CN107433204A - Reduce load-type iron-based catalyst of sulfur dioxide in flue gas and nitrogen oxides and preparation method and application simultaneously - Google Patents
Reduce load-type iron-based catalyst of sulfur dioxide in flue gas and nitrogen oxides and preparation method and application simultaneously Download PDFInfo
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Abstract
The invention discloses load-type iron-based catalyst for reducing sulfur dioxide in flue gas and nitrogen oxides simultaneously and preparation method and application.Load-type iron-based catalyst is made up of ferro element, transition metal M and carrier containing zirconium, the composition formula of catalyst is M (y)-Fe/Zr (a)-ZSM-5, M is one or both of transition metal Cr and Ce, and the percentage that M element accounts for carrier quality with Fe element quality sums is 5~30%；Y is M/ (M+Fe) mol ratio, and Zr (a)-ZSM-5 is the carrier of zirconium, and wherein a is Zr/Al mol ratios.Active testing result is shown, is 20000~80000ml/gh in air speed, under conditions of temperature is 300~550 DEG C, catalyst can realize the desulphurization denitration rate close to 100% and the S selectivity and N close to 100%2Selectivity.
Description
Technical field
The present invention relates to load-type iron-based catalyst, and sulfur dioxide in flue gas and nitrogen oxygen are reduced simultaneously more particularly to a kind of
Load-type iron-based catalyst of compound and preparation method thereof；Belong to environmental protection science field.
Background technology
Industrial flue gas desulfurization is mainly wet desulphurization at present, and wet process of FGD is washed using liquid (alkali lye) absorbent
Flue gas is washed, absorbs SO contained in flue gas2Although wet desulphurization desulfuration efficiency is high, waste water, waste residue can be produced, it is necessary to enter one
Step post processing, while wet absorption needs huge equipment and place, cost of a relatively high.In addition, industrial denitrating flue gas master
If SCR (the NH of ammonia3- SCR), the catalyst of use is mostly V2O5-WO3-TiO2The oxide of class, although de-
Nitre efficiency high, but the storage of ammonia and transport are relatively inconvenient, the while the problem of leakage that ammonia be present causes secondary pollution, in addition ammonia
The problem of corrosion to equipment is also to be solved.At present, it is the flue gas for studying most hot most prospect that CO, which is used for flue gas desulfurization and denitrification,
One of desulphurization denitration technology.It is primarily due in actual flue gas often contain a certain amount of CO, utilizes existing CO in flue gas
SO is reduced as reducing agent2It is respectively corresponding elemental sulfur and N with NO2, CO, SO can be not only removed simultaneously2With tri- kinds of pollutions of NO
Thing, the amount of the reducing agent of addition can also be reduced, it is cost-effective.
More catalyst or noble metal catalyst, noble metal are used currently used for the flue gas desulfurization of CO reducing process or denitration
Although catalyst removal effect is good, cost, which is undoubtedly, restricts one of biggest obstacle of its large-scale application.Use transition metal
Substitute noble metal and have that removal efficiency is not high, reaction temperature is high again (>500 DEG C), the problems such as accessory substance is more.Such as Chinese invention patent
Application CN102836717A discloses spinel oxide simultaneous SO_2 and NO removal, but there is removal efficiency it is not high (desulfurization degree 95%,
Denitration rate 55%), reaction temperature it is high (>600 DEG C) the problem of；Chinese invention patent application CN106268296A proposes lanthanum base calcium
The method of titanium ore composite oxides simultaneous SO_2 and NO removal, but reaction temperature is higher (500~600 DEG C), and do not account for desulfurization
During sulphur selective problems；Chinese invention patent application CN10179345A reports ferrum-based catalyst and is used for flue gas simultaneously
Desulphurization denitration, but the catalyst needs presulfurization before test, this undoubtedly the complexity of increased operation and presulfurization it
Catalyst afterwards is also easy to produce the COS of severe toxicity when in use.Therefore, catalyst reported above also has some limitations.
The content of the invention
In order to overcome the shortcomings and deficiencies of the prior art described above, primary and foremost purpose of the invention is to provide a kind of approach
100% desulphurization denitration rate and close to 100% S selectivity and N2Selectivity, and with good water-resistance, antioxidant it is same
When selective reduction sulfur dioxide in flue gas and nitrogen oxides iron-based composite oxide catalysts.
Another object of the present invention is to provide the preparation method of described iron-based composite oxides.
It is still another object of the present invention to provide the application of described iron-based composite oxides.
The purpose of the present invention is achieved through the following technical solutions：
The load-type iron-based catalyst of sulfur dioxide in flue gas and nitrogen oxides is reduced simultaneously：By ferro element, transition metal
Element M and the carrier composition containing zirconium, the composition formula of described catalyst is M (y)-Fe/Zr (a)-ZSM-5, and M is transition metal member
One or both of plain Cr and Ce, the percentage that M element accounts for carrier quality with Fe element quality sums is 5~30%；Y is M/
(M+Fe) mol ratio, 0.1<y<0.9；Zr (a)-ZSM-5 is the carrier of zirconium, and wherein a is Zr/Al mol ratios, 0.5<a<5, carrier
Si/ (Al+Zr) mol ratio be 30~60.
The preparation method of the load-type iron-based catalyst of sulfur dioxide in flue gas and nitrogen oxides, bag are reduced while described
Include following steps：
1) preparation of the carrier of zirconium-containing ZSM-5-5：Zirconium zeolite molecular sieve, tetraethyl orthosilicate (TEOS) are synthesized using hydrothermal crystallization method
For silicon source, using zirconyl nitrate as zirconium source, aluminum nitrate is silicon source, and 4-propyl bromide (TPABr) is template, according to mol ratio n
(Si)：n(Al+Zr)：n(TPABr)：n(H2O)=30~60：1：8~12：2000~6000, with NaOH regulation pH value be 10~
12, stir, then 24~72h of crystallization at a temperature of 140~170 DEG C, at 400~600 DEG C after centrifugation, washing, drying
3~6h of roasting temperature obtains the carrier of zirconium-containing ZSM-5-5.
2) preparation of catalyst：Using citric acid method, the carrier of zirconium-containing ZSM-5-5, ferric nitrate, mistake are added into citric acid solution
Metal nitrate is crossed, stirs 1~4h at room temperature；
3) metal salt obtained by step 2) is dried at 50~120 DEG C, 3~6h is then calcined at 400~600 DEG C；
4) metal composite oxide grinding, tabletting, the sieving prepared step 3), obtains the catalysis of simultaneous SO_2 and NO removal
Agent.
Further to realize the object of the invention, it is preferable that the concentration of the citric acid solution described in step 1) be 2~
3mol/L, the mole of total metal of the amount of the citric acid of addition with adding are equal.
Preferably, the sieve diameter of the sieving is 40~80 mesh.
Preferably, the time to stir is 1~4h.
Preferably, the time of the step 3) drying is 12-15h.
The application of load-type iron-based catalyst that is described while reducing sulfur dioxide in flue gas and nitrogen oxides, its feature exist
In the air speed that flue gas passes through catalyst is 20000~80000ml/gh.
Preferably, the NO concentration of the flue gas is 500~1500mg/m3, SO2Concentration is 1000~2500mg/m3, temperature
For 300~550 DEG C.
The redox reaction that the present invention occurs is NOx+CO→N2+CO2, SOx+CO→S+CO2。
Relative to prior art, the invention has the advantages that and beneficial effect：
(1) catalyst that the present invention reports has excellent activity, and at 350~550 DEG C, 20000~80000ml/gh is empty
Under the conditions of speed, 100% desulfurization degree and denitration rate can be achieved, while almost there is no COS and N2The generation of the accessory substances such as O.
(2) COS generation has been reduced or avoided without presulfurization before use in the catalyst that the present invention reports, simplifies again
Operation.
(3) catalyst reported of the present invention has good water-resistance, adds 6% vapor in reaction gas, 450 DEG C with
On, vapor has little to no effect to catalyst activity.
(4) catalyst that the present invention reports has preferable antioxidant, and when adding oxygen, the amount of total oxide is gone back with total
When former agent CO amount is roughly equal, more than 600 DEG C, the activity of catalyst does not significantly decrease, still keep close to 100% it is de-
Nitre rate and more than 80% desulfurization degree.
(5) compared to the reducing process simultaneous SO_2 and NO removal technology reported, not only desulphurization denitration has well the present invention
Effect, and the temperature in use of catalyst can be significantly reduced, without pre-vulcanization process, preparation method is simple, raw material sources
Extensively.
Brief description of the drawings
Fig. 1 is that catalyst is simultaneously by Cr (y)-Fe/Zr (1)-ZSM-5 (y=0.1,04,0.5) for preparing in embodiment 1~3
The denitration rate of desulphurization denitration varies with temperature curve.
Fig. 2 is that catalyst is simultaneously by Cr (y)-Fe/Zr (1)-ZSM-5 (y=0.1,04,0.5) for preparing in embodiment 1~3
The desulfurization degree of desulphurization denitration varies with temperature curve.
Fig. 3 is that catalyst is simultaneously by Cr (y)-Fe/Zr (1)-ZSM-5 (y=0.1,04,0.5) for preparing in embodiment 1~3
The N of desulphurization denitration2Curve is varied with temperature with S selectivity.
Fig. 4 is that catalyst is simultaneously by Ce (y)-Fe/Zr (1)-ZSM-5 (y=0.1,04,0.5) for preparing in embodiment 4~6
The denitration rate of desulphurization denitration varies with temperature curve.
Fig. 5 is that catalyst is simultaneously by Ce (y)-Fe/Zr (1)-ZSM-5 (y=0.1,04,0.5) for preparing in embodiment 4~6
The desulfurization degree of desulphurization denitration varies with temperature curve.
Fig. 6 is that catalyst is simultaneously by Ce (y)-Fe/Zr (1)-ZSM-5 (y=0.1,04,0.5) for preparing in embodiment 4~6
The N of desulphurization denitration2Curve is varied with temperature with S selectivity.
Embodiment
Preferably to support the present invention, the invention will be further described with reference to the accompanying drawings and examples, but the present invention
Embodiment not limited to this.
Embodiment 1
The preparation of Cr (0.1)-Fe/Zr (1)-ZSM-5 catalyst：According to mol ratio n (Si)：n(Al+Zr)：n(TPABr)：
n(H2O)=30：1：10：2000 ratio dispensing (wherein Al/Zr mol ratio=1), sequentially adds 0.389g ZrO (NO3)2、
0.632g Al(NO3)3·9H2O, 5.430g 4-propyl bromides (TPABr), 62ml H2O, stir, add
21.26ml tetraethyl orthosilicates (TEOS), are quickly stirred until homogeneous, and 1.0mol/L NaOH solutions control mixed liquor is then added dropwise
PH value is 11, continues to stir 2h, mixed liquor then is transferred into 150ml reactors crystallization 48h at 160 DEG C.By the sample after crystallization
3h is calcined at 550 DEG C after product centrifugation, washing, drying, obtains the ZSM-5 carriers containing zirconium.
Weigh 4.00g Zr (1)-ZSM-5 carriers, 0.577g Cr (NO3)3·9H2O and 5.243g Fe (NO3)3·9H2O
And it is mixed (load capacity 20wt%), 7.2ml 2mol/L citric acid is added, stirs 1h, then in 120 DEG C of bakings
10h is to drying, and finally 450 DEG C of roasting 3h in Muffle furnace, tabletting, the particle for being ground into 40~80 mesh obtain being used for CO reducing process
The catalyst of simultaneous SO_2 and NO removal.
The catalyst of above-mentioned gained is evaluated：
The composition of simulated flue gas is used as 1000ppmNO, 800ppmSO2, 0.7%CO, N2For Balance Air, pass through quality stream
It is 1.0L/min that gauge, which controls total gas couette, 1g catalyst (WSHV=60000ml/gh) is put into quartz ampoule, mould
Intend gas and pass through catalyst, heat up from 300 DEG C to 550 DEG C, tested after each temperature spot keeps 30min.Adopt
Flue gas analyzer (Ecom, D-58640, Germany) tests NO, NO2And SO2Inlet and outlet concentration, COS test uses
Gas chromatograph (Agilent, 7820A, pillar model HP-PLOT Q, column length 30m, thermal conductivity detector (TCD)).Pass through below equation meter
Calculate NO conversion ratio, N2Selectivity, SO2Conversion ratio and S selectivity：
[NO]in、[NO]out、[SO2]in[SO2]outRespectively NO inlet concentration, NO exit concentration, SO2Import
Concentration and SO2Exit concentration, [N2O] and [COS] respectively outlet N2O and COS concentration, formula (1), (2), (3) and (4)
Respectively NO conversion ratio, N2Selectivity, SO2Conversion ratio and S simple substance selectivity.
Activity evaluation as depicted in figs. 1 and 2, in the range of 300~400 DEG C, NO and SO2Conversion ratio with temperature
Rise and gradually rise；In the range of 400~550 DEG C, NO and SO2Conversion ratio be held essentially constant.In 400 DEG C of catalyst
100% desulphurization denitration rate is can be achieved with, illustrates that the catalyst has good desulphurization denitration performance.
Embodiment 2
The preparation of Cr (0.4)-Fe/Zr (1)-ZSM-5 catalyst：According to mol ratio n (Si)：n(Al+Zr)：n(TPABr)：
n(H2O)=30：1：10：2000 ratio dispensing (wherein Al/Zr mol ratio=1), sequentially adds 0.389g ZrO (NO3)2、
0.632g Al(NO3)3·9H2O, 5.430g 4-propyl bromides (TPABr), 62ml H2O, stir, add
21.26ml tetraethyl orthosilicates (TEOS), are quickly stirred until homogeneous, and 1.0mol/L NaOH solutions control mixed liquor is then added dropwise
PH value is 11, continues to stir 2h, mixed liquor then is transferred into 150ml reactors crystallization 48h at 160 DEG C.By the sample after crystallization
3h is calcined at 550 DEG C after product centrifugation, washing, drying, obtains the ZSM-5 carriers containing zirconium.
Weigh 4.00g Zr (1)-ZSM-5 carriers, 2.358g Cr (NO3)3·9H2O and 3.571g Fe (NO3)3·9H2O
And it is mixed (load capacity 20wt%), 7.4ml 2mol/L citric acid is added, stirs 1h, then in 120 DEG C of bakings
10h is to drying, and finally 450 DEG C of roasting 3h in Muffle furnace, tabletting, the particle for being ground into 40~80 mesh obtain being used for CO reducing process
The catalyst of simultaneous SO_2 and NO removal.
The catalyst of above-mentioned gained is evaluated
The composition of simulated flue gas is used as 1000ppmNO, 800ppmSO2, 0.7%CO, N2For Balance Air, pass through quality stream
It is 1.0L/min that gauge, which controls total gas couette, 1g catalyst (WSHV=60000ml/gh) is put into quartz ampoule, mould
Intend gas and pass through catalyst, heat up from 300 DEG C to 550 DEG C, tested after each temperature spot keeps 30min.Adopt
Flue gas analyzer (Ecom, D-58640, Germany) tests NO, NO2And SO2Inlet and outlet concentration, N2O infrared spectrum analysers
(T320, API, America) tests N2O exit concentration, COS test use gas chromatograph (Agilent, 7820A, post
Subtype HP-PLOT Q, column length 30m, thermal conductivity detector (TCD)).
Activity evaluation such as Fig. 1,2 and 3 are shown, in the range of 300~350 DEG C, NO and SO2Conversion ratio and N2And S
Selectivity gradually risen with the rising of temperature；In the range of 350~500 DEG C, the activity and selectivity of the catalyst is basic
Keep constant.100% desulphurization denitration rate and 100% N are can be achieved with 350 DEG C of catalyst2With S selectivity, say
The bright catalyst possesses excellent desulphurization denitration performance.Existing reducing process simultaneous SO_2 and NO removal technology is contrasted, the present invention is implemented
Desulfurization nitre effect while the catalyst reported in example 2 not only shows fabulous, and can significantly lower the use of catalyst
Temperature.For example, Chinese invention patent application CN106179345A proposes a kind of ferrum-based catalyst of the support type of vulcanization, this is urged
Agent could realize 100%NO conversion ratios and 91% SO more than 400 DEG C2Conversion ratio, and this method does not account for N2And S
Selective problems.Chinese invention patent application CN102989466A reports catalyst has more than 90% in 350 DEG C and the above
Desulphurization denitration rate, but the air speed used only have 4500h-1, also without consideration N2With S selective problems.
Embodiment 3
The preparation of Cr (0.5)-Fe/Zr (1)-ZSM-5 catalyst：According to mol ratio n (Si)：n(Al+Zr)：n(TPABr)：
n(H2O)=30：1：10：2000 ratio dispensing (wherein Al/Zr mol ratio=1), sequentially adds 0.389g ZrO (NO3)2、
0.632g Al(NO3)3·9H2O, 5.430g 4-propyl bromides (TPABr), 62ml H2O, stir, add
21.26ml tetraethyl orthosilicates (TEOS), are quickly stirred until homogeneous, and 1.0mol/L NaOH solutions control mixed liquor is then added dropwise
PH value is 11, continues to stir 2h, mixed liquor then is transferred into 150ml reactors crystallization 48h at 160 DEG C.By the sample after crystallization
3h is calcined at 550 DEG C after product centrifugation, washing, drying, obtains the ZSM-5 carriers containing zirconium.
Weigh 4.00g Zr (1)-ZSM-5 carriers, 2.968g Cr (NO3)3·9H2O and 2.998g Fe (NO3)3·9H2O
And it is mixed (load capacity 20wt%), 7.5ml 2mol/L citric acid is added, stirs 1h, then in 120 DEG C of bakings
10h is to drying, and finally 450 DEG C of roasting 3h in Muffle furnace, tabletting, the particle for being ground into 40~80 mesh obtain being used for CO reducing process
The catalyst of simultaneous SO_2 and NO removal.
The catalyst of above-mentioned gained is evaluated
The composition of simulated flue gas is used as 1000ppmNO, 800ppmSO2, 0.7%CO, N2For Balance Air, pass through quality stream
It is 1.0L/min that gauge, which controls total gas couette, 1g catalyst (WSHV=60000ml/gh) is put into quartz ampoule, mould
Intend gas and pass through catalyst, heat up from 300 DEG C to 550 DEG C, tested after each temperature spot keeps 30min.Adopt
Flue gas analyzer (Ecom, D-58640, Germany) tests NO, NO2And SO2Inlet and outlet concentration, N2O infrared spectrum analysers
(T320, API, America) tests N2O exit concentration, COS test use gas chromatograph (Agilent, 7820A, post
Subtype HP-PLOT Q, column length 30m, thermal conductivity detector (TCD)).
For Activity evaluation catalyst as illustrated in figs. 1 and 2 at 350 DEG C, NO conversion ratios are 79%, SO2Conversion ratio is less than
20%.But realize 100%NO and SO in 400 DEG C and the above catalyst2Conversion ratio, it is good to illustrate that the catalyst has
Desulphurization denitration activity.
Embodiment 4
The preparation of Ce (0.1)-Fe/Zr (1)-ZSM-5 catalyst：According to mol ratio n (Si)：n(Al+Zr)：n(TPABr)：
n(H2O)=30：1：10：2000 ratio dispensing (wherein Al/Zr mol ratio=1), sequentially adds 0.389g ZrO (NO3)2、
0.632g Al(NO3)3·9H2O, 5.430g 4-propyl bromides (TPABr), 62ml H2O, stir, add
21.26ml tetraethyl orthosilicates (TEOS), are quickly stirred until homogeneous, and 1.0mol/L NaOH solutions control mixed liquor is then added dropwise
PH value is 11, continues to stir 2h, mixed liquor then is transferred into 150ml reactors crystallization 48h at 160 DEG C.By the sample after crystallization
3h is calcined at 550 DEG C after product centrifugation, washing, drying, obtains the ZSM-5 carriers containing zirconium.
Weigh 4.00g Zr (1)-ZSM-5 carriers, 0.542g Ce (NO3)3·6H2O and 4.527g Fe (NO3)3·9H2O
And it is mixed (load capacity 20wt%), 6.2ml 2mol/L citric acid is added, stirs 1h, then in 120 DEG C of bakings
10h is to drying, and finally 450 DEG C of roasting 3h in Muffle furnace, tabletting, the particle for being ground into 40~80 mesh obtain being used for CO reducing process
The catalyst of simultaneous SO_2 and NO removal.
The catalyst of above-mentioned gained is evaluated
The composition of simulated flue gas is used as 1000ppmNO, 800ppmSO2, 0.7%CO, N2For Balance Air, pass through quality stream
It is 1.0L/min that gauge, which controls total gas couette, and 1.0g catalyst (WSHV=60000ml/gh) is put into quartz ampoule,
Simulation gas passes through catalyst, heats up from 300 DEG C to 550 DEG C, is tested after each temperature spot keeps 30min.
Flue gas analyzer (Ecom, D-58640, Germany) test NO, NO of use2And SO2Inlet and outlet concentration, N2O infrared analysis
Instrument (T320, API, America) tests N2O exit concentration, COS test using gas chromatograph (Agilent, 7820A,
Pillar model HP-PLOT Q, column length 30m, thermal conductivity detector (TCD)).
Activity evaluation such as Figure 4 and 5 are shown, in the range of 300~375 DEG C, NO and SO2Conversion ratio with the upper of temperature
Rise and gradually rise；In the range of 375~500 DEG C, NO and SO2Conversion ratio be held essentially constant.In 375 DEG C of catalyst just
More than 95% desulphurization denitration rate can be realized, illustrates that the catalyst has good desulphurization denitration performance.
Embodiment 5
The preparation of Ce (0.4)-Fe/Zr (1)-ZSM-5 catalyst：According to mol ratio n (Si)：n(Al+Zr)：n(TPABr)：
n(H2O)=30：1：10：2000 ratio dispensing (wherein Al/Zr mol ratio=1), sequentially adds 0.389g ZrO (NO3)2、
0.632g Al(NO3)3·9H2O, 5.430g 4-propyl bromides (TPABr), 62ml H2O, stir, add
21.26ml tetraethyl orthosilicates (TEOS), are quickly stirred until homogeneous, and 1.0mol/L NaOH solutions control mixed liquor is then added dropwise
PH value is 11, continues to stir 2h, mixed liquor then is transferred into 150ml reactors crystallization 48h at 160 DEG C.By the sample after crystallization
3h is calcined at 550 DEG C after product centrifugation, washing, drying, obtains the ZSM-5 carriers containing zirconium.
Weigh 4.00g Zr (1)-ZSM-5 carriers, 1.552g Ce (NO3)3·6H2O and 2.165g Fe (NO3)3·9H2O
And it is mixed (load capacity 20wt%), 4.5ml 2mol/L citric acid is added, stirs 1h, then in 120 DEG C of bakings
10h is to drying, and finally 450 DEG C of roasting 3h in Muffle furnace, tabletting, the particle for being ground into 40~80 mesh obtain being used for CO reducing process
The catalyst of simultaneous SO_2 and NO removal.
The catalyst of above-mentioned gained is evaluated
The composition of simulated flue gas is used as 1000ppmNO, 800ppmSO2, 0.7%CO, N2For Balance Air, pass through quality stream
It is 1.0L/min that gauge, which controls total gas couette, and 1.0g catalyst (WSHV=60000ml/gh) is put into quartz ampoule,
Simulation gas passes through catalyst, heats up from 300 DEG C to 550 DEG C, is tested after each temperature spot keeps 30min.
Flue gas analyzer (Ecom, D-58640, Germany) test NO, NO of use2And SO2Inlet and outlet concentration, N2O infrared analysis
Instrument (T320, API, America) tests N2O exit concentration, COS test using gas chromatograph (Agilent, 7820A,
Pillar model HP-PLOT Q, column length 30m, thermal conductivity detector (TCD)).
Activity evaluation such as Fig. 4,5 and 6 are shown, in the range of 300~350 DEG C, NO and SO2Conversion ratio and N2And S
Selectivity gradually risen with the rising of temperature；In the range of 350~500 DEG C, the activity and selectivity of the catalyst is basic
Keep constant.100% desulphurization denitration rate and 100%N are can be achieved with 350 DEG C of catalyst2With S selectivity, explanation
The catalyst possesses excellent desulphurization denitration performance.Contrast existing reducing process simultaneous SO_2 and NO removal technology, the embodiment of the present invention 5
Desulfurization nitre effect while the catalyst of middle report does not only have fabulous, and can significantly lower the temperature in use of catalyst.Example
Such as, Chinese invention patent application CN106179345A proposes a kind of ferrum-based catalyst of the support type of vulcanization, and the catalyst exists
More than 400 DEG C could realize 100%NO conversion ratios and 91% SO2Conversion ratio, and this method does not account for N2With S selection
Sex chromosome mosaicism.Chinese invention patent application CN102989466A, which reports catalyst, more than 90% desulfurization in 350 DEG C and the above
Denitration rate, but the air speed used only has 4500h-1, also without consideration N2With S selective problems.
Embodiment 6
The preparation of Ce (0.5)-Fe/Zr (1)-ZSM-5 catalyst：According to mol ratio n (Si)：n(Al+Zr)：n(TPABr)：
n(H2O)=30：1：10：2000 ratio dispensing (wherein Al/Zr mol ratio=1), sequentially adds 0.389g ZrO (NO3)2、
0.632g Al(NO3)3·9H2O, 5.430g 4-propyl bromides (TPABr), 62ml H2O, stir, add
21.26ml tetraethyl orthosilicates (TEOS), are quickly stirred until homogeneous, and 1.0mol/L NaOH solutions control mixed liquor is then added dropwise
PH value is 11, continues to stir 2h, mixed liquor then is transferred into 150ml reactors crystallization 48h at 160 DEG C.By the sample after crystallization
3h is calcined at 550 DEG C after product centrifugation, washing, drying, obtains the ZSM-5 carriers containing zirconium.
Weigh 4.00g Zr (1)-ZSM-5 carriers, 1.773g Ce (NO3)3·6H2O and 1.650g Fe (NO3)3·9H2O
And it is mixed (load capacity 20wt%), 4.1ml 2mol/L citric acid is added, stirs 1h, then in 120 DEG C of bakings
10h is to drying, and finally 450 DEG C of roasting 3h in Muffle furnace, tabletting, the particle for being ground into 40~80 mesh obtain being used for CO reducing process
The catalyst of simultaneous SO_2 and NO removal.
The catalyst of above-mentioned gained is evaluated
The composition of simulated flue gas is used as 1000ppmNO, 800ppmSO2, 0.7%CO, N2For Balance Air, pass through quality stream
It is 1.0L/min that gauge, which controls total gas couette, and 1.0g catalyst (WSHV=60000ml/gh) is put into quartz ampoule,
Simulation gas passes through catalyst, heats up from 300 DEG C to 550 DEG C, is tested after each temperature spot keeps 30min.
Flue gas analyzer (Ecom, D-58640, Germany) test NO, NO of use2And SO2Inlet and outlet concentration, N2O infrared analysis
Instrument (T320, API, America) tests N2O exit concentration, COS test using gas chromatograph (Agilent, 7820A,
Pillar model HP-PLOT Q, column length 30m, thermal conductivity detector (TCD)).
Activity evaluation such as Figure 4 and 5 are shown, in the range of 300~375 DEG C, NO and SO2Conversion ratio with the upper of temperature
Rise and gradually rise；In the range of 375~500 DEG C, NO and SO2Conversion ratio be held essentially constant.In 375 DEG C of catalyst just
More than 95% desulphurization denitration rate can be realized, illustrates that the catalyst has excellent desulphurization denitration performance.
The catalyst that the present invention reports possesses good water-resistance, antioxidant.The feature is by following examples 7 and implements
Example 8 is verified.
Embodiment 7
The test of Cr (0.4)-Fe/Zr (1)-ZSM-5 catalyst water-resistance：Often containing substantial amounts of in the flue gas of reality
Vapor, therefore the water repelling property of catalyst is investigated, there is very important practical significance.Specific embodiment, to reaction gas
The water repelling property of the middle vapor investigation catalyst for adding 6%, when temperature is less than 450 DEG C, vapor has brighter to catalyst
Aobvious inhibitory action；When temperature rises to 450 DEG C and the above, the inhibitory action of vapor is wholly absent, and illustrates that the catalyst has
Preferable water-resistance.
Embodiment 8
The test of Cr (0.4)-Fe/Zr (1)-ZSM-5 catalyst antioxidants：Often containing a certain amount of in the flue gas of reality
Oxygen, the same antioxygen property for investigating catalyst, for the actual using significant of catalyst.Specific embodiment party
Case, 0.2% oxygen (amount of total oxide is substantially equal to the amount of total reducing agent) is added into reaction gas and investigates catalyst
Antioxygen property, when temperature is less than 600 DEG C, O2There is obvious inhibitory action to catalyst；When temperature rise to 600 DEG C and more than
When, NO conversion ratios return to 100%, SO2Conversion ratio returns to more than 81%, illustrates that the catalyst has preferable antioxygen property,
Possess the potentiality of practical application.
It should be noted that embodiments of the present invention and be not restricted to the described embodiments, it is other it is any without departing from
The Spirit Essence of the present invention with made under principle change, modification, replacement, combine, simplification, should be equivalent substitute mode,
It is included in protection scope of the present invention etc.
Claims (8)
1. the load-type iron-based catalyst of sulfur dioxide in flue gas and nitrogen oxides is reduced simultaneously, it is characterised in that the load
Type ferrum-based catalyst is made up of ferro element, transition metal M and carrier containing zirconium, and the composition formula of described catalyst is M
(y)-Fe/Zr (a)-ZSM-5, M are one or both of transition metal Cr and Ce, M element and Fe element quality sums
The percentage for accounting for carrier quality is 5~30%；Y is M/ (M+Fe) mol ratio, 0.1<y<0.9；Zr (a)-ZSM-5 is the load of zirconium
Body, wherein a are Zr/Al mol ratios, 0.5<a<5, Si/ (Al+Zr) mol ratio of carrier is 30~60.
2. the preparation of the load-type iron-based catalyst of sulfur dioxide in flue gas and nitrogen oxides is reduced while described in claim 1
Method, it is characterised in that comprise the following steps：
1) preparation of the carrier of zirconium-containing ZSM-5-5：Zirconium zeolite molecular sieve is synthesized using hydrothermal crystallization method, tetraethyl orthosilicate (TEOS) is silicon
Source, using zirconyl nitrate as zirconium source, aluminum nitrate is silicon source, and 4-propyl bromide (TPABr) is template, according to mol ratio n (Si)：
n(Al+Zr)：n(TPABr)：n(H2O)=30~60：1：8~12：2000~6000, it is 10~12 with NaOH regulation pH value, stirs
Mix uniformly, then 24~72h of crystallization at a temperature of 140~170 DEG C, after centrifugation, washing, drying at a temperature of 400~600 DEG C
3~6h of roasting obtains the carrier of zirconium-containing ZSM-5-5.
2) preparation of catalyst：Using citric acid method, the carrier of zirconium-containing ZSM-5-5, ferric nitrate, transition gold are added into citric acid solution
Genus nitrobacter, 1~4h is stirred at room temperature；
3) metal salt obtained by step 2) is dried at 50~120 DEG C, 3~6h is then calcined at 400~600 DEG C；
4) metal composite oxide grinding, tabletting, the sieving prepared step 3), obtains the catalyst of simultaneous SO_2 and NO removal.
3. preparation method according to claim 2, it is characterised in that the concentration of the citric acid solution described in step 1) is
2~3mol/L, the mole of total metal of the amount of the citric acid of addition with adding are equal.
4. preparation method according to claim 2, it is characterised in that the sieve diameter of the sieving is 40~80 mesh.
5. preparation method according to claim 2, it is characterised in that the time to stir is 1~4h.
6. preparation method according to claim 2, it is characterised in that the time of the step 3) drying is 12-15h.
7. the application of the load-type iron-based catalyst of sulfur dioxide in flue gas and nitrogen oxides is reduced described in claim 1 simultaneously,
Characterized in that, the air speed that flue gas passes through catalyst is 20000~80000ml/gh.
8. load-type iron-based catalyst that is according to claim 7 while reducing sulfur dioxide in flue gas and nitrogen oxides
Using, it is characterised in that the NO concentration of the flue gas is 500~1500mg/m3, SO2Concentration is 1000~2500mg/m3, temperature
For 300~550 DEG C.
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Application publication date: 20171205 |