CN109012744B - Method for degrading nitrogen oxide by visible light catalysis - Google Patents
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- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 title claims abstract description 126
- 238000000034 method Methods 0.000 title claims abstract description 59
- 230000000593 degrading effect Effects 0.000 title claims abstract description 24
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 18
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- 230000015556 catabolic process Effects 0.000 claims abstract description 41
- 238000006731 degradation reaction Methods 0.000 claims abstract description 41
- QMBQEXOLIRBNPN-UHFFFAOYSA-L zirconocene dichloride Chemical compound [Cl-].[Cl-].[Zr+4].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 QMBQEXOLIRBNPN-UHFFFAOYSA-L 0.000 claims abstract description 29
- 239000011941 photocatalyst Substances 0.000 claims abstract description 10
- 238000001704 evaporation Methods 0.000 claims description 37
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 32
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- 229910001507 metal halide Inorganic materials 0.000 claims description 14
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- 238000003756 stirring Methods 0.000 claims description 13
- 230000003197 catalytic effect Effects 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 25
- 239000003054 catalyst Substances 0.000 abstract description 16
- 239000004408 titanium dioxide Substances 0.000 abstract description 10
- 150000002500 ions Chemical class 0.000 abstract description 6
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- 230000001699 photocatalysis Effects 0.000 description 7
- 239000004065 semiconductor Substances 0.000 description 6
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
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- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 3
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- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
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- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
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- GRJWDJVTZAUGDZ-UHFFFAOYSA-N anthracene;magnesium Chemical compound [Mg].C1=CC=CC2=CC3=CC=CC=C3C=C21 GRJWDJVTZAUGDZ-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- 229910052726 zirconium Inorganic materials 0.000 description 1
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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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0231—Halogen-containing compounds
- B01J31/0232—Halogen-containing compounds also containing elements or functional groups covered by B01J31/0201 - B01J31/0228
-
- 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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- B01J35/39—
Abstract
The invention discloses a method for degrading nitrogen oxides by visible light catalysis, which takes zirconocene dichloride as a photocatalyst and adopts a photocatalytic degradation method to catalyze and degrade the nitrogen oxides. Compared with the existing titanium dioxide catalyst, the catalyst has high visible light utilization rate, nitrogen oxides can be directly catalyzed in a visible light range by using the catalyst to carry out photocatalytic degradation, the NO degradation rate can reach 65.8 percent, the titanium dioxide catalyst is directly catalyzed in the visible light range, the NO degradation rate is lower than 10 percent, and the NO degradation rate is only about 50 percent even after the procedures of ion doping and the like are carried out. Therefore, the method can directly catalyze the nitrogen oxide under the irradiation of visible light while ensuring the degradation rate of the nitrogen oxide, improves the utilization rate of solar energy, avoids the procedures of ion doping and the like, has simpler process and is more beneficial to the industrial implementation of photocatalytic degradation of the nitrogen oxide.
Description
Technical Field
The invention relates to a method for degrading nitrogen oxides by visible light catalysis.
Background
Nitrogen Oxides (NO)x) Mainly comprises NO and NO2The emission of nitrogen oxides in 2007 in China is 1643.4 ten thousand tons, and the method is one of the main constituents of atmospheric pollutants. NO in the atmospherexIrradiated by sunlight and O in the air2And reacting with organic matters to form aldehyde, ketone and organic acid, which causes photochemical smog and acid rain. With the rapid development of industry, the treatment of nitrogen oxides has become a serious issueAnd urgent research content. Currently mature NO removalxThe method is a catalytic reduction method, but the method has the disadvantages of high equipment investment and operation cost, secondary pollution and limitation to fixed source NOxRemoving and the like. In recent years, many researches show that the photocatalytic technology has good application prospect in the aspect of environmental pollution treatment.
The photocatalytic degradation of pollutants takes semiconductor oxide as a catalyst, and light energy is converted into chemical energy under the irradiation of a light source to promote the pollutants to be degraded into harmless substances.
TiO2Has better catalytic activity and is TiO2Has high chemical stability, is resistant to light corrosion, has deeper valence band energy level, and can enable certain chemical reactions to be carried out on the TiO irradiated by light2Surface is realized and accelerated while TiO2Has no toxic and harmful effect on human body, so the TiO is used for treating2The photocatalytic reaction has been studied most actively, and the photocatalytic reaction has also become a main material of a photocatalyst.
But TiO 22The photocatalyst has a wide band gap (Eg is 3.2eV, and λ is 1239.8/Eg, so that λ is 387nm), and can only be excited by ultraviolet light with a wavelength of no more than 387nm, and the ultraviolet light (300-400 nm) only accounts for 4-6% of solar energy reaching the ground, so that the solar energy utilization rate is very low. And 45% of solar energy is in a visible light region, so that a method for degrading nitrogen oxides by visible light catalysis is needed to be researched, the utilization rate of visible light is increased, and the utilization rate of solar energy is improved.
Disclosure of Invention
In view of the above, the present invention provides a method for degrading nitrogen oxide by visible light catalysis, which improves the utilization rate of visible light while ensuring the degradation rate of nitrogen oxide.
In order to solve the technical problems, the technical scheme of the invention is a method for degrading nitrogen oxide by visible light catalysis, which takes zirconocene dichloride as a photocatalyst and adopts a photocatalytic degradation method to catalyze and degrade the nitrogen oxide.
The technology for degrading nitrogen oxides by photocatalysis is an environment-friendly treatment process for a flue gas purification process, and has the advantages of mild reaction conditions, energy conservation, environmental friendliness, strong redox capability and the like. The photocatalytic material can drive oxidation-reduction reaction by utilizing a special semiconductor energy band structure of the photocatalytic material, and is used for oxidative decomposition of organic pollutants, flue gas purification and the like. The essence of photocatalysis is the activation of semiconductors under the action of natural or artificial light sources. Under illumination, the semiconductor absorbs sufficient energy from the photon to cause an electron to transit from the valence band of the catalyst to the conduction band, and the atom is excited with energy to form an electron-hole pair. Those holes are capable of generating OH from water molecules-Free radicals are adsorbed on the surface of semiconductor, the nitrogen oxide is converted by the active radicals, and the electrons and oxygen molecules form superoxide anion O2 -A strong oxidizer is formed that oxidizes nitrogen oxides.
The photocatalytic material most studied at present is TiO2Due to TiO2The photocatalyst has a wide band gap (Eg is 3.2eV, and λ is 1239.8/Eg, so that λ is 387nm), and can only be excited by ultraviolet light with a wavelength of no more than 387nm, and the ultraviolet light (300-400 nm) only accounts for 4-6% of solar energy reaching the ground, so that the solar energy utilization rate is very low. The visible light (400-700 nm) accounts for 45% of the total energy of the solar energy, so that the technical key for improving the solar energy utilization rate is to reduce the width of the forbidden band Eg of the catalyst and expand the absorption spectrum to the visible light.
The invention adopts zirconocene dichloride as a catalyst, zirconium as a same-group element of titanium, has the property of a semiconductor, has a relatively small band gap (Eg ═ 2.88eV) of the zirconocene dichloride, has the wavelength of incident light of λ ═ 430nm, and belongs to the range of visible light blue light. Referring to fig. 2, the absorption spectrum of zirconocene dichloride is compared with that of the existing photocatalyst titanium dioxide, and in the range of visible light (430nm), zirconocene dichloride has a strong absorption peak, which lays a basic condition for catalyzing and degrading nitrogen oxide, while the absorption peak of titanium dioxide is very small.
The zirconocene dichloride used in the method can adopt a Grignard method, a sodium cyclopentadienyl method, a lithium method, an anthracene magnesium method and a diethylamine methodObtained by synthesis, preferably by the diethylamine method, which is ZrCl4Mixing with cyclopentadiene in mixed solvent [ V (dichloromethane): V (THF): 3: 7]The invention relates to a method for synthesizing zirconocene dichloride through a medium reflux reaction for 6 hours, and a specific synthesis method of the zirconocene dichloride is described in detail in a journal (No. 18, No. 4, pages 484-486 in 2010).
Further, the method for degrading nitrogen oxides by visible light catalysis provided by the invention specifically comprises the following two steps:
(1) dispersing 100mg of zirconocene dichloride in 50mL of solvent ethanol, performing ultrasonic treatment for 40-60 min, stirring for 1.5h, uniformly mixing to form a mixed solution, transferring the mixed solution into an evaporation dish, and evaporating the solvent at 60-70 ℃; the solvent ethanol is preferably absolute ethanol, so that the zirconocene dichloride can be uniformly dispersed in the solvent, the evaporation of the solvent can be accelerated, and the time is saved;
the step enables the zirconocene dichloride catalyst to be dispersed uniformly, so that the zirconocene dichloride catalyst can fully play the role of the catalyst in the next photocatalytic degradation device.
(2) And (2) placing the evaporation pan treated in the step (1) in a photocatalytic degradation device, introducing NO and dry air into the photocatalytic degradation device, circulating the NO in the photocatalytic degradation device for 8-12min, and catalytically degrading the NO under the irradiation of a light source.
Wherein the flow rate of NO introduced into the photocatalytic degradation device is 2-10mL/min, and the flow rate of dry air is 1-2L/min; preferably, the flow rate of NO is 5mL/min and the flow rate of dry air is 1.5L/min.
When the method is applied to actual production, the light source is natural light irradiated by the sun; when used for experimental studies under laboratory conditions, the light source used was 150w of light from a metal halide lamp. The metal halide lamp has the characteristics of high luminous efficiency, good color rendering performance, long service life and the like, and is a novel energy-saving light source which is close to daylight color.
Further, the time for the light irradiation cyclic degradation of NO in the photocatalytic degradation device in the step (2) is preferably 10 min.
Compared with the prior art, the method for degrading nitrogen oxide by visible light catalysis provided by the invention adopts a photocatalytic degradation method, has the advantages of mild reaction conditions, energy conservation, environmental protection, strong oxidation reduction capability and the like, takes zirconocene dichloride as a photocatalyst, has high visible light utilization rate compared with the existing titanium dioxide catalyst, can catalyze nitrogen oxide by photocatalysis by using the catalyst, and has the NO degradation rate of 65.8 percent, while the method adopts the titanium dioxide catalyst, directly catalyzes nitrogen oxide by using the catalyst in the visible light range, has the NO degradation rate of less than 10 percent, and has the NO degradation rate of only about 50 percent even after processes such as ion doping and the like are carried out. Therefore, the method can directly catalyze the nitrogen oxide under the irradiation of visible light while ensuring the degradation rate of the nitrogen oxide, improves the utilization rate of solar energy, avoids the procedures of ion doping and the like, has simpler process and is more beneficial to the industrial implementation of photocatalytic degradation of the nitrogen oxide.
Drawings
FIG. 1 is a graph showing the degradation rate of zirconocene dichloride for the catalytic degradation of NO;
FIG. 2 is an absorption spectrum diagram of zirconocene dichloride and titanium dioxide.
Detailed Description
In order to make the technical solutions of the present invention better understood by those skilled in the art, the present invention will be described in further detail with reference to preferred embodiments. It should be noted that the following preferred embodiments should not be construed as limiting the invention, which is to be limited only by the scope of the appended claims. It will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the spirit and scope of the invention, and these modifications and adaptations should be considered within the scope of the invention.
The zirconocene dichloride used in the following examples was synthesized by the diethylamine method disclosed by the present inventors.
The photocatalytic degradation device is made of a phi 170 multiplied by 500mm glass tube, the middle part of the glass tube is divided into an upper part and a lower part by a glass plate, a catalyst is placed on the upper part, and NO and dry air are introduced; the lower part is sealed and is not aerated.
One end of the photocatalytic degradation device is provided with an NO air inlet, a dry air inlet and a circulating gas inlet, and the NO air inlet and the dry air inlet are respectively provided with a gas flow controller for controlling the flow rate of NO and dry air; the other end of the photocatalytic degradation device is provided with a circulating gas outlet and a tail gas discharge port, the circulating gas outlet is connected with the circulating gas inlet through a circulating pipe, and a valve is arranged on the tail gas discharge port to control the opening and the closing of the tail gas discharge port. And a metal halide lamp is arranged above the photocatalytic degradation device to provide a light source for the photocatalytic degradation device.
Example 1
Dispersing 100mg of zirconocene dichloride in 50ml of ethanol, performing ultrasonic treatment for 50min, stirring for 1.5h, uniformly mixing, transferring to an evaporation dish, and evaporating the solvent at 60-70 ℃. Placing an evaporation pan in a photocatalytic degradation device, detecting the photocatalytic degradation activity of NO, adjusting the flow rate of NO to be 5mL/min, and the drying air flow rate to be 1.5L/min, wherein the concentration of NO is 600ppb, starting a 150W metal halide lamp, irradiating visible light to degrade NO circularly, opening a tail gas discharge port valve to discharge tail gas every 1min of degradation, and detecting the NO content in the tail gas through a gas chromatography, thereby drawing a graph of the degradation rate of NO catalytically degraded by zirconocene dichloride (FIG. 1). As can be seen from fig. 1, when the visible light illumination cycle degradation time is 10min, the content of NO in the tail gas is the lowest, and the degradation rate of NO reaches the highest and is 65.8%; when the visible light illumination cyclic degradation time is 8-12min, the NO degradation rate is better.
Example 2
Dispersing 100mg of zirconocene dichloride in 50ml of ethanol, performing ultrasonic treatment for 40min, stirring for 1.5h, uniformly mixing, transferring to an evaporation dish, and evaporating the solvent at 60-70 ℃. The evaporation pan is placed in a photocatalytic degradation device for detecting the photocatalytic degradation activity of NO, the flow rate of NO is adjusted to be 5mL/min, the dry air flow rate is 1.5L/min, the concentration of NO at the moment is 600ppb, a 150W metal halide lamp is started, after the visible light illumination cyclic degradation time is 10 minutes, a tail gas discharge port valve is opened to discharge tail gas, the NO content in the tail gas is 326.4ppb measured through a gas chromatography, and therefore the degradation rate of NO is 45.6%.
Example 3
Dispersing 100mg of zirconocene dichloride in 50ml of ethanol, performing ultrasonic treatment for 60min, stirring for 1.5h, uniformly mixing, transferring to an evaporation dish, and evaporating the solvent at 60-70 ℃. The evaporation pan is placed in a photocatalytic degradation device for detecting the photocatalytic degradation activity of NO, the flow rate of NO is adjusted to be 5mL/min, the dry air flow rate is 1.5L/min, the concentration of NO at the moment is 600ppb, a 150W metal halide lamp is started, the visible light illumination cyclic degradation time is 10 minutes, a tail gas discharge port valve is opened to discharge tail gas, the NO content in the tail gas is 296.4ppb measured through a gas chromatography, and therefore the degradation rate of NO is 50.6%.
Example 4
Dispersing 100mg of zirconocene dichloride in 50ml of ethanol, performing ultrasonic treatment for 50min, stirring for 1.5h, uniformly mixing, transferring to an evaporation dish, and evaporating the solvent at 60-70 ℃. The evaporation pan is placed in a photocatalytic degradation device for detecting the photocatalytic degradation activity of NO, the flow rate of NO is adjusted to be 2mL/min, the dry air flow rate is 1.5L/min, the concentration of NO at the moment is 240ppb, a 150W metal halide lamp is started, the visible light illumination cyclic degradation time is 10 minutes, a tail gas discharge port valve is opened to discharge tail gas, the NO content in the tail gas is 118.3ppb measured through a gas chromatography, and therefore the degradation rate of NO is 50.7%.
Example 5
Dispersing 100mg of zirconocene dichloride in 50ml of ethanol, performing ultrasonic treatment for 50min, stirring for 1.5h, uniformly mixing, transferring to an evaporation dish, and evaporating the solvent at 60-70 ℃. The evaporation pan is placed in a photocatalytic degradation device for detecting the photocatalytic degradation activity of NO, the flow rate of NO is adjusted to be 8mL/min, the dry air flow rate is 1.5L/min, the concentration of NO at this time is 960ppb, a 150W metal halide lamp is started, the visible light illumination cyclic degradation time is 10 minutes, a tail gas discharge port valve is opened to discharge tail gas, the NO content in the tail gas is 525.1ppb measured through a gas chromatography, and therefore the degradation rate of NO is 45.3%.
Example 6
Dispersing 100mg of zirconocene dichloride in 50ml of ethanol, performing ultrasonic treatment for 50min, stirring for 1.5h, uniformly mixing, transferring to an evaporation dish, and evaporating the solvent at 60-70 ℃. The evaporation pan is placed in a photocatalytic degradation device for detecting the photocatalytic degradation activity of NO, the flow rate of NO is adjusted to be 10mL/min, the dry air flow rate is 1.5L/min, the concentration of NO at the moment is 1120ppb, a 150W metal halide lamp is started, the visible light illumination cyclic degradation time is 10 minutes, a tail gas discharge port valve is opened to discharge tail gas, the NO content in the tail gas is 725.76ppb measured through a gas chromatography, and therefore the degradation rate of NO is 35.2%.
Example 7
Dispersing 100mg of zirconocene dichloride in 50ml of ethanol, performing ultrasonic treatment for 50min, stirring for 1.5h, uniformly mixing, transferring to an evaporation dish, and evaporating the solvent at 60-70 ℃. The evaporation pan is placed in a photocatalytic degradation device for detecting the photocatalytic degradation activity of NO, the flow rate of NO is adjusted to be 5mL/min, the dry air flow rate is 1.5L/min, the concentration of NO at the moment is 600ppb, a 150W metal halide lamp is started, the visible light illumination cyclic degradation time is 8 minutes, a tail gas discharge port valve is opened to discharge tail gas, the NO content in the tail gas is 330.6ppb measured through a gas chromatography, and therefore the degradation rate of NO is 44.9%.
Example 8
Dispersing 100mg of zirconocene dichloride in 50ml of ethanol, performing ultrasonic treatment for 50min, stirring for 1.5h, uniformly mixing, transferring to an evaporation dish, and evaporating the solvent at 60-70 ℃. The evaporation pan is placed in a photocatalytic degradation device for detecting the photocatalytic degradation activity of NO, the flow rate of NO is adjusted to be 5mL/min, the dry air flow rate is 1.5L/min, the concentration of NO at the moment is 600ppb, a 150W metal halide lamp is started, the visible light illumination cyclic degradation time is 12 minutes, a tail gas discharge port valve is opened to discharge tail gas, the NO content in the tail gas is 301.8ppb measured through a gas chromatography, and therefore the degradation rate of NO is 49.7%.
Comparative example 1
In the prior art, TiO is used2The steps of using the photocatalyst to catalyze and degrade nitrogen oxides are as follows:
dispersing 100mg of titanium dioxide in 50ml of ethanol, performing ultrasonic treatment, stirring, uniformly mixing, transferring to an evaporation dish, and evaporating the solvent. Placing the evaporating dish in a photocatalytic degradation device, detecting the photocatalytic degradation activity of NO, adjusting the flow rate of NO to be 5mL/min and the drying air flow rate to be 1.5L/min, wherein the concentration of NO is 600ppb, starting a 150W metal halide lamp, irradiating visible light for cyclic degradation for 10 minutes, opening a tail gas discharge port valve to discharge tail gas, and measuring the NO content in the tail gas through a gas chromatography to calculate the NO degradation rate. The NO degradation rate of the method is less than 10 percent.
It follows that titanium dioxide has little catalytic activity in the visible range.
Comparative example 2
In the prior art, TiO is used2As photocatalyst, ion doping is adopted to reduce band gap, and Fe is used below3+The steps for catalytic degradation of nitrogen oxides are, for example, as follows:
mixing titanium dioxide 100mg and FeCl3Dispersing 50mg in 50ml ethanol, performing ultrasonic treatment, stirring, mixing uniformly, transferring to an evaporation dish, and evaporating the solvent. The evaporation pan is placed in a photocatalytic degradation device for detecting the photocatalytic degradation activity of NO, the flow rate of NO is adjusted to be 5mL/min, the drying air flow rate is 1.5L/min, the concentration of NO at the moment is 600ppb, a metal halide lamp with a light source of 150W is started, the visible light illumination cycle degradation time is 10 minutes, a tail gas discharge port valve is opened to discharge tail gas, the NO content in the tail gas is 387.6ppb measured through a gas chromatography, and therefore the NO degradation rate is 35.4%.
It can be seen from the above examples and comparative examples that the method of the present invention can directly catalyze under visible light irradiation while ensuring the degradation rate of nitrogen oxides, thereby improving the utilization rate of solar energy, avoiding the procedures of ion doping, etc., and the process is simpler, and is more conducive to the industrial implementation of photocatalytic degradation of nitrogen oxides.
Claims (10)
1. A method for degrading nitrogen oxides by visible light catalysis is characterized by comprising the following steps: the NO is catalytically degraded by taking zirconocene dichloride as a photocatalyst and adopting a photocatalytic degradation method.
2. The method for degrading nitrogen oxides by visible light catalysis according to claim 1, wherein the method comprises the following steps: the method comprises the following steps:
(1) dispersing zirconocene dichloride in ethanol serving as a solvent, uniformly mixing by ultrasonic and stirring to form a mixed solution, transferring the mixed solution into an evaporation dish, and evaporating the solvent at the temperature of 60-70 ℃;
(2) and (2) placing the evaporation pan treated in the step (1) in a photocatalytic degradation device, introducing NO and dry air into the photocatalytic degradation device, and catalytically degrading NO under the irradiation of a light source.
3. The method for degrading nitrogen oxides by visible light catalysis as claimed in claim 2, wherein the method comprises the following steps: the dosage of the zirconocene dichloride in the step (1) is 100mg, and the dosage of the ethanol is 50 mL.
4. The method for visible light catalytic degradation of nitrogen oxides according to claim 2 or 3, wherein: the ethanol is absolute ethanol.
5. The method for degrading nitrogen oxides by visible light catalysis as claimed in claim 2, wherein the method comprises the following steps: in the step (1), the ultrasonic time is 40-60 min, and the stirring time is 1.5 h.
6. The method for degrading nitrogen oxides by visible light catalysis as claimed in claim 2, wherein the method comprises the following steps: the flow rate of NO introduced into the photocatalytic degradation device in the step (2) is 2-10mL/min, and the flow rate of dry air is 1-2L/min.
7. The method for degrading nitrogen oxides by visible light catalysis according to claim 6, wherein the method comprises the following steps: the flow rate of NO introduced into the photocatalytic degradation device in the step (2) is 5mL/min, and the flow rate of dry air is 1.5L/min.
8. The method for degrading nitrogen oxides by visible light catalysis as claimed in claim 2, wherein the method comprises the following steps: the light source in the step (2) is sunlight or light emitted by a metal halide lamp.
9. The method for degrading nitrogen oxides by visible light catalysis as claimed in claim 2, wherein the method comprises the following steps: and (3) circularly degrading NO in the step (2) in a photocatalytic degradation device, wherein the circular degradation time is 8-12 min.
10. The method for degrading nitrogen oxides by visible light catalysis as claimed in claim 2, wherein the method comprises the following steps: and (3) the time for circularly degrading NO in the photocatalytic degradation device in the step (2) is 10 min.
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