CN106799224A - A kind of preparation method of sol-gel-dip method SCR denitration - Google Patents
A kind of preparation method of sol-gel-dip method SCR denitration Download PDFInfo
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- CN106799224A CN106799224A CN201710002170.7A CN201710002170A CN106799224A CN 106799224 A CN106799224 A CN 106799224A CN 201710002170 A CN201710002170 A CN 201710002170A CN 106799224 A CN106799224 A CN 106799224A
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- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
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- B01J23/16—Catalysts 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
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Abstract
The invention belongs to SCR denitration preparation field, and in particular to a kind of sol-gel-dip method SCR denitration and its preparation method and application.A kind of preparation method of sol-gel-dip method SCR denitration, comprises the following steps：The preparation of colloidal sol, nano-TiO2The preparation of suspension, TiO2‑SiO2The preparation of carrier and the preparation of denitrating catalyst.V prepared by the present invention2O5‑WO3/TiO2‑SiO2Specific surface area of catalyst increase, efficiency are improved, and improve the temperature range and stability of catalyst；Its preparation method is simple and easy to do, and the cost of nitrogen oxides treatment has been saved more to a certain extent, for the preparation of SCR denitration provides new approaches.
Description
Technical field
The invention belongs to SCR denitration preparation field, and in particular to a kind of sol-gel-dip method SCR denitration catalysis
Agent and its preparation method and application.
Background technology
For NH3- SCR processes, are widely used in NO in coal fired thermal power plantXTreatment is TiO2It is the denitration catalyst of carrier
Agent, conventional active component is mainly one or more of the metal oxides such as V, Fe, Mn, Cu.Because single metal oxidation
Thing catalyst denitration efficiency is low compared to composite type metallic oxide catalyst, so present researchers are for composite metal
The research of oxide catalyst is wider.At present, it is widely used in NO in coal fired thermal power plantXTreatment is V2O5-WO3(MoO3)/
TiO2Denitrating catalyst.
Because such catalyst is after load active component, specific surface area of catalyst reduction, average pore size increase take off it
Nitre temperature window is narrow, and low NO conversion ratios occur in low temperature and high-temperature region, and result of study shows that the high activity of catalyst has benefited from
The structure of carrier and catalyst.At present, catalyst modification is the research direction of the more SCR catalyst of report.There is scholar to adopt
With sol-gal process by ceramic load in TiO2Upper preparation contains SiO2Denitrating catalyst, find the significant increase catalyst of Si modification
Acidity, and its resistance to SO_2 and anti-K poisoning performances show superior.Also have by micro SiO2Deposition improves low temperature NH3-SCR
The water resistance of catalyst, finds SiO2The modified aperture that can improve denitrating catalyst, larger aperture can prevent water in catalysis
Condensed in agent, show good water resistance.These researchs show, V2O5-WO3/TiO2Catalyst modification research is to improve to urge
The effective means of agent service life.SiO2It is a kind of stable chemical nature, melts boiling point compound higher, SiO2Doping also by
Proof can improve acidity, specific surface area and the heat endurance of various SCR catalysts.
Therefore, the present invention is raw material using tetraethyl orthosilicate, using sol-gal process to carrier TiO2It is modified, prepares
SiO2The V of doping2O5-WO3/TiO2A kind of catalyst, there is provided preparation of sol-gel-dip method SCR denitration, and in mould
Intend realizing NH under conditions of flue gas3Selective Catalytic Reduction of NO.
The information for being disclosed in the background section is merely intended to increase the understanding to general background of the invention, without answering
In being considered as recognizing or imply in any form that the information structure has been the prior art well known to persons skilled in the art.
The content of the invention
In view of the shortcomings of the prior art, it is an object of the invention to provide a kind of sol-gel-dip method SCR denitration
And preparation method thereof, and NH is realized under conditions of simulated flue gas3Selective Catalytic Reduction of NO.
The present invention provide concrete technical scheme be：
A kind of preparation method of sol-gel-dip method SCR denitration, comprises the following steps：
(1) deionized water of 18mL and the 36-38% hydrochloric acid solutions of 0.8mL are measured respectively, is mixed, be slowly dropped to
In the tetraethyl orthosilicate of 23.1mL and the absolute ethyl alcohol mixed solution of 17.5mL, 1h is persistently stirred, colloidal sol is obtained；
(2) 3.9935-15.9740g nano-TiOs are weighed respectively2Powder in beaker, add 50mL absolute ethyl alcohol and
50mL deionized waters mix, ultrasonic disperse 30min, and nano-TiO is obtained2Suspension；
(3) by gained nano-TiO in step (2)2Suspension is added in step (1) gained colloidal sol, lasting stirring, slow drop
The ammonification aqueous solution, until gel-forming；The gel of gained is dried at 105 DEG C, is dried after 500 DEG C of roastings in Muffle furnace
2h, grinds and crosses 60 mesh sieves, and TiO is obtained2-SiO2Carrier；
(4) catalyst V is selected2O5：WO3：(TiO2-SiO2) mass ratio is 1：5：100, measure 5% oxalic acid of 100mL
Solution for standby, weighs 0.295g ammonium tungstates and 0.065g ammonium metavanadates in conical flask, adds part oxalic acid solution to be completely dissolved,
Obtain mixed liquor；
(5) TiO of 5g is weighed respectively2-SiO2In mixed liquor of the powder infusion in step (4), add remaining oxalic acid molten
Liquid, is placed in after stirring 1h in 60 DEG C of waters bath with thermostatic control, stands 1h, is dried at 105 DEG C, through 400-600 DEG C of roasting 5h, grinds and mistake
60 mesh sieves, that is, obtain denitrating catalyst.
Preferably, the rotating speed of stirring is 250r/min in step (1).
Preferably, the running parameter of ultrasound is in step (2)：Temperature 60 C, frequency 40KHz, power is 40W.
Preferably, the rotating speed of stirring is 300r/min in step (3).
Preferably, the concentration of ammonia spirit is 2mol/L in step (3).
Preferably, the rotating speed of stirring is 300r/min in step (5).
Compared with prior art, the present invention has the advantages that：
(1) traditional V2O5-WO3/TiO2In catalyst preparation process, after load active component, specific surface area can reduce,
And V prepared by the present invention2O5-WO3/TiO2-SiO2Specific surface area of catalyst increase, efficiency are improved, and again improve catalyst
Temperature range and stability.This is because sol-gal process synthesis has the advantages that adjustable porosity and specific surface area.
(2) V of the invention2O5-WO3/TiO2-SiO2The SiO that the preparation method of catalyst is used2Raw material are positive silicic acid second
Ester, compared with the raw material such as ceramics used in the prior art, its preparation method is simple and easy to do, saves more to a certain extent
The cost of nitrogen oxides treatment, for the preparation of SCR denitration provides new approaches.
Brief description of the drawings
Fig. 1 is the NH of simulated flue gas3- SCR activity test device figure；
Fig. 2 is doping SiO2Influence figure to catalyst denitration performance；
Fig. 3 is TiO2/SiO2Mol ratio is 0.5 influence figure of the different sintering temperatures to catalyst denitration performance；
Fig. 4 is TiO2/SiO2Mol ratio is 1 influence figure of the different sintering temperatures to catalyst denitration performance；
Fig. 5 is TiO2/SiO2Mol ratio is 2 influence figure of the different sintering temperatures to catalyst denitration performance；
Fig. 6 is V2O5-WO3/TiO2-SiO2Catalyst is in the active testing time that reaction temperature is 300 DEG C to denitration performance
Influence figure.
Specific embodiment
With reference to concrete example, the present invention is further detailed explanation.
Embodiment 1：
A kind of preparation method of sol-gel-dip method SCR denitration, comprises the following steps：
(1) deionized water of 18mL and 36% hydrochloric acid solution of 0.8mL are measured respectively, is mixed, be slowly dropped to
In the tetraethyl orthosilicate of 23.1mL and the absolute ethyl alcohol mixed solution of 17.5mL, 1h is persistently stirred, colloidal sol is obtained；The rotating speed of stirring
It is 250r/min；
(2) 3.9935g nano-TiOs are weighed respectively2Powder adds the absolute ethyl alcohol and 50mL deionizations of 50mL in beaker
Water mixes, ultrasonic disperse 30min, and nano-TiO is obtained2Suspension；Ultrasound running parameter be：Temperature 60 C, frequency 40KHz,
Power is 40W；
(3) by gained nano-TiO in step (2)2Suspension is added in step (1) gained colloidal sol, lasting stirring, slow drop
The ammonification aqueous solution, until gel-forming；The gel of gained is dried at 105 DEG C, is dried after 500 DEG C of roastings in Muffle furnace
2h, grinds and crosses 60 mesh sieves, and TiO is obtained2-SiO2Carrier；The rotating speed of stirring is 300r/min；The concentration of ammonia spirit is 2mol/
L；
(4) catalyst V is selected2O5：WO3：(TiO2-SiO2) mass ratio is 1：5：100, measure 5% oxalic acid of 100mL
Solution for standby, weighs 0.295g ammonium tungstates and 0.065g ammonium metavanadates in conical flask, adds part oxalic acid solution to be completely dissolved,
Obtain mixed liquor；
(5) TiO of 5g is weighed respectively2-SiO2In mixed liquor of the powder infusion in step (4), add remaining oxalic acid molten
Liquid, is placed in after stirring 1h in 60 DEG C of waters bath with thermostatic control, stands 1h, is dried at 105 DEG C, through 400 DEG C of roasting 5h, grinds and cross 60 mesh
Sieve, that is, obtain denitrating catalyst；The rotating speed of stirring is 300r/min.
Embodiment 2：
A kind of preparation method of sol-gel-dip method SCR denitration, comprises the following steps：
(1) deionized water of 18mL and 36% hydrochloric acid solution of 0.8mL are measured respectively, is mixed, be slowly dropped to
In the tetraethyl orthosilicate of 23.1mL and the absolute ethyl alcohol mixed solution of 17.5mL, 1h is persistently stirred, colloidal sol is obtained；The rotating speed of stirring
It is 250r/min；
(2) 3.9935g nano-TiOs are weighed respectively2Powder adds the absolute ethyl alcohol and 50mL deionizations of 50mL in beaker
Water mixes, ultrasonic disperse 30min, and nano-TiO is obtained2Suspension；Ultrasound running parameter be：Temperature 60 C, frequency 40KHz,
Power is 40W；
(3) by gained nano-TiO in step (2)2Suspension is added in step (1) gained colloidal sol, lasting stirring, slow drop
The ammonification aqueous solution, until gel-forming；The gel of gained is dried at 105 DEG C, is dried after 500 DEG C of roastings in Muffle furnace
2h, grinds and crosses 60 mesh sieves, and TiO is obtained2-SiO2Carrier；The rotating speed of stirring is 300r/min；The concentration of ammonia spirit is 2mol/
L；
(4) catalyst V is selected2O5：WO3：(TiO2-SiO2) mass ratio is 1：5：100, measure 5% oxalic acid of 100mL
Solution for standby, weighs 0.295g ammonium tungstates and 0.065g ammonium metavanadates in conical flask, adds part oxalic acid solution to be completely dissolved,
Obtain mixed liquor；
(5) TiO of 5g is weighed respectively2-SiO2In mixed liquor of the powder infusion in step (4), add remaining oxalic acid molten
Liquid, is placed in after stirring 1h in 60 DEG C of waters bath with thermostatic control, stands 1h, is dried at 105 DEG C, through 500 DEG C of roasting 5h, grinds and cross 60 mesh
Sieve, that is, obtain denitrating catalyst；The rotating speed of stirring is 300r/min.
Embodiment 3：
A kind of preparation method of sol-gel-dip method SCR denitration, comprises the following steps：
(1) deionized water of 18mL and 36% hydrochloric acid solution of 0.8mL are measured respectively, is mixed, be slowly dropped to
In the tetraethyl orthosilicate of 23.1mL and the absolute ethyl alcohol mixed solution of 17.5mL, 1h is persistently stirred, colloidal sol is obtained；The rotating speed of stirring
It is 250r/min；
(2) 3.9935g nano-TiOs are weighed respectively2Powder adds the absolute ethyl alcohol and 50mL deionizations of 50mL in beaker
Water mixes, ultrasonic disperse 30min, and nano-TiO is obtained2Suspension；Ultrasound running parameter be：Temperature 60 C, frequency 40KHz,
Power is 40W；
(3) by gained nano-TiO in step (2)2Suspension is added in step (1) gained colloidal sol, lasting stirring, slow drop
The ammonification aqueous solution, until gel-forming；The gel of gained is dried at 105 DEG C, is dried after 500 DEG C of roastings in Muffle furnace
2h, grinds and crosses 60 mesh sieves, and TiO is obtained2-SiO2Carrier；The rotating speed of stirring is 300r/min；The concentration of ammonia spirit is 2mol/
L；
(4) catalyst V is selected2O5：WO3：(TiO2-SiO2) mass ratio is 1：5：100, measure 5% oxalic acid of 100mL
Solution for standby, weighs 0.295g ammonium tungstates and 0.065g ammonium metavanadates in conical flask, adds part oxalic acid solution to be completely dissolved,
Obtain mixed liquor；
(5) TiO of 5g is weighed respectively2-SiO2In mixed liquor of the powder infusion in step (4), add remaining oxalic acid molten
Liquid, is placed in after stirring 1h in 60 DEG C of waters bath with thermostatic control, stands 1h, is dried at 105 DEG C, through 600 DEG C of roasting 5h, grinds and cross 60 mesh
Sieve, that is, obtain denitrating catalyst；The rotating speed of stirring is 300r/min.
Embodiment 4：
A kind of preparation method of sol-gel-dip method SCR denitration, comprises the following steps：
(1) deionized water of 18mL and the 36-38% hydrochloric acid solutions of 0.8mL are measured respectively, is mixed, be slowly dropped to
In the tetraethyl orthosilicate of 23.1mL and the absolute ethyl alcohol mixed solution of 17.5mL, 1h is persistently stirred, colloidal sol is obtained；The rotating speed of stirring
It is 250r/min；
(2) 7.9870g nano-TiOs are weighed respectively2Powder adds the absolute ethyl alcohol and 50mL deionizations of 50mL in beaker
Water mixes, ultrasonic disperse 30min, and nano-TiO is obtained2Suspension；Ultrasound running parameter be：Temperature 60 C, frequency 40KHz,
Power is 40W；
(3) by gained nano-TiO in step (2)2Suspension is added in step (1) gained colloidal sol, lasting stirring, slow drop
The ammonification aqueous solution, until gel-forming；The gel of gained is dried at 105 DEG C, is dried after 500 DEG C of roastings in Muffle furnace
2h, grinds and crosses 60 mesh sieves, and TiO is obtained2-SiO2Carrier；The rotating speed of stirring is 300r/min；The concentration of ammonia spirit is 2mol/
L；
(4) catalyst V is selected2O5：WO3：(TiO2-SiO2) mass ratio is 1：5：100, measure 5% oxalic acid of 100mL
Solution for standby, weighs 0.295g ammonium tungstates and 0.065g ammonium metavanadates in conical flask, adds part oxalic acid solution to be completely dissolved,
Obtain mixed liquor；
(5) TiO of 5g is weighed respectively2-SiO2In mixed liquor of the powder infusion in step (4), add remaining oxalic acid molten
Liquid, is placed in after stirring 1h in 60 DEG C of waters bath with thermostatic control, stands 1h, is dried at 105 DEG C, through 400 DEG C of roasting 5h, grinds and cross 60 mesh
Sieve, that is, obtain denitrating catalyst；The rotating speed of stirring is 300r/min.
Embodiment 5：
A kind of preparation method of sol-gel-dip method SCR denitration, comprises the following steps：
(1) deionized water of 18mL and the 36-38% hydrochloric acid solutions of 0.8mL are measured respectively, is mixed, be slowly dropped to
In the tetraethyl orthosilicate of 23.1mL and the absolute ethyl alcohol mixed solution of 17.5mL, 1h is persistently stirred, colloidal sol is obtained；The rotating speed of stirring
It is 250r/min；
(2) 7.9870g nano-TiOs are weighed respectively2Powder adds the absolute ethyl alcohol and 50mL deionizations of 50mL in beaker
Water mixes, ultrasonic disperse 30min, and nano-TiO is obtained2Suspension；Ultrasound running parameter be：Temperature 60 C, frequency 40KHz,
Power is 40W；
(3) by gained nano-TiO in step (2)2Suspension is added in step (1) gained colloidal sol, lasting stirring, slow drop
The ammonification aqueous solution, until gel-forming；The gel of gained is dried at 105 DEG C, is dried after 500 DEG C of roastings in Muffle furnace
2h, grinds and crosses 60 mesh sieves, and TiO is obtained2-SiO2Carrier；The rotating speed of stirring is 300r/min；The concentration of ammonia spirit is 2mol/
L；
(4) catalyst V is selected2O5：WO3：(TiO2-SiO2) mass ratio is 1：5：100, measure 5% oxalic acid of 100mL
Solution for standby, weighs 0.295g ammonium tungstates and 0.065g ammonium metavanadates in conical flask, adds part oxalic acid solution to be completely dissolved,
Obtain mixed liquor；
(5) TiO of 5g is weighed respectively2-SiO2In mixed liquor of the powder infusion in step (4), add remaining oxalic acid molten
Liquid, is placed in after stirring 1h in 60 DEG C of waters bath with thermostatic control, stands 1h, is dried at 105 DEG C, through 500 DEG C of roasting 5h, grinds and cross 60 mesh
Sieve, that is, obtain denitrating catalyst；The rotating speed of stirring is 300r/min.
Embodiment 6：
A kind of preparation method of sol-gel-dip method SCR denitration, comprises the following steps：
(1) deionized water of 18mL and the 36-38% hydrochloric acid solutions of 0.8mL are measured respectively, is mixed, be slowly dropped to
In the tetraethyl orthosilicate of 23.1mL and the absolute ethyl alcohol mixed solution of 17.5mL, 1h is persistently stirred, colloidal sol is obtained；The rotating speed of stirring
It is 250r/min；
(2) 7.9870g nano-TiOs are weighed respectively2Powder adds the absolute ethyl alcohol and 50mL deionizations of 50mL in beaker
Water mixes, ultrasonic disperse 30min, and nano-TiO is obtained2Suspension；Ultrasound running parameter be：Temperature 60 C, frequency 40KHz,
Power is 40W；
(3) by gained nano-TiO in step (2)2Suspension is added in step (1) gained colloidal sol, lasting stirring, slow drop
The ammonification aqueous solution, until gel-forming；The gel of gained is dried at 105 DEG C, is dried after 500 DEG C of roastings in Muffle furnace
2h, grinds and crosses 60 mesh sieves, and TiO is obtained2-SiO2Carrier；The rotating speed of stirring is 300r/min；The concentration of ammonia spirit is 2mol/
L；
(4) catalyst V is selected2O5：WO3：(TiO2-SiO2) mass ratio is 1：5：100, measure 5% oxalic acid of 100mL
Solution for standby, weighs 0.295g ammonium tungstates and 0.065g ammonium metavanadates in conical flask, adds part oxalic acid solution to be completely dissolved,
Obtain mixed liquor；
(5) TiO of 5g is weighed respectively2-SiO2In mixed liquor of the powder infusion in step (4), add remaining oxalic acid molten
Liquid, is placed in after stirring 1h in 60 DEG C of waters bath with thermostatic control, stands 1h, is dried at 105 DEG C, through 600 DEG C of roasting 5h, grinds and cross 60 mesh
Sieve, that is, obtain denitrating catalyst；The rotating speed of stirring is 300r/min.
Embodiment 7：
A kind of preparation method of sol-gel-dip method SCR denitration, comprises the following steps：
(1) deionized water of 18mL and the 36-38% hydrochloric acid solutions of 0.8mL are measured respectively, is mixed, be slowly dropped to
In the tetraethyl orthosilicate of 23.1mL and the absolute ethyl alcohol mixed solution of 17.5mL, 1h is persistently stirred, colloidal sol is obtained；The rotating speed of stirring
It is 250r/min；
(2) 15.9740g nano-TiOs are weighed respectively2Powder in beaker, add 50mL absolute ethyl alcohol and 50mL go from
Sub- water mixing, ultrasonic disperse 30min is obtained nano-TiO2Suspension；Ultrasound running parameter be：Temperature 60 C, frequency
40KHz, power is 40W；
(3) by gained nano-TiO in step (2)2Suspension is added in step (1) gained colloidal sol, lasting stirring, slow drop
The ammonification aqueous solution, until gel-forming；The gel of gained is dried at 105 DEG C, is dried after 500 DEG C of roastings in Muffle furnace
2h, grinds and crosses 60 mesh sieves, and TiO is obtained2-SiO2Carrier；The rotating speed of stirring is 300r/min；The concentration of ammonia spirit is 2mol/
L；
(4) catalyst V is selected2O5：WO3：(TiO2-SiO2) mass ratio is 1：5：100, measure 5% oxalic acid of 100mL
Solution for standby, weighs 0.295g ammonium tungstates and 0.065g ammonium metavanadates in conical flask, adds part oxalic acid solution to be completely dissolved,
Obtain mixed liquor；
(5) TiO of 5g is weighed respectively2-SiO2In mixed liquor of the powder infusion in step (4), add remaining oxalic acid molten
Liquid, is placed in after stirring 1h in 60 DEG C of waters bath with thermostatic control, stands 1h, is dried at 105 DEG C, through 400 DEG C of roasting 5h, grinds and cross 60 mesh
Sieve, that is, obtain denitrating catalyst；The rotating speed of stirring is 300r/min.
Embodiment 8：
A kind of preparation method of sol-gel-dip method SCR denitration, comprises the following steps：
(1) deionized water of 18mL and the 36-38% hydrochloric acid solutions of 0.8mL are measured respectively, is mixed, be slowly dropped to
In the tetraethyl orthosilicate of 23.1mL and the absolute ethyl alcohol mixed solution of 17.5mL, 1h is persistently stirred, colloidal sol is obtained；The rotating speed of stirring
It is 250r/min；
(2) 15.9740g nano-TiOs are weighed respectively2Powder in beaker, add 50mL absolute ethyl alcohol and 50mL go from
Sub- water mixing, ultrasonic disperse 30min is obtained nano-TiO2Suspension；Ultrasound running parameter be：Temperature 60 C, frequency
40KHz, power is 40W；
(3) by gained nano-TiO in step (2)2Suspension is added in step (1) gained colloidal sol, lasting stirring, slow drop
The ammonification aqueous solution, until gel-forming；The gel of gained is dried at 105 DEG C, is dried after 500 DEG C of roastings in Muffle furnace
2h, grinds and crosses 60 mesh sieves, and TiO is obtained2-SiO2Carrier；The rotating speed of stirring is 300r/min；The concentration of ammonia spirit is 2mol/
L；
(4) catalyst V is selected2O5：WO3：(TiO2-SiO2) mass ratio is 1：5：100, measure 5% oxalic acid of 100mL
Solution for standby, weighs 0.295g ammonium tungstates and 0.065g ammonium metavanadates in conical flask, adds part oxalic acid solution to be completely dissolved,
Obtain mixed liquor；
(5) TiO of 5g is weighed respectively2-SiO2In mixed liquor of the powder infusion in step (4), add remaining oxalic acid molten
Liquid, is placed in after stirring 1h in 60 DEG C of waters bath with thermostatic control, stands 1h, is dried at 105 DEG C, through 500 DEG C of roasting 5h, grinds and cross 60 mesh
Sieve, that is, obtain denitrating catalyst；The rotating speed of stirring is 300r/min.
Embodiment 9：
A kind of preparation method of sol-gel-dip method SCR denitration, comprises the following steps：
(1) deionized water of 18mL and the 36-38% hydrochloric acid solutions of 0.8mL are measured respectively, is mixed, be slowly dropped to
In the tetraethyl orthosilicate of 23.1mL and the absolute ethyl alcohol mixed solution of 17.5mL, 1h is persistently stirred, colloidal sol is obtained；The rotating speed of stirring
It is 250r/min
(2) 15.9740g nano-TiOs are weighed respectively2Powder in beaker, add 50mL absolute ethyl alcohol and 50mL go from
Sub- water mixing, ultrasonic disperse 30min is obtained nano-TiO2Suspension；Ultrasound running parameter be：Temperature 60 C, frequency
40KHz, power is 40W；
(3) by gained nano-TiO in step (2)2Suspension is added in step (1) gained colloidal sol, lasting stirring, slow drop
The ammonification aqueous solution, until gel-forming；The gel of gained is dried at 105 DEG C, is dried after 500 DEG C of roastings in Muffle furnace
2h, grinds and crosses 60 mesh sieves, and TiO is obtained2-SiO2Carrier；The rotating speed of stirring is 300r/min；The concentration of ammonia spirit is 2mol/
L；
(4) catalyst V is selected2O5：WO3：(TiO2-SiO2) mass ratio is 1：5：100, measure 5% oxalic acid of 100mL
Solution for standby, weighs 0.295g ammonium tungstates and 0.065g ammonium metavanadates in conical flask, adds part oxalic acid solution to be completely dissolved,
Obtain mixed liquor；
(5) TiO of 5g is weighed respectively2-SiO2In mixed liquor of the powder infusion in step (4), add remaining oxalic acid molten
Liquid, is placed in after stirring 1h in 60 DEG C of waters bath with thermostatic control, stands 1h, is dried at 105 DEG C, through 600 DEG C of roasting 5h, grinds and cross 60 mesh
Sieve, that is, obtain denitrating catalyst；The rotating speed of stirring is 300r/min.
Control：
A kind of preparation method of infusion process SCR denitration, comprises the following steps：
(1) catalyst V is selected2O5：WO3：TiO2Mass ratio is 1：5：100,5% oxalic acid solution for measuring 100mL is standby
With, 0.295g ammonium tungstates and 0.065g ammonium metavanadates are weighed in conical flask, add part oxalic acid solution to be completely dissolved, mixed
Close liquid；
(2) nano-TiO of 5g is weighed2In mixed liquor of the powder infusion in step (1), remaining oxalic acid solution is added,
It is placed in after stirring 1h in 60 DEG C of waters bath with thermostatic control, stands 1h, dried at 105 DEG C, through 500 DEG C of roasting 5h, grinds and cross 60 mesh sieves,
Denitrating catalyst is obtained, the rotating speed of stirring is 300r/min.
Carry out simulated flue gas with steel gas cylinder to constitute, including NO, O2、N2Deng NH3It is reducing gas.Simulated flue gas NH3、NO、O2With
N2Flow respectively by mass flowmenter control, reactor is entered after being well mixed, reactor lower end is placed silica wool and is fixed
Catalyst (referring to accompanying drawing 1).Experiment starts, and the 0.9g catalyst prepared in embodiment 1-9 is weighed respectively and is put into reactor, if
Determine heating schedule (10 DEG C/min of heating rate), be measured data, NO initial concentrations and reaction tail successively from low temperature to high temperature
Gas concentration is determined using flue gas analyzer, and each temperature residence time is 1h.
The specific surface area and pore property figure of the catalyst of table 1
To embodiment 1-9 with compare in the denitration rate of catalyst that obtains be measured, as a result as shown in figures 2-6.
As shown in Figure 2, undoped p SiO2V2O5-WO3/TiO2Catalyst is also constantly carried with the rising of temperature, denitration rate
Height, it is 97% that maximum denitration rate is reached at 350 DEG C, and when temperature is more than 350 DEG C, denitration rate is reduced with the rising of temperature,
71% is dropped at 450 DEG C.Three kinds of V2O5-WO3/TiO2-SiO2The denitration rate variation tendency of catalyst is similar to, with reaction temperature
Rising and raise, stabilization can be kept at 250-350 DEG C, and all more than 90%, from 400 DEG C begin with it is obvious under
Drop.With V2O5-WO3/TiO2COMPARATIVE CATALYST, adulterate SiO2V2O5-WO3/TiO2-SiO2Catalyst denitration rate is to the maximum
100%, although little is improved to denitration rate, but can be to make catalyst that there is temperature range wider, and can keep good
Stability.
As shown in Fig. 3-5, three kinds of SiO2The V of doping2O5-WO3/TiO2-SiO2Catalyst is warmed up to 450 DEG C from 200 DEG C
When, denitration rate is gradually stepped up as reaction temperature is raised, and occurs optimal reaction temperature at 300-350 DEG C, but on
It is raised to after 350 DEG C, denitration rate has different degrees of decline.TiO in Fig. 32/SiO2When=0.5,400 DEG C, 500 DEG C and 600
DEG C roasting catalyst maximum denitration rate be respectively 100%, 98% and 99%.TiO in Fig. 42/SiO2When=1,400 DEG C, 500 DEG C
Catalyst maximum denitration rate with 600 DEG C of roastings is respectively 99%, 99% and 96%.TiO in Fig. 52/SiO2When=2,400 DEG C,
The catalyst maximum denitration rate of 500 DEG C and 600 DEG C roastings is respectively 98%, 94% and 100%.
As shown in Figure 6, when just having started reaction, V2O5-WO3/TiO2-SiO2Catalyst denitration rate is 97%, as activity is surveyed
The examination time is 12h, 24h, 36h and 48h, and the denitration rate of catalyst has almost no change, and is attained by 99%, illustrates with activity
Testing time is constantly elongated, and catalyst can also keep good denitration performance.
The foregoing description to specific illustrative embodiment of the invention be in order to illustrate and illustration purpose.These descriptions
It is not wishing to limit the invention to disclosed precise forms, and it will be apparent that according to above-mentioned teaching, can be much changed
And change.The purpose of selecting and describing the exemplary embodiment is that explaining that certain principles of the invention and its reality should
With so that those skilled in the art can realize and using a variety of exemplaries of the invention and
A variety of selections and change.The scope of the present invention is intended to be limited by claims and its equivalents.
Claims (6)
1. a kind of preparation method of sol-gel-dip method SCR denitration, it is characterised in that comprise the following steps：
(1) deionized water of 18mL and the 36-38% hydrochloric acid solutions of 0.8mL are measured respectively, is mixed, be slowly dropped to
In the tetraethyl orthosilicate of 23.1mL and the absolute ethyl alcohol mixed solution of 17.5mL, 1h is persistently stirred, colloidal sol is obtained；
(2) 3.9935-15.9740g nano-TiOs are weighed respectively2Powder adds the absolute ethyl alcohol and 50mL of 50mL to go in beaker
Ionized water mixes, ultrasonic disperse 30min, and nano-TiO is obtained2Suspension；
(3) by gained nano-TiO in step (2)2Suspension is added in step (1) gained colloidal sol, and lasting stirring is slowly added dropwise ammonia
The aqueous solution, until gel-forming；The gel of gained is dried at 105 DEG C, is dried after 500 DEG C of roasting 2h in Muffle furnace, ground
60 mesh sieves are ground and crossed, TiO is obtained2-SiO2Carrier；
(4) catalyst V is selected2O5：WO3：(TiO2-SiO2) mass ratio is 1：5：100, measure 5% oxalic acid solution of 100mL
It is standby, 0.295g ammonium tungstates and 0.065g ammonium metavanadates are weighed in conical flask, add part oxalic acid solution to be completely dissolved, obtain
Mixed liquor；
(5) TiO of 5g is weighed respectively2-SiO2In mixed liquor of the powder infusion in step (4), remaining oxalic acid solution is added,
It is placed in after stirring 1h in 60 DEG C of waters bath with thermostatic control, stands 1h, dried at 105 DEG C, through 400-600 DEG C of roasting 5h, grinds and cross 60
Mesh sieve, that is, obtain denitrating catalyst.
2. the preparation method of sol-gel-dip method SCR denitration according to claim 1, it is characterised in that step
Suddenly the rotating speed of stirring is 250r/min in (1).
3. the preparation method of sol-gel-dip method SCR denitration according to claim 1, it is characterised in that step
Suddenly the running parameter of ultrasound is in (2)：Temperature 60 C, frequency 40KHz, power is 40W.
4. the preparation method of sol-gel-dip method SCR denitration according to claim 1, it is characterised in that step
Suddenly the rotating speed of stirring is 300r/min in (3).
5. the preparation method of sol-gel-dip method SCR denitration according to claim 1, it is characterised in that step
Suddenly the concentration of ammonia spirit is 2mol/L in (3).
6. the preparation method of sol-gel-dip method SCR denitration according to claim 1, it is characterised in that step
Suddenly the rotating speed of stirring is 300r/min in (5).
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| CN108855044A (en) * | 2018-04-18 | 2018-11-23 | 浙江工业大学 | Preparation method of vanadium-tungsten catalyst |
| CN110038554A (en) * | 2019-06-03 | 2019-07-23 | 运城学院 | A kind of V that mica supports2O5-WO3/TiO2The preparation method of catalyst |
| CN110694638A (en) * | 2019-10-14 | 2020-01-17 | 西安热工研究院有限公司 | Modified low-temperature SCR (Selective catalytic reduction) active coke catalyst with hydrophobicity and preparation method thereof |
| CN113107650A (en) * | 2020-01-09 | 2021-07-13 | 广西大学 | Dynamic mixer for diesel engine urea-SCR system |
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| CN101954290A (en) * | 2010-08-23 | 2011-01-26 | 北京科技大学 | Novel composite carrier SCR flue gas denitration catalyst |
| CN103769137A (en) * | 2012-10-25 | 2014-05-07 | 中国石油化工股份有限公司 | Preparation method of high-strength flue gas denitration catalyst |
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| CN110038554A (en) * | 2019-06-03 | 2019-07-23 | 运城学院 | A kind of V that mica supports2O5-WO3/TiO2The preparation method of catalyst |
| CN110694638A (en) * | 2019-10-14 | 2020-01-17 | 西安热工研究院有限公司 | Modified low-temperature SCR (Selective catalytic reduction) active coke catalyst with hydrophobicity and preparation method thereof |
| CN110694638B (en) * | 2019-10-14 | 2022-12-09 | 西安热工研究院有限公司 | Modified low-temperature SCR (Selective catalytic reduction) active coke catalyst with hydrophobicity and preparation method thereof |
| CN113107650A (en) * | 2020-01-09 | 2021-07-13 | 广西大学 | Dynamic mixer for diesel engine urea-SCR system |
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