxidized, 600 ~
800 DEG C are carbonized, and finally obtain Fe2O3The microporous carbon fiber of nanometer particle load, wherein Fe2O3Nanoparticle average grain diameter
For 18 nm, it is uniformly dispersed, is embedded in inside carbon fiber；Microporous carbon fiber local graphite；
V2O5Catalyst and CeO2The load of auxiliary agent: first by 2.98 g V (NO3)5With 0.50 g Ce (NO3)3·6H2O
Wiring solution-forming is dissolved, is poured into water heating kettle, then by Fe2O3The microporous carbon fiber of nanometer particle load is added, seals, 180
DEG C heating 2 h.The sample of hydro-thermal process is roasted at 400 ~ 500 DEG C, obtains catalyst V2O5, auxiliary agent CeO2And Fe2O3Nanometer
The composite carbon fiber catalyst of particle load, catalyst V2O5, auxiliary agent CeO2Average grain diameter is 25 nm, evenly dispersed.
The catalyst is used for the SCR method denitration of flue gas, flue gas GHSV (gas space velocity per hour)=40000 h-1,
Middle NOX、NH3、O2、SO2Volume fraction be respectively 0.05%, 0.05%, 5%, 0.1%, N2For Balance Air, other compositions and practical cigarette
Gas composition is almost the same.Experimental result: when temperature is 120 DEG C, NOXRemoval efficiency is 95%, SO2Conversion ratio is 1.3%, catalyst mill
Damage amount is 27 mg；Temperature is 99 DEG C when denitrification rate is up to 80%.
Above embodiments are only the preferred embodiment of the present invention, should not be construed as limiting the invention.Obviously originally
The technical solution of invention is not limited to the above embodiments, and can also have many variations.Those skilled in the art, with the present invention
It defines that written description disclosed or according to file is undoubted to be obtained, is considered as the claimed model of this patent
It encloses.
Claims (5)
1. a kind of high efficient cryogenic denitration composite catalyst, it is characterised in that: the composite catalyst includes carrier, catalyst and helps
Agent；The carrier is microporous carbon fiber, and the catalyst is V2O5, the auxiliary agent is Fe2O3And CeO2；The V2O5、Fe2O3With
CeO2Weight fraction be respectively 4 ~ 18wt%, 0.25 ~ 2wt%, 0.25 ~ 2wt%, surplus is microporous carbon fiber carrier；
The preparation method of the composite catalyst has following preparation step:
(1) preparation of microporous carbon fiber and Fe2O3The load of auxiliary agent: by the co-blended spinning of Fe organic precursor and polyacrylonitrile,
Pre-oxidation, carbonization, obtain Fe2O3The microporous carbon fiber of nanometer particle load；
(2) V2O5Catalyst and CeO2The load of auxiliary agent: by V, Ce presoma in Fe2O3On nanometer particle load microporous carbon fiber
Hydro-thermal load, roasting, obtain denitration composite catalyst.
2. high efficient cryogenic denitration composite catalyst according to claim 1, which is characterized in that the preparation method step (1)
Middle Fe organic precursor is ferric acetate, ferric oxalate.
3. high efficient cryogenic denitration composite catalyst according to claim 1, which is characterized in that the preparation method step (2)
Middle V, Ce presoma is nitrate.
4. high efficient cryogenic denitration composite catalyst according to claim 1, which is characterized in that the preparation method step (1)
Middle Pre oxidation is 200 ~ 250 DEG C；Carburizing temperature is 600 ~ 800 DEG C.
5. high efficient cryogenic denitration composite catalyst according to claim 1, which is characterized in that the preparation method step (2)
Middle maturing temperature is 400 ~ 500 DEG C.
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| CN113457731B (en) * | 2021-07-06 | 2022-08-19 | 中国科学院过程工程研究所 | Molecular sieve catalytic inorganic fiber, preparation method thereof and dust removal and denitration integrated application |
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