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CN109331835A - A kind of ammonia-selective catalytic reduction of nitrogen oxides catalyst and preparation method and application thereof - Google Patents

A kind of ammonia-selective catalytic reduction of nitrogen oxides catalyst and preparation method and application thereof Download PDF

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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
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catalyst
ammonia
composite oxide
metal composite
nitrogen oxides
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朱宇君
马士博
牛晓宇
袁福龙
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Heilongjiang University
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Heilongjiang University
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    • 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

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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

A kind of ammonia-selective catalyst reduction of nitrogen oxides catalyst and preparation method thereof and Using
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)

1.一种氨气-选择性催化还原氮氧化物催化剂，其特征在于氨气-选择性催化还原氮氧化物催化剂为复合金属氧化物，所述复合金属氧化物中金属元素为Cu、Fe、W和Ti，且Cu、Fe、W与Ti的物质的量比为0.02:0.2:x:1，其中x为0.01～0.03。1. Ammonia-selective catalytic reduction of nitrogen oxides catalyst is characterized in that ammonia-selective catalytic reduction of nitrogen oxides catalyst is a composite metal oxide, and in the composite metal oxide, metal elements are Cu, Fe, The material ratio of W and Ti, and Cu, Fe, W and Ti is 0.02:0.2:x:1, wherein x is 0.01-0.03. 2.如权利要求1所述的一种氨气-选择性催化还原氮氧化物催化剂的制备方法，其特征在于它是按以下步骤完成的：2. the preparation method of a kind of ammonia-selective catalytic reduction of nitrogen oxides catalyst as claimed in claim 1 is characterized in that it is completed by the following steps: 一、混合：将铜盐、铁盐和含钨盐溶解于蒸馏水-冰醋酸混合液中，得到混合盐溶液；所述混合盐溶液中Fe的浓度为0.3mol/L～0.4mol/L，且混合盐溶液中Cu、Fe与W的物质的量比为0.02:0.2:x，其中x为0.01～0.03；所述蒸馏水-冰醋酸混合液中蒸馏水与冰醋酸的体积比为(2～4):10；1. Mixing: dissolving copper salt, iron salt and tungsten-containing salt in distilled water-glacial acetic acid mixed solution to obtain a mixed salt solution; the concentration of Fe in the mixed salt solution is 0.3mol/L～0.4mol/L, and The substance ratio of Cu, Fe and W in the mixed salt solution is 0.02:0.2:x, wherein x is 0.01～0.03; the volume ratio of distilled water and glacial acetic acid in the distilled water-glacial acetic acid mixed solution is (2～4) :10; 二、制备含Ti溶液：将钛酸四丁酯溶解于乙醇中，得到钛酸四丁酯的醇溶液；所述钛酸四丁酯的醇溶液中钛酸四丁酯的浓度为1.0mol/L～2.0mol/L；2. Preparation of Ti-containing solution: dissolving tetrabutyl titanate in ethanol to obtain an alcohol solution of tetrabutyl titanate; the concentration of tetrabutyl titanate in the alcohol solution of tetrabutyl titanate is 1.0 mol/ L～2.0mol/L; 三、制备催化剂前驱体：将混合盐溶液与钛酸四丁酯的醇溶液混和，先搅拌反应1h～6h，然后在室温下静置4天～6天，最后置于烘箱中，在温度为90℃～140℃下烘干10h～18h，得到催化剂前驱体；所述催化剂前驱体中Cu、Fe、W与Ti的物质的量比为0.02:0.2:x:1，其中x为0.01～0.03；3. Preparation of catalyst precursor: Mix the mixed salt solution with the alcoholic solution of tetrabutyl titanate, first stir for 1h to 6h, then stand at room temperature for 4 to 6 days, and finally place it in an oven at a temperature of Drying at 90°C～140°C for 10h～18h to obtain a catalyst precursor; the material ratio of Cu, Fe, W and Ti in the catalyst precursor is 0.02:0.2:x:1, wherein x is 0.01～0.03 ; 四、高温处理：先将催化剂前驱体碾磨成粉末，然后置于马弗炉中，以5℃/min～15℃/min的升温速率升温至400℃～600℃，并在温度为400℃～600℃处理3h～6h，冷却至室温，经研磨、压片和造粒，得到复合金属氧化物，即为氨气-选择性催化还原氮氧化物催化剂。4. High temperature treatment: First grind the catalyst precursor into powder, then place it in a muffle furnace, and heat it up to 400°C to 600°C at a heating rate of 5°C/min to 15°C/min, and at a temperature of 400°C ～600℃ for 3h～6h, cooled to room temperature, ground, tableted and granulated to obtain composite metal oxide, which is ammonia-selective catalytic reduction of nitrogen oxides catalyst. 3.根据权利要求1所述的一种氨气-选择性催化还原氮氧化物催化剂的制备方法，其特征在于步骤一中所述的铜盐为硝酸铜。3. the preparation method of a kind of ammonia-selective catalytic reduction of nitrogen oxides catalyst according to claim 1, is characterized in that the copper salt described in step 1 is copper nitrate. 4.根据权利要求1所述的一种氨气-选择性催化还原氮氧化物催化剂的制备方法，其特征在于步骤一中所述的铁盐为硝酸铁。4. the preparation method of a kind of ammonia-selective catalytic reduction of nitrogen oxides catalyst according to claim 1, is characterized in that the iron salt described in the step 1 is ferric nitrate. 5.根据权利要求1所述的一种氨气-选择性催化还原氮氧化物催化剂的制备方法，其特征在于步骤一中所述的含钨盐为偏钨酸铵。5. The preparation method of an ammonia-selective catalytic reduction of nitrogen oxide catalyst according to claim 1, wherein the tungsten-containing salt described in the step 1 is ammonium metatungstate. 6.如权利要求1所述的一种氨气-选择性催化还原氮氧化物催化剂的应用，其特征在于氨气-选择性催化还原氮氧化物催化剂用于脱硝。6. The application of an ammonia-selective catalytic reduction of nitrogen oxides catalyst as claimed in claim 1, characterized in that the ammonia-selective catalytic reduction of nitrogen oxides catalyst is used for denitration.
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