CN109331835A - A kind of ammonia-selective catalyst reduction of nitrogen oxides catalyst and its preparation method and application - Google Patents
A kind of ammonia-selective catalyst reduction of nitrogen oxides catalyst and its preparation method and application Download PDFInfo
- Publication number
- CN109331835A CN109331835A CN201811481221.XA CN201811481221A CN109331835A CN 109331835 A CN109331835 A CN 109331835A CN 201811481221 A CN201811481221 A CN 201811481221A CN 109331835 A CN109331835 A CN 109331835A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- composite oxide
- metal composite
- ammonia
- nitrogen oxides
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/888—Tungsten
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation 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
- B01D53/34—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
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
Abstract
A kind of ammonia-selective catalyst reduction of nitrogen oxides catalyst and its preparation method and application, it is related to a kind of catalyst and its preparation method and application.The invention aims to solve existing copper ferrotitanium system's oxide catalyst in anti-H2O poisoning capability is weaker, the poor problem of high-temperature selective.A kind of ammonia-selective catalyst reduction of nitrogen oxides catalyst is metal composite oxide, and metallic element is Cu, Fe, W and Ti in the metal composite oxide.Preparation method: one, it is mixed to get mixing salt solution；Two, solution containing Ti is prepared；Three, catalyst precursor is prepared；Four, high-temperature process obtains metal composite oxide, as ammonia-selective catalyst reduction of nitrogen oxides catalyst.Ammonia-selective catalyst reduction of nitrogen oxides catalyst is used for denitration.Advantage: excellent NO conversion ratio and N are shown in broad temperature range2Selectivity；And anti-H under the conditions of 240 DEG C2O and SO2Poisoning capability is excellent.
Description
Technical field
The present invention relates to a kind of catalyst and its preparation method and application.
Background technique
Nitrogen oxides (NOx) be severe air pollution one of major pollutants, seriously endanger ecological environment and human body
Health.NH at present3- SCR (ammonia-selective catalytic reduction) technology has become the main means of stationary source denitration, is effectively controlling
Manage NOxPollution aspect played an important role.Catalyst is then NH3The key of SCR denitration technology.The catalysis of traditional commerce
Agent is mostly V-Ti series catalysts (V2O5/TiO2、V2O5-WO3/TiO2、V2O5-WO3/TiO2Deng), it is only applicable in 300-400 DEG C
The denitration reaction in high temperature section, warm area is relatively narrow to be difficult to directly utilize on middle and small burn coal boiler and Industrial Stoves.The catalysis of vanadium base
Agent is vulnerable to SO2It is poisoned with dust, and itself has bio-toxicity, endangers ecological environment and human health.Therefore research is in medium temperature
Non- vanadium based denitration catalyst of the section with wider operation temperature window is current with the denitration demand for adapting to more Industrial Boilers
Research direction has practical application value.Copper and iron titanium (CuFeTi) is that oxide catalyst is environmental-friendly, in NH3- SCR reaction
In show excellent low temperature and medium temperature denitration activity, however, this kind of catalyst is in anti-H2O poisoning capability is weaker, high temperature selection
Property is poor, limits its application.
Summary of the invention
The invention aims to solve existing copper ferrotitanium system's oxide catalyst in anti-H2O poisoning capability is weaker, high temperature
Catalytic activity and N2The poor problem of selectivity, and provide a kind of ammonia-selective catalyst reduction of nitrogen oxides catalyst and its
Preparation method and application.
A kind of ammonia-selective catalyst reduction of nitrogen oxides catalyst, it is metal composite oxide, the composition metal
Metallic element is Cu, Fe, W and Ti in oxide, and the mass ratio of the material of Cu, Fe, W and Ti are 0.02:0.2:x:1, and wherein x is
0.01~0.03.
A kind of preparation method of ammonia-selective catalyst reduction of nitrogen oxides catalyst, is specifically realized by the following steps
:
One, it mixes: mantoquita, molysite and tungsten salt being dissolved in distilled water-glacial acetic acid mixed liquor, it is molten to obtain salt-mixture
Liquid；In the mixing salt solution concentration of Fe be 0.3mol/L~0.4mol/L, and in mixing salt solution Cu, Fe and W substance
Amount ratio be 0.02:0.2:x, wherein x be 0.01~0.03；Distilled water and glacial acetic acid in the distilled water-glacial acetic acid mixed liquor
Volume ratio be (2~4): 10；
Two, it prepares solution containing Ti: butyl titanate being dissolved in ethyl alcohol, the alcoholic solution of butyl titanate is obtained；It is described
The concentration of butyl titanate is 1.0mol/L~2.0mol/L in the alcoholic solution of butyl titanate；
Three, it prepares catalyst precursor: the alcoholic solution of mixing salt solution and butyl titanate being mixed, 1h is first stirred to react
~6h, then at room temperature stand 4 days~6 days, be finally placed in baking oven, temperature be 90 DEG C~140 DEG C at dry 10h~
18h obtains catalyst precursor；The mass ratio of the material of Cu, Fe, W and Ti are 0.02:0.2:x:1 in the catalyst precursor,
Wherein x is 0.01~0.03；
Four, high-temperature process: being first milled into powder for catalyst precursor, is subsequently placed in Muffle furnace, with 5 DEG C/min~15
DEG C/heating rate of min is warming up to 400 DEG C~600 DEG C, and is 400 DEG C~600 DEG C processing 3h~6h in temperature, it is cooled to room
Temperature, ground, tabletting and granulation, obtain metal composite oxide, as ammonia-selective catalyst reduction of nitrogen oxides catalysis
Agent.
A kind of application of ammonia-selective catalyst reduction of nitrogen oxides catalyst, ammonia-selective catalytic reduction nitrogen oxidation
Object catalyst is used for denitration.
The invention has the advantages that
One, catalyst Cu prepared by the present invention0.02Fe0.2WxTi (x=0.01~0.03) metal composite oxide (ammonia-
Selective catalyst reduction of nitrogen oxides catalyst) it is at low cost, environmental-friendly, synthetic method is simple and stable structure；
Two, catalyst Cu0.02Fe0.2Wx(ammonia-selective catalysis is also for Ti (x=0.01~0.03) metal composite oxide
Former nitrogen oxide catalyst) excellent NO conversion ratio and N are shown in broad temperature range2Selectivity；Wherein catalyst
Cu0.02Fe0.2W0.02Ti is in 200~460 DEG C of temperature ranges, the NO conversion ratio and N greater than 95% that show 100%2Selection
Property, and anti-H under the conditions of 240 DEG C2O and SO2Poisoning capability is excellent, and NO conversion ratio is still 100%.The reason is that suitable copper, iron
There is interaction between tungsten, change the redox property of catalyst, the presence of tungsten improves the thermal stability of catalyst
And acidity, these factors are conducive to the NH of high temperature range3N at-SCR reaction, raising high temperature2Selective and anti-H2O and
SO2Poisoning capability.According to NH3- TPD and in-situ ft-ir confirm catalyst Cu0.02Fe0.2W0.02Ti metal composite oxide
(ammonia-selective catalyst reduction of nitrogen oxides catalyst) acidity with higher, and there are acidic site abundant, H on surface2-
TPR confirms there is interaction between copper, iron and tungsten；So catalyst Cu prepared by the present invention0.02Fe0.2W0.02Ti composition metal
Oxide (ammonia-selective catalyst reduction of nitrogen oxides catalyst) has high urge for (200~460 DEG C) under the conditions of high temperature
Change activity, and can be applied under the conditions of space velocity range is biggish, sulfur resistive water repelling property is excellent, the with good stability and longevity
Life.
Detailed description of the invention
Fig. 1 is NO conversion ratio-temperature profile, and ★ indicates catalyst Cu in figure0.02Fe0.2Ti metal composite oxide
NO conversion ratio-temperature curve, ■ indicates catalyst Cu in figure0.02Fe0.2W0.01NO conversion ratio-temperature of Ti metal composite oxide
Curve, in figure ● indicate catalyst Cu0.02Fe0.2W0.02NO conversion ratio-temperature curve of Ti metal composite oxide, in figure ▲ table
Show catalyst Cu0.02Fe0.2W0.03NO conversion ratio-temperature curve of Ti metal composite oxide；
Fig. 2 is N2Selectivity-temperature profile, ★ indicates catalyst Cu in figure0.02Fe0.2The N of Ti metal composite oxide2
Selectivity-temperature curve, ■ indicates catalyst Cu in figure0.02Fe0.2W0.01The N of Ti metal composite oxide2Selectivity-temperature is bent
Line, in figure ● indicate catalyst Cu0.02Fe0.2W0.02The N of Ti metal composite oxide2Selectivity-temperature curve, in figure ▲ indicate
Catalyst Cu0.02Fe0.2W0.03The N of Ti metal composite oxide2Selectivity-temperature curve；
Fig. 3 is NO conversion ratio-temperature profile, in figure ● indicates GHSV 40000h-1NO conversion ratio-temperature curve, figure
Middle ■ indicates GHSV 80000h-1NO conversion ratio-temperature curve, in figure ◆ indicate GHSV 100000h-1NO conversion ratio-temperature
It writes music line；
Fig. 4 is NO conversion-time plot figure；
Fig. 5 is NO conversion ratio-temperature profile；.
Fig. 6 is NO2Concentration-temperature curve graph, ★ indicates catalyst Cu in figure0.02Fe0.2The NO of Ti metal composite oxide2
Concentration-temperature curve, ■ indicates catalyst Cu in figure0.02Fe0.2W0.01The NO of Ti metal composite oxide2Concentration-temperature curve,
In figure ● indicate catalyst Cu0.02Fe0.2W0.02The NO of Ti metal composite oxide2Concentration-temperature curve, in figure ▲ indicate catalysis
Agent Cu0.02Fe0.2W0.03The NO of Ti metal composite oxide2Concentration-temperature curve；
Fig. 7 is NH3Concentration-temperature curve graph, ★ indicates catalyst Cu in figure0.02Fe0.2The NH of Ti metal composite oxide3
Concentration-temperature curve, ■ indicates catalyst Cu in figure0.02Fe0.2W0.01The NH of Ti metal composite oxide3Concentration-temperature curve,
In figure ● indicate catalyst Cu0.02Fe0.2W0.02The NH of Ti metal composite oxide3Concentration-temperature curve, in figure ▲ indicate catalysis
Agent Cu0.02Fe0.2W0.03The NH of Ti metal composite oxide3Concentration-temperature curve；
Fig. 8 is H2- TPR spectrogram, a indicates catalyst Cu in figure0.02Fe0.2The H of Ti metal composite oxide2- TPR spectrogram, b
Indicate catalyst Cu0.02Fe0.2W0.01The H of Ti metal composite oxide2- TPR spectrogram, c indicate catalyst Cu0.02Fe0.2W0.02Ti
The H of metal composite oxide2- TPR spectrogram, d indicate catalyst Cu0.02Fe0.2W0.03The H of Ti metal composite oxide2- TPR spectrum
Figure；
Fig. 9 is H2- TPR spectrogram, a indicates catalyst Cu in figure0.1The H of Ti metal composite oxide2- TPR spectrogram, b are indicated
Catalyst Fe0.1The H of Ti metal composite oxide2- TPR spectrogram, c indicate catalyst Cu0.02Fe0.2Ti metal composite oxide
H2- TPR spectrogram, d indicate catalyst Cu0.02Fe0.2W0.02The H of Ti metal composite oxide2- TPR spectrogram, e indicate catalyst
Cu0.02W0.02The H of Ti metal composite oxide2- TPR spectrogram, f indicate catalyst Fe0.2W0.02The H of Ti metal composite oxide2-
TPR spectrogram；
Figure 10 is NH3- TPD map, a indicates catalyst Cu in figure0.02Fe0.2The NH of Ti metal composite oxide3- TPD figure
Spectrum, b indicate catalyst Cu0.02Fe0.2W0.01The NH of Ti metal composite oxide3- TPD map, c indicate catalyst
Cu0.02Fe0.2W0.02The NH of Ti metal composite oxide3- TPD map, d indicate catalyst Cu0.02Fe0.2W0.03Ti composition metal oxygen
The NH of compound3- TPD map.
Specific embodiment
Specific embodiment 1: present embodiment is a kind of ammonia-selective catalyst reduction of nitrogen oxides catalyst, it is
Metal composite oxide, metallic element is Cu, Fe, W and Ti in the metal composite oxide, and the substance of Cu, Fe, W and Ti
Amount ratio be 0.02:0.2:x:1, wherein x be 0.01~0.03.
Specific embodiment 2: present embodiment is a kind of system of ammonia-selective catalyst reduction of nitrogen oxides catalyst
Preparation Method is specifically realized by the following steps:
One, it mixes: mantoquita, molysite and tungsten salt being dissolved in distilled water-glacial acetic acid mixed liquor, it is molten to obtain salt-mixture
Liquid；In the mixing salt solution concentration of Fe be 0.3mol/L~0.4mol/L, and in mixing salt solution Cu, Fe and W substance
Amount ratio be 0.02:0.2:x, wherein x be 0.01~0.03；Distilled water and glacial acetic acid in the distilled water-glacial acetic acid mixed liquor
Volume ratio be (2~4): 10；
Two, it prepares solution containing Ti: butyl titanate being dissolved in ethyl alcohol, the alcoholic solution of butyl titanate is obtained；It is described
The concentration of butyl titanate is 1.0mol/L~2.0mol/L in the alcoholic solution of butyl titanate；
Three, it prepares catalyst precursor: the alcoholic solution of mixing salt solution and butyl titanate being mixed, 1h is first stirred to react
~6h, then at room temperature stand 4 days~6 days, be finally placed in baking oven, temperature be 90 DEG C~140 DEG C at dry 10h~
18h obtains catalyst precursor；The mass ratio of the material of Cu, Fe, W and Ti are 0.02:0.2:x:1 in the catalyst precursor,
Wherein x is 0.01~0.03；
Four, high-temperature process: being first milled into powder for catalyst precursor, is subsequently placed in Muffle furnace, with 5 DEG C/min~15
DEG C/heating rate of min is warming up to 400 DEG C~600 DEG C, and is 400 DEG C~600 DEG C processing 3h~6h in temperature, it is cooled to room
Temperature, ground, tabletting and granulation, obtain metal composite oxide, as ammonia-selective catalyst reduction of nitrogen oxides catalysis
Agent.
Specific embodiment 3: the difference of present embodiment and specific embodiment two is: copper described in step 1
Salt is copper nitrate.Other are identical with embodiment two.
Specific embodiment 4: one of present embodiment and specific embodiment two or three difference are: institute in step 1
The molysite stated is ferric nitrate.Other are identical as specific embodiment two or three.
Specific embodiment 5: one of present embodiment and specific embodiment two to four difference are: institute in step 1
The tungsten salt stated is ammonium metatungstate.Other are identical as specific embodiment two to four.
Specific embodiment 6: present embodiment is a kind of answering for ammonia-selective catalyst reduction of nitrogen oxides catalyst
With ammonia-selective catalyst reduction of nitrogen oxides catalyst is used for denitration.
Use ammonia-selective catalyst reduction of nitrogen oxides catalyst in NO concentration for 600ppm~1200ppm, NH3It is dense
Degree is 500ppm~1300ppm, O2Volumetric concentration is 2%~6%, N2Do Balance Air, air speed 30000h-1~120000h-1's
Under the conditions of denitration, wherein ammonia-selective catalyst reduction of nitrogen oxides catalyst dosage be 0.2g~0.5g.
Using following verification experimental verifications effect of the present invention
A kind of embodiment 1: preparation method of ammonia-selective catalyst reduction of nitrogen oxides catalyst, it is characterised in that it
It is completed by the following steps:
One, it mixes: mantoquita, molysite and tungsten salt being dissolved in distilled water-glacial acetic acid mixed liquor, it is molten to obtain salt-mixture
Liquid；The concentration of Fe is 0.31mol/L in the mixing salt solution, and the mass ratio of the material of Cu, Fe and W are in mixing salt solution
0.02:0.2:0.01；The distilled water-glacial acetic acid mixed liquor is mixed by 15mL distilled water and 50mL glacial acetic acid；
Two, it prepares solution containing Ti: butyl titanate being dissolved in ethyl alcohol, the alcoholic solution of butyl titanate is obtained；It is described
The concentration of butyl titanate is 1.2mol/L in the alcoholic solution of butyl titanate；
Three, it prepares catalyst precursor: the alcoholic solution of mixing salt solution and butyl titanate being mixed, is first stirred to react
Then 5h stands 5 days at room temperature, is finally placed in baking oven, dry 14h at being 110 DEG C in temperature, obtain complex catalyst precursor
Body；The mass ratio of the material of Cu, Fe, W and Ti are 0.02:0.2:0.01:1 in the catalyst precursor,
Four, high-temperature process: being first milled into powder for catalyst precursor, is subsequently placed in Muffle furnace, with 10 DEG C/min's
Heating rate is warming up to 500 DEG C, and is 500 DEG C of processing 4h in temperature, is cooled to room temperature, ground, tabletting and granulation are urged
Agent Cu0.02Fe0.2W0.01Ti metal composite oxide, as ammonia-selective catalyst reduction of nitrogen oxides catalyst.
A kind of embodiment 2: preparation method of ammonia-selective catalyst reduction of nitrogen oxides catalyst, it is characterised in that it
It is completed by the following steps:
One, it mixes: mantoquita, molysite and tungsten salt being dissolved in distilled water-glacial acetic acid mixed liquor, it is molten to obtain salt-mixture
Liquid；The concentration of Fe is 0.31mol/L in the mixing salt solution, and the mass ratio of the material of Cu, Fe and W are in mixing salt solution
0.02:0.2:0.02；The distilled water-glacial acetic acid mixed liquor is mixed by 15mL distilled water and 50mL glacial acetic acid；
Two, it prepares solution containing Ti: butyl titanate being dissolved in ethyl alcohol, the alcoholic solution of butyl titanate is obtained；It is described
The concentration of butyl titanate is 1.2mol/L in the alcoholic solution of butyl titanate；
Three, it prepares catalyst precursor: the alcoholic solution of mixing salt solution and butyl titanate being mixed, is first stirred to react
Then 5h stands 5 days at room temperature, is finally placed in baking oven, dry 14h at being 110 DEG C in temperature, obtain complex catalyst precursor
Body；The mass ratio of the material of Cu, Fe, W and Ti are 0.02:0.2:0.02:1 in the catalyst precursor,
Four, high-temperature process: being first milled into powder for catalyst precursor, is subsequently placed in Muffle furnace, with 10 DEG C/min's
Heating rate is warming up to 500 DEG C, and is 500 DEG C of processing 4h in temperature, is cooled to room temperature, ground, tabletting and granulation are urged
Agent Cu0.02Fe0.2W0.02Ti metal composite oxide, as ammonia-selective catalyst reduction of nitrogen oxides catalyst.
A kind of embodiment 3: preparation method of ammonia-selective catalyst reduction of nitrogen oxides catalyst, it is characterised in that it
It is completed by the following steps:
One, it mixes: mantoquita, molysite and tungsten salt being dissolved in distilled water-glacial acetic acid mixed liquor, it is molten to obtain salt-mixture
Liquid；The concentration of Fe is 0.31mol/L in the mixing salt solution, and the mass ratio of the material of Cu, Fe and W are in mixing salt solution
0.02:0.2:0.03；The distilled water-glacial acetic acid mixed liquor is mixed by 15mL distilled water and 50mL glacial acetic acid；
Two, it prepares solution containing Ti: butyl titanate being dissolved in ethyl alcohol, the alcoholic solution of butyl titanate is obtained；It is described
The concentration of butyl titanate is 1.2mol/L in the alcoholic solution of butyl titanate；
Three, it prepares catalyst precursor: the alcoholic solution of mixing salt solution and butyl titanate being mixed, is first stirred to react
Then 5h stands 5 days at room temperature, is finally placed in baking oven, dry 14h at being 110 DEG C in temperature, obtain complex catalyst precursor
Body；The mass ratio of the material of Cu, Fe, W and Ti are 0.02:0.2:0.03:1 in the catalyst precursor,
Four, high-temperature process: being first milled into powder for catalyst precursor, is subsequently placed in Muffle furnace, with 10 DEG C/min's
Heating rate is warming up to 500 DEG C, and is 500 DEG C of processing 4h in temperature, is cooled to room temperature, ground, tabletting and granulation are urged
Agent Cu0.02Fe0.2W0.03Ti metal composite oxide, as ammonia-selective catalyst reduction of nitrogen oxides catalyst.
Different catalysts are to detect within the scope of 100~460 DEG C to NO conversion ratio in temperature:
0.35g catalyst Cu is respectively adopted0.02Fe0.2Ti metal composite oxide (Cu0.02Fe0.2Ti), 0.35g catalyst
Cu0.02Fe0.2W0.01Ti metal composite oxide (Cu0.02Fe0.2W0.01Ti), 0.35g catalyst Cu0.02Fe0.2W0.02The compound gold of Ti
Belong to oxide (Cu0.02Fe0.2W0.02) and 0.35g catalyst Cu Ti0.02Fe0.2W0.03Ti metal composite oxide
(Cu0.02Fe0.2W0.03It Ti), is 1000ppm, NH in NO concentration3Concentration is 1000ppm, O2Volumetric concentration is 3%, N2It balances
Gas, air speed 40000h-1Under conditions of denitration, denitration temperature is followed successively by 100 DEG C, 130 DEG C, 160 DEG C, 200 DEG C, 240 DEG C, 280
DEG C, 310 DEG C, 350 DEG C, 400 DEG C, 430 DEG C, 450 DEG C and 460 DEG C, testing result is as shown in table 1 and Fig. 1.
Table 1
Fig. 1 is NO conversion ratio-temperature profile, and ★ indicates catalyst Cu in figure0.02Fe0.2Ti metal composite oxide
NO conversion ratio-temperature curve, ■ indicates catalyst Cu in figure0.02Fe0.2W0.01NO conversion ratio-temperature of Ti metal composite oxide
Curve, in figure ● indicate catalyst Cu0.02Fe0.2W0.02NO conversion ratio-temperature curve of Ti metal composite oxide, in figure ▲ table
Show catalyst Cu0.02Fe0.2W0.03NO conversion ratio-temperature curve of Ti metal composite oxide illustrates to be catalyzed by table 1 and Fig. 1
Agent Cu0.02Fe0.2After introducing tungsten in Ti, high temperature active is increased dramatically, and catalyst Cu0.02Fe0.2W0.02Ti has widest
Temperature window (100%:200-460 DEG C of NO conversion ratio), compared with catalyst Cu0.02Fe0.2Ti raising (90% or more NO conversion ratio:
200-460℃)70℃。
Different catalysts are within the scope of 100~460 DEG C to N in temperature2Selective enumeration method:
0.35g catalyst Cu is respectively adopted0.02Fe0.2Ti metal composite oxide (Cu0.02Fe0.2Ti), 0.35g catalyst
Cu0.02Fe0.2W0.01Ti metal composite oxide (Cu0.02Fe0.2W0.01Ti), 0.35g catalyst Cu0.02Fe0.2W0.02The compound gold of Ti
Belong to oxide (Cu0.02Fe0.2W0.02) and 0.35g catalyst Cu Ti0.02Fe0.2W0.03Ti metal composite oxide
(Cu0.02Fe0.2W0.03It Ti), is 1000ppm, NH in NO concentration3Concentration is 1000ppm, O2Volumetric concentration is 3%, N2It balances
Gas, air speed 40000h-1Under conditions of denitration, denitration temperature is followed successively by 100 DEG C, 130 DEG C, 160 DEG C, 200 DEG C, 240 DEG C, 280
DEG C, 310 DEG C, 350 DEG C, 400 DEG C, 430 DEG C, 450 DEG C and 460 DEG C, testing result is as shown in table 2 and figure 2.
Table 2
Fig. 2 is N2Selectivity-temperature profile, ★ indicates catalyst Cu in figure0.02Fe0.2The N of Ti metal composite oxide2
Selectivity-temperature curve, ■ indicates catalyst Cu in figure0.02Fe0.2W0.01The N of Ti metal composite oxide2Selectivity-temperature is bent
Line, in figure ● indicate catalyst Cu0.02Fe0.2W0.02The N of Ti metal composite oxide2Selectivity-temperature curve, in figure ▲ indicate
Catalyst Cu0.02Fe0.2W0.03The N of Ti metal composite oxide2Selectivity-temperature curve passes through table 2 and Fig. 2, catalyst
Cu0.02Fe0.2After introducing tungsten in Ti, N2Selectivity (high temperature, especially at 310 DEG C or more) is improved, catalyst
Cu0.02Fe0.2W0.02Ti high-temperature selective is improved to the greatest extent, within the scope of 100~460 DEG C, catalyst
Cu0.02Fe0.2W0.02The N of Ti2Selectivity is 95% or more.
Detect catalyst Cu0.02Fe0.2W0.02Ti metal composite oxide (Cu0.02Fe0.2W0.02Ti) temperature be 100~
Within the scope of 450 DEG C, air speed 40000h-1~100000h-1To NO conversion ratio in range:
Using 0.35g catalyst Cu0.02Fe0.2W0.02Ti metal composite oxide (Cu0.02Fe0.2W0.02Ti), in NO concentration
For 1000ppm, NH3Concentration is 1000ppm, O2Volumetric concentration is 3%, N2Denitration under the conditions of Balance Air is done, denitration temperature is followed successively by
100 DEG C, 130 DEG C, 160 DEG C, 200 DEG C, 240 DEG C, 280 DEG C, 310 DEG C, 350 DEG C, 400 DEG C, 430 DEG C, 450 DEG C and 460 DEG C, air speed
(GHSV) it is followed successively by 40000h-1、80000h-1And 100000h-1, testing result is as shown in table 3 and figure 3.
Table 3
Fig. 3 is NO conversion ratio-temperature profile, in figure ● indicates GHSV 40000h-1NO conversion ratio-temperature curve, figure
Middle ■ indicates GHSV 80000h-1NO conversion ratio-temperature curve, in figure ◆ indicate GHSV 100000h-1NO conversion ratio-temperature
It writes music line, passes through table 3 and Fig. 3, catalyst Cu0.02Fe0.2W0.02Ti can also have good catalysis under biggish space velocities
Activity.
Detect catalyst Cu0.02Fe0.2W0.02Ti metal composite oxide (Cu0.02Fe0.2W0.02Ti) in SO2/H2Under the conditions of O
NO conversion ratio, long run test is carried out in 0~34.5h time range, without SO in 0~3h2And H2O's is passed through, and opens from 3h
Beginning is passed through H2O, since 11.5h be passed through SO2, stopping is passed through H from 21.5h2O, stopping is passed through SO from 31.5h2, until
34.5h terminates, and detailed process is as follows:
One, in 0~3h: using 0.35g catalyst Cu0.02Fe0.2W0.02Ti metal composite oxide
(Cu0.02Fe0.2W0.02It Ti), is 1000ppm, NH in NO concentration3Concentration is 1000ppm, O2Volumetric concentration is 3%, N2Do Balance Air
Under the conditions of denitration, denitration temperature be 240 DEG C, air speed (GHSV) be 40000h-1；
Two, in 3h~11.5h: using 0.35g catalyst Cu0.02Fe0.2W0.02Ti metal composite oxide
(Cu0.02Fe0.2W0.02Ti), in H2O volumetric concentration is 5%, NO concentration is 1000ppm, NH3Concentration is 1000ppm, O2Volume is dense
Degree is 3%, N2Denitration under the conditions of Balance Air is done, denitration temperature is 240 DEG C, and air speed (GHSV) is 40000h-1；
Three, in 11.5h~21.5h: using 0.35g catalyst Cu0.02Fe0.2W0.02Ti metal composite oxide
(Cu0.02Fe0.2W0.02Ti), in H2O volumetric concentration is 5%, SO2Concentration is that 100ppm, NO concentration are 1000ppm, NH3Concentration is
1000ppm、O2Volumetric concentration is 3%, N2Denitration under the conditions of Balance Air is done, denitration temperature is 240 DEG C, and air speed (GHSV) is
40000h-1；
Four, in 21.5h~31.5h: using 0.35g catalyst Cu0.02Fe0.2W0.02Ti metal composite oxide
(Cu0.02Fe0.2W0.02Ti), in SO2Concentration is that 100ppm, NO concentration are 1000ppm, NH3Concentration is 1000ppm, O2Volumetric concentration
For 3%, N2Denitration under the conditions of Balance Air is done, denitration temperature is 240 DEG C, and air speed (GHSV) is 40000h-1；
Five, in 31.5h~34.5h: using 0.35g catalyst Cu0.02Fe0.2W0.02Ti metal composite oxide
(Cu0.02Fe0.2W0.02It Ti), is 1000ppm, NH in NO concentration3Concentration is 1000ppm, O2Volumetric concentration is 3%, N2Do Balance Air
Under the conditions of denitration, denitration temperature be 240 DEG C, air speed (GHSV) be 40000h-1；Testing result is as shown in table 4 and figure 4.
Table 4
Fig. 4 is NO conversion-time plot figure, passes through table 4 and Fig. 4, catalyst Cu0.02Fe0.2W0.02Ti is empty at 240 DEG C
Fast (GHSV) is 40000h-1Condition, a certain amount of water and SO2On catalytic performance without influence, illustrate catalyst
Cu0.02Fe0.2W0.02Ti has excellent water resistant, sulfur poisoning ability；After reaction in 34.5 hours, catalyst
Cu0.02Fe0.2W0.02Ti still has good catalytic activity, while illustrating its energy with good stability.
Detect catalyst Cu0.02Fe0.2W0.02Ti metal composite oxide (Cu0.02Fe0.2W0.02Ti) in 5%H2O and air speed
It (GHSV) is 100000h-1Under the conditions of, it is the NO conversion ratio within the scope of 100~470 DEG C in temperature:
Using 0.35g catalyst Cu0.02Fe0.2W0.02Ti metal composite oxide (Cu0.02Fe0.2W0.02Ti), in H2O volume
Concentration is 5%, NO concentration is 1000ppm, NH3Concentration is 1000ppm, O2Volumetric concentration is 3%, N2It does and takes off under the conditions of Balance Air
Nitre, denitration temperature are followed successively by 100 DEG C, 130 DEG C, 160 DEG C, 200 DEG C, 240 DEG C, 280 DEG C, 310 DEG C, 350 DEG C, 400 DEG C, 450 DEG C
With 470 DEG C, air speed (GHSV) be 100000h-1, testing result is as shown in table 5 and Fig. 5.
Table 5
| Temperature (T/ DEG C) | NO conversion ratio |
| 100 | 1 |
| 130 | 1 |
| 160 | 9 |
| 200 | 42 |
| 240 | 96 |
| 280 | 100 |
| 310 | 100 |
| 350 | 100 |
| 400 | 100 |
| 450 | 100 |
| 470 | 100 |
Fig. 5 is that NO conversion ratio-temperature profile by table 5 and Fig. 5 illustrates catalyst Cu0.02Fe0.2W0.02Ti is in air speed
It (GHSV) is 100000h-1, and have water it is existing under the conditions of, still there is good catalytic activity and wider temperature window (240-
470℃)。
Detect the influence of the NO oxidation reaction of different W content catalyst:
0.35g catalyst Cu is respectively adopted0.02Fe0.2Ti metal composite oxide (Cu0.02Fe0.2Ti), 0.35g catalyst
Cu0.02Fe0.2W0.01Ti metal composite oxide (Cu0.02Fe0.2W0.01Ti), 0.35g catalyst Cu0.02Fe0.2W0.02The compound gold of Ti
Belong to oxide (Cu0.02Fe0.2W0.02) and 0.35g catalyst Cu Ti0.02Fe0.2W0.03Ti metal composite oxide
(Cu0.02Fe0.2W0.03Ti), NO concentration is 1000ppm, NH3Concentration is 1000ppm, O2Volumetric concentration is 3%, N2Do Balance Air,
Air speed is 40000h-1Under conditions of denitration, denitration temperature is followed successively by 25 DEG C, 80 DEG C, 100 DEG C, 130 DEG C, 160 DEG C, 190 DEG C, 200
DEG C, 240 DEG C, 280 DEG C, 310 DEG C, 350 DEG C, 400 DEG C, 430 DEG C, 450 DEG C, 460 DEG C and 470 DEG C, testing result is as shown in Figure 6.
Fig. 6 is NO2Concentration-temperature curve graph, ★ indicates catalyst Cu in figure0.02Fe0.2The NO of Ti metal composite oxide2
Concentration-temperature curve, ■ indicates catalyst Cu in figure0.02Fe0.2W0.01The NO of Ti metal composite oxide2Concentration-temperature curve,
In figure ● indicate catalyst Cu0.02Fe0.2W0.02The NO of Ti metal composite oxide2Concentration-temperature curve, in figure ▲ indicate catalysis
Agent Cu0.02Fe0.2W0.03The NO of Ti metal composite oxide2Concentration-temperature curve, Fig. 6 indicate the energy of different catalysts oxidation NO
Power, catalyst Cu0.02Fe0.2After introducing tungsten in Ti, oxidation NO ability is substantially reduced.
Different W contents are detected to the NH of catalyst3The influence of oxidation reaction:
0.35g catalyst Cu is respectively adopted0.02Fe0.2Ti metal composite oxide (Cu0.02Fe0.2Ti), 0.35g catalyst
Cu0.02Fe0.2W0.01Ti metal composite oxide (Cu0.02Fe0.2W0.01Ti), 0.35g catalyst Cu0.02Fe0.2W0.02The compound gold of Ti
Belong to oxide (Cu0.02Fe0.2W0.02) and 0.35g catalyst Cu Ti0.02Fe0.2W0.03Ti metal composite oxide
(Cu0.02Fe0.2W0.03Ti), NO concentration is 1000ppm, NH3Concentration is 1000ppm, O2Volumetric concentration is 3%, N2Do Balance Air,
Air speed is 40000h-1Under conditions of denitration, denitration temperature be 25 DEG C, 100 DEG C, 130 DEG C, 160 DEG C, 190 DEG C, 200 DEG C, 220 DEG C,
240 DEG C, 250 DEG C, 280 DEG C, 310 DEG C, 340 DEG C, 350 DEG C, 400 DEG C and 450 DEG C, testing result is as shown in Figure 7.
Fig. 7 is NH3Concentration-temperature curve graph, ★ indicates catalyst Cu in figure0.02Fe0.2The NH of Ti metal composite oxide3
Concentration-temperature curve, ■ indicates catalyst Cu in figure0.02Fe0.2W0.01The NH of Ti metal composite oxide3Concentration-temperature curve,
In figure ● indicate catalyst Cu0.02Fe0.2W0.02The NH of Ti metal composite oxide3Concentration-temperature curve, in figure ▲ indicate catalysis
Agent Cu0.02Fe0.2W0.03The NH of Ti metal composite oxide3Concentration-temperature curve, Fig. 7 indicate that different catalysts aoxidize NH3Energy
Power illustrates the catalyst after tungsten is modified, and aoxidizes NH3Ability be suppressed, this can effectively be reduced in high-temperature region NH3's
Excessive oxidation, to improve catalyst high-temperature catalytic activity and N2Selectivity.In conjunction with Fig. 6 and Fig. 7 it is found that and catalyst
Cu0.02Fe0.2Ti metal composite oxide is compared, catalyst Cu0.02Fe0.2W0.01Ti metal composite oxide, catalyst
Cu0.02Fe0.2W0.02Ti metal composite oxide and catalyst Cu0.02Fe0.2W0.01Ti metal composite oxide is to NO/NH3Oxygen
Change ability is weakened, and illustrates that catalyst redox ability is declined, while reducing NH3Excessive oxidation at high temperature.This
It is also Cu0.02Fe0.2WaTi catalyst series (i.e. catalyst Cu0.02Fe0.2W0.01Ti metal composite oxide, catalyst
Cu0.02Fe0.2W0.02Ti metal composite oxide and catalyst Cu0.02Fe0.2W0.01Ti metal composite oxide) with good
High temperature active and N2One of the reason of selectivity.
Respectively to catalyst Cu0.02Fe0.2Ti metal composite oxide (Cu0.02Fe0.2Ti), catalyst
Cu0.02Fe0.2W0.01Ti metal composite oxide (Cu0.02Fe0.2W0.01Ti), catalyst Cu0.02Fe0.2W0.02Ti composition metal oxygen
Compound (Cu0.02Fe0.2W0.02) and catalyst Cu Ti0.02Fe0.2W0.03Ti metal composite oxide (Cu0.02Fe0.2W0.03Ti it) carries out
H2- TPR detection, testing result are as shown in Figure 8.
Fig. 8 is H2- TPR spectrogram, a indicates catalyst Cu in figure0.02Fe0.2The H of Ti metal composite oxide2- TPR spectrogram, b
Indicate catalyst Cu0.02Fe0.2W0.01The H of Ti metal composite oxide2- TPR spectrogram, c indicate catalyst Cu0.02Fe0.2W0.02Ti
The H of metal composite oxide2- TPR spectrogram, d indicate catalyst Cu0.02Fe0.2W0.03The H of Ti metal composite oxide2- TPR spectrum
Figure, passes through H2- TPR carrys out the redox ability of Study of Catalyst, and with increasing for W amount, each reduction peak is to high-temperature mobile, explanation
Cu0.02Fe0.2Tungsten is added in Ti can inhibit catalyst (Cu0.02Fe0.2W0.01Ti、Cu0.02Fe0.2W0.02Ti and
Cu0.02Fe0.2W0.03Ti redox ability).
Fig. 9 is H2- TPR spectrogram, a indicates catalyst Fe in figure0.2W0.02The H of Ti metal composite oxide2- TPR spectrogram, b
Indicate catalyst Cu0.02W0.02The H of Ti metal composite oxide2- TPR spectrogram, c indicate catalyst Cu0.02Fe0.2W0.02Ti is compound
The H of metal oxide2- TPR spectrogram, d indicate catalyst Cu0.02Fe0.2The H of Ti metal composite oxide2- TPR spectrogram, e are indicated
Catalyst Fe0.1The H of Ti metal composite oxide2- TPR spectrogram, f indicate catalyst Cu0.1The H of Ti metal composite oxide2-TPR
Spectrogram passes through catalyst Cu as shown in Figure 90.1Ti metal composite oxide, catalyst Fe0.1Ti metal composite oxide, catalysis
Agent Cu0.02Fe0.2Ti metal composite oxide, catalyst Cu0.02Fe0.2W0.02Ti metal composite oxide, catalyst
Cu0.02W0.02Ti metal composite oxide and catalyst Fe0.2W0.02Ti metal composite oxide compares, it is known that copper, iron, between tungsten
There are stronger interactions, this is also catalyst Cu0.02Fe0.2W0.02Ti metal composite oxide can have low in preferable
The reason of warm activity.
Figure 10 is NH3- TPD map, a indicates catalyst Cu in figure0.02Fe0.2The NH of Ti metal composite oxide3- TPD figure
Spectrum, b indicate catalyst Cu0.02Fe0.2W0.01The NH of Ti metal composite oxide3- TPD map, c indicate catalyst
Cu0.02Fe0.2W0.02The NH of Ti metal composite oxide3- TPD map, d indicate catalyst Cu0.02Fe0.2W0.03Ti composition metal oxygen
The NH of compound3- TPD map shows catalyst Cu by Figure 100.02Fe0.2W0.02Ti metal composite oxide has maximal acid amount,
This is catalyst Cu0.02Fe0.2W0.02Ti metal composite oxide has good high temperature N2The reason of selectivity and high temperature active.
Claims (6)
1. a kind of ammonia-selective catalyst reduction of nitrogen oxides catalyst, it is characterised in that ammonia-selective catalytic reduction nitrogen oxygen
Compound catalyst is metal composite oxide, and metallic element is Cu, Fe, W and Ti in the metal composite oxide, and Cu, Fe,
The mass ratio of the material of W and Ti is 0.02:0.2:x:1, and wherein x is 0.01~0.03.
2. a kind of preparation method of ammonia-selective catalyst reduction of nitrogen oxides catalyst as described in claim 1, feature
It is that it is completed by the following steps:
One, it mixes: mantoquita, molysite and tungsten salt being dissolved in distilled water-glacial acetic acid mixed liquor, mixing salt solution is obtained；Institute
State Fe in mixing salt solution concentration be 0.3mol/L~0.4mol/L, and in mixing salt solution Cu, Fe and W the mass ratio of the material
For 0.02:0.2:x, wherein x is 0.01~0.03；The volume of distilled water and glacial acetic acid in the distilled water-glacial acetic acid mixed liquor
Than for (2~4): 10；
Two, it prepares solution containing Ti: butyl titanate being dissolved in ethyl alcohol, the alcoholic solution of butyl titanate is obtained；The metatitanic acid
The concentration of butyl titanate is 1.0mol/L~2.0mol/L in the alcoholic solution of four butyl esters；
Three, prepare catalyst precursor: by the alcoholic solution of mixing salt solution and butyl titanate mix, be first stirred to react 1h~
Then 6h stands 4 days~6 days at room temperature, is finally placed in baking oven, dry 10h~18h at being 90 DEG C~140 DEG C in temperature,
Obtain catalyst precursor；The mass ratio of the material of Cu, Fe, W and Ti are 0.02:0.2:x:1 in the catalyst precursor, wherein
X is 0.01~0.03；
Four, high-temperature process: being first milled into powder for catalyst precursor, is subsequently placed in Muffle furnace, with 5 DEG C/min~15 DEG C/
The heating rate of min is warming up to 400 DEG C~600 DEG C, and is 400 DEG C~600 DEG C processing 3h~6h in temperature, is cooled to room temperature,
Ground, tabletting and granulation obtain metal composite oxide, as ammonia-selective catalyst reduction of nitrogen oxides catalyst.
3. a kind of preparation method of ammonia-selective catalyst reduction of nitrogen oxides catalyst according to claim 1, special
Sign is that mantoquita described in step 1 is copper nitrate.
4. a kind of preparation method of ammonia-selective catalyst reduction of nitrogen oxides catalyst according to claim 1, special
Sign is that molysite described in step 1 is ferric nitrate.
5. a kind of preparation method of ammonia-selective catalyst reduction of nitrogen oxides catalyst according to claim 1, special
Sign is that tungsten salt described in step 1 is ammonium metatungstate.
6. a kind of application of ammonia-selective catalyst reduction of nitrogen oxides catalyst as described in claim 1, it is characterised in that
Ammonia-selective catalyst reduction of nitrogen oxides catalyst is used for denitration.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811481221.XA CN109331835A (en) | 2018-12-05 | 2018-12-05 | A kind of ammonia-selective catalyst reduction of nitrogen oxides catalyst and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811481221.XA CN109331835A (en) | 2018-12-05 | 2018-12-05 | A kind of ammonia-selective catalyst reduction of nitrogen oxides catalyst and its preparation method and application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109331835A true CN109331835A (en) | 2019-02-15 |
Family
ID=65319926
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811481221.XA Pending CN109331835A (en) | 2018-12-05 | 2018-12-05 | A kind of ammonia-selective catalyst reduction of nitrogen oxides catalyst and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109331835A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110548516A (en) * | 2019-09-10 | 2019-12-10 | 黑龙江大学 | Catalyst for ammonia selective catalytic reduction of nitrogen oxides and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1153648A1 (en) * | 2000-05-10 | 2001-11-14 | OMG AG & Co. KG | Structured catalyst for the selective reduction of nitrogen oxides by ammonia using a hydrolisable compound |
| CN103170346A (en) * | 2013-04-10 | 2013-06-26 | 中国科学院生态环境研究中心 | Tungsten oxide surface modified Fe2O3 catalyst as well as preparation method and application thereof |
| CN105148928A (en) * | 2015-08-17 | 2015-12-16 | 中国石油大学(北京) | Water-resistant and sulfur-resistant powder catalyst for flue gas denitrification, preparation method and application of water-resistant and sulfur-resistant powder catalyst |
| CN106334573A (en) * | 2016-09-18 | 2017-01-18 | 黑龙江大学 | Preparation method of catalyst for selectively catalyzing and reducing nitrogen oxide |
| CN107626342A (en) * | 2017-09-18 | 2018-01-26 | 中节能万润股份有限公司 | A kind of iron copper modified molecular screen base honeycomb type denitrification catalyst and preparation method thereof |
-
2018
- 2018-12-05 CN CN201811481221.XA patent/CN109331835A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1153648A1 (en) * | 2000-05-10 | 2001-11-14 | OMG AG & Co. KG | Structured catalyst for the selective reduction of nitrogen oxides by ammonia using a hydrolisable compound |
| CN103170346A (en) * | 2013-04-10 | 2013-06-26 | 中国科学院生态环境研究中心 | Tungsten oxide surface modified Fe2O3 catalyst as well as preparation method and application thereof |
| CN105148928A (en) * | 2015-08-17 | 2015-12-16 | 中国石油大学(北京) | Water-resistant and sulfur-resistant powder catalyst for flue gas denitrification, preparation method and application of water-resistant and sulfur-resistant powder catalyst |
| CN106334573A (en) * | 2016-09-18 | 2017-01-18 | 黑龙江大学 | Preparation method of catalyst for selectively catalyzing and reducing nitrogen oxide |
| CN107626342A (en) * | 2017-09-18 | 2018-01-26 | 中节能万润股份有限公司 | A kind of iron copper modified molecular screen base honeycomb type denitrification catalyst and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| LIN ZHU ET AL.: "Comparison study of Cu-Fe-Ti and Co-Fe-Ti oxide catalysts for selective catalytic reduction of NO with NH3 at low temperature", 《JOURNAL OF COLLOID AND INTERFACE SCIENCE》 * |
| 马士博等: "W改性CuFeTiOx催化剂对NH3-SCR脱硝性能的研究", 《第十一届全国环境催化与环境材料学术会议论文集》 * |
| 马士博等: "W改性CuFeTiOx催化剂对NH3-SCR脱硝性能的研究", 《第十一届全国环境催化与黄环境材料学术会议论文集》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110548516A (en) * | 2019-09-10 | 2019-12-10 | 黑龙江大学 | Catalyst for ammonia selective catalytic reduction of nitrogen oxides and preparation method and application thereof |
| CN110548516B (en) * | 2019-09-10 | 2022-07-26 | 黑龙江大学 | Catalyst for ammonia selective catalytic reduction of nitrogen oxides and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105817220B (en) | A kind of rare earth modified sulfur resistive low-temperature SCR catalyst and preparation method thereof | |
| CN102266761B (en) | SCR (selective catalyctic reduction) flue gas denitration catalyst based on TiO2-ZrO2 composite carrier and preparation method thereof | |
| CN105289644B (en) | A kind of flat sulfur resistive low temperature SCR denitration catalyst and preparation method thereof | |
| CN101254464A (en) | Composite catalyst flue gas denitrating under low-temperature condition and method of preparing the same | |
| CN105727936A (en) | Low-temperature sulfur-resistant denitration catalyst and preparation method thereof | |
| CN101480611B (en) | Vanadium-doped titanium-base flue gas denitration catalyst material and preparation method thereof | |
| CN101879452B (en) | Manganese-based low-temperature denitration catalyst and preparation method thereof | |
| CN102205240B (en) | Based on TiO 2-SnO 2the SCR catalyst for denitrating flue gas of complex carrier and preparation method | |
| CN103638942A (en) | SCR (selective catalytic reduction) catalyst for denitrating low-temperature smoke of cement kiln and preparation method thereof | |
| CN101862651B (en) | V-Sb-Nb/Ti catalyst for selective catalytic reduction of nitric oxide and preparation method | |
| CN101898136A (en) | Titanium-based multi-metal oxide catalyst for removing diesel engine NOx by NH3-SCR in wide temperature window | |
| CN101507928A (en) | Ferro manganese composite oxides catalyst and preparation method and use thereof | |
| CN109092323A (en) | Low-temperature SCR catalyst for denitrating flue gas and its preparation method and application | |
| CN102658161A (en) | Supported iron-based composite oxide catalyst and preparation method thereof | |
| CN107224989B (en) | Acid modified cerium-based catalyst and preparation method and application thereof | |
| CN110773153B (en) | Supported manganese-based medium-low temperature denitration catalyst, preparation method and application thereof | |
| CN102600832A (en) | Combined catalyst for improving denitration performance and application thereof | |
| CN111167487B (en) | Multifunctional catalyst, preparation method and application thereof | |
| CN106475129A (en) | The preparation method of the composite oxides denitrating catalyst with hexagonal boron nitride as carrier | |
| CN100493699C (en) | Intermediate temperate carbonyl sulfur hydrolyst and method of preparing the same and use thereof | |
| CN105413677A (en) | Low-temperature denitration catalyst used after dedusting of power plant and preparation method of catalyst | |
| WO2021180142A1 (en) | Hybrid synergistically-enhanced low-temperature scr denitration catalyst and preparation method therefor | |
| CN109331835A (en) | A kind of ammonia-selective catalyst reduction of nitrogen oxides catalyst and its preparation method and application | |
| CN103394369A (en) | Non-noble metal molecular sieve catalyst for low concentration gas combustion and preparation method thereof | |
| CN114832829A (en) | High-temperature denitration catalyst for gas tail gas and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190215 |
|
| RJ01 | Rejection of invention patent application after publication |