CN113769731B - VO for degrading dioxin at low temperature x -MoO x /TiO 2 Method for preparing and using catalyst - Google Patents
VO for degrading dioxin at low temperature x -MoO x /TiO 2 Method for preparing and using catalyst Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 58
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 229910010413 TiO 2 Inorganic materials 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 13
- 230000000593 degrading effect Effects 0.000 title claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 41
- 230000003197 catalytic effect Effects 0.000 claims abstract description 14
- 239000000843 powder Substances 0.000 claims abstract description 14
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 238000001354 calcination Methods 0.000 claims abstract description 7
- 239000002243 precursor Substances 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 7
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims abstract description 4
- 229940010552 ammonium molybdate Drugs 0.000 claims abstract description 4
- 235000018660 ammonium molybdate Nutrition 0.000 claims abstract description 4
- 239000011609 ammonium molybdate Substances 0.000 claims abstract description 4
- 239000000969 carrier Substances 0.000 claims abstract description 4
- 238000007873 sieving Methods 0.000 claims abstract description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 26
- 239000006004 Quartz sand Substances 0.000 claims description 11
- 239000012159 carrier gas Substances 0.000 claims description 11
- 239000012378 ammonium molybdate tetrahydrate Substances 0.000 claims description 7
- FIXLYHHVMHXSCP-UHFFFAOYSA-H azane;dihydroxy(dioxo)molybdenum;trioxomolybdenum;tetrahydrate Chemical compound N.N.N.N.N.N.O.O.O.O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O FIXLYHHVMHXSCP-UHFFFAOYSA-H 0.000 claims description 7
- 239000003546 flue gas Substances 0.000 claims description 7
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 6
- 238000006731 degradation reaction Methods 0.000 claims description 6
- 230000000630 rising effect Effects 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 230000015556 catabolic process Effects 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000004090 dissolution Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000010298 pulverizing process Methods 0.000 claims description 3
- 238000011049 filling Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 6
- 239000012855 volatile organic compound Substances 0.000 abstract description 5
- 238000001035 drying Methods 0.000 abstract description 3
- 230000004913 activation Effects 0.000 abstract description 2
- 230000009467 reduction Effects 0.000 abstract description 2
- 239000004566 building material Substances 0.000 abstract 1
- 238000000465 moulding Methods 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 45
- 239000007789 gas Substances 0.000 description 26
- 238000005406 washing Methods 0.000 description 15
- 239000010453 quartz Substances 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- 238000001514 detection method Methods 0.000 description 9
- 239000010936 titanium Substances 0.000 description 9
- 238000004458 analytical method Methods 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 238000005070 sampling Methods 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 239000000779 smoke Substances 0.000 description 4
- 229910000314 transition metal oxide Inorganic materials 0.000 description 4
- 229920000742 Cotton Polymers 0.000 description 3
- 239000012494 Quartz wool Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000005457 ice water Substances 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 239000011550 stock solution Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 229910003208 (NH4)6Mo7O24·4H2O Inorganic materials 0.000 description 1
- 231100000770 Toxic Equivalency Factor Toxicity 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 150000004827 dibenzo-1,4-dioxins Chemical class 0.000 description 1
- 150000004826 dibenzofurans Chemical class 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000000520 microinjection Methods 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000004056 waste incineration Methods 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01D53/8659—Removing halogens or halogen compounds
- B01D53/8662—Organic halogen compounds
-
- 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
- B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
-
- 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/28—Molybdenum
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to the technical field of building materials, and aims to provide a VO for degrading dioxin at low temperature x ‑MoO x /TiO 2 Methods of preparing and using the catalyst. The preparation method comprises the following steps: mixing ammonium metavanadate solution and ammonium molybdate solution to prepare precursor solution, and then mixing with nano TiO 2 Mixing and stirring the carriers to obtain a viscous paste; standing, drying, crushing, sieving and calcining to obtain the powder catalyst. The invention adds active component MoO x Modified VO x /TiO 2 The catalyst reduces the initial reduction temperature of the catalyst, reduces the activation energy required by chemical reaction, and obviously improves the catalytic removal efficiency of dioxin. The conversion rate of VOCs is obviously higher than that of other V-Ti catalysts, and the conversion rate reaches more than 90% at 250 ℃. The raw materials are relatively low, the preparation process is simple, the batch molding can be realized, and the popularization of industrial application is facilitated.
Description
Technical Field
The invention belongs to the technical field of flue gas treatment, and particularly relates to VO for degrading dioxin at low temperature x -MoO x /TiO 2 Methods of preparing and using the catalyst.
Background
Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) are highly toxic persistent organic pollutants that are typically produced during general combustion, metallurgical-related reactions, and municipal waste incineration. Due to its extremely high toxicity, emissions of PCDD/Fs in the environment must be tightly controlled. The catalytic degradation technology can thoroughly destroy dioxin, and is the most promising technology for controlling the tail end of flue gas.
Current studies show that catalysts can be divided into two classes according to the active component: noble metal catalysts and transition metal oxide catalysts. The noble metal catalyst is prepared by loading Pd, pt and the like to Al 2 O 3 、TiO 2 On the adsorption materials such as metal oxides or activated carbon, the mechanism of degrading dioxin is mainly hydrodechlorination reaction, because noble metal can lead H to 2 Or H 2 O and the like generate free hydrogen [ H ] which can generate reduction reaction with dioxin molecules on the surface of the catalyst]. However, noble metals are costly and very susceptible to SO in flue gases 2 And the acid gases react to cause poisoning, so that the industrial large-scale application is difficult. At this time, the transition metal oxide catalyst is in the field of view of researchers.
The transition metal oxide catalyst is usually a catalyst carrier having a transition metal such as a transition metal V, cr, mn, fe, ce, mo, cu supported thereon, for example, tiO 2 ，Al 2 O 3 And activated carbon. Common catalysts are SCR, V-Ti, mn-Ce catalysts, etc., but the catalytic degradation reaction of these catalysts is usually carried out at 160-300 ℃. If the catalytic efficiency of these catalysts is relatively low (150-190 ℃) to dioxin, the degradation efficiency of V-Ti catalyst to dioxin at 160℃is relatively reduced by 50% or more than 300 ℃.
Therefore, a VO capable of degrading dioxin under relatively low temperature conditions was developed x -MoO x /TiO 2 The catalyst has special significance for reducing the energy consumption of enterprises and realizing clean and environment-friendly production process.
Disclosure of Invention
The invention aims to solve the technical problems of overcoming the defects in the prior art and providing a VO for degrading dioxin at low temperature x -MoO x /TiO 2 Methods of preparing and using the catalyst.
In order to solve the technical problems, the invention adopts the following solutions:
provides VO for degrading dioxin at low temperature x -MoO x /TiO 2 A method for preparing a catalyst comprising the steps of:
(1) Dissolving ammonium metavanadate in ethanolamine to prepare ammonium metavanadate solution, and dissolving ammonium molybdate tetrahydrate in deionized water to prepare ammonium molybdate solution; then mixing the two to prepare a precursor solution;
(2) Precursor solution and nano TiO 2 Mixing and stirring the carriers to obtain a viscous paste; standing the paste for 36h, and drying at 105 ℃ for 24h;
(3) Pulverizing the dried block material, sieving with 60 mesh sieve, calcining at 450deg.C in air atmosphere for 3 hr to obtain VO x -MoO x /TiO 2 A powder catalyst;
the mass ratio of the raw material components is nano TiO 2 Ammonium metavanadate: ammonium molybdate tetrahydrate = 6:0.429:0.409.
Preferably, in the step (1), the solution is prepared by heating in a water bath at 50 ℃ and stirring sufficiently by magnetic force to promote dissolution.
In the step (3), the temperature rising rate is controlled to be 5 ℃/min during calcination, and standard air with the flow rate of 750mL/min is introduced.
The invention also provides a VO using the VO x -MoO x /TiO 2 Method for catalytic degradation of dioxin by powder catalyst, VO is carried out x -MoO x /TiO 2 Mixing the powder catalyst and quartz sand according to the volume ratio of 1:1, and filling the mixture into a reaction tube; introducing carrier gas containing dioxin to simulate flue gas, and realizing the degradation of the dioxin through catalytic oxidation reaction; the flow rate of simulated flue gas in the reaction tube is controlled to be 500mL/min, and the air-speed ratio is 10000h -1 The reaction temperature is 150-190 ℃.
Preferably, in the carrier gas, N 2 :O 2 The mass ratio of (2) is 89% to 11%.
Compared with the prior art, the invention has the beneficial effects that:
(1) The invention adds active component MoO x Modified VO x /TiO 2 Catalyst, reduced initial reduction of catalystThe temperature reduces the activation energy required by chemical reaction and obviously improves the catalytic removal efficiency of dioxin.
(2) The conversion rate of the V-Mo-Ti catalyst prepared by the method to VOCs (such as toluene) is obviously higher than that of other V-Ti catalysts, and the conversion rate at 250 ℃ is more than 90%.
(3) The catalyst prepared by the invention has the advantages of low raw materials, simple preparation process, batch forming and the like, and is beneficial to VO x -MoO x /TiO 2 The catalyst is popularized in industrial application.
Drawings
FIG. 1 is a graph showing the relationship between the removal efficiency (in terms of total TEQ) of dioxin and the temperature of the powder V5-Mo5-Ti catalyst in application examples 1 to 3.
FIG. 2 is a graph showing the conversion rate of 3 kinds of powder V-Ti based catalysts (V5-Mo 5-Ti, V5-Ti and V5-Ce 5-Ti) to toluene as a function of temperature by comparing example 4 with comparative examples 1 to 2.
Detailed Description
The invention provides a VO which is applied to a dioxin generating source device and a VOCs generating device and is used for treating refractory dioxin and VOCs x -MoO x /TiO 2 A catalyst. The catalyst is Nano-TiO 2 (nanometer TiO) 2 )、NH 4 VO 3 (ammonium metavanadate), (NH 4) 6 Mo 7 O 24 ·4H 2 O (ammonium molybdate tetrahydrate) as raw material and VO is prepared by wet impregnation method x -MoO x /TiO 2 A catalyst.
For better understanding of the technical solution of the present invention, application embodiments of the present invention will now be described.
Preparation example 1
VO x -MoO x /TiO 2 The preparation method of the powder catalyst comprises the following steps:
(1) Dissolving ammonium metavanadate in ethanolamine to prepare ammonium metavanadate solution, and dissolving ammonium molybdate tetrahydrate in deionized water to prepare ammonium molybdate solution; heating in 50deg.C water bath, and stirring with magnetic force to promote dissolution; then mixing the two to prepare a precursor solution;
(2) Precursor solution and nano TiO 2 Mixing and stirring the carriers to obtain a viscous paste; standing the paste for 36h, and drying at 105 ℃ for 24h; the mass ratio of the raw material components is nano TiO 2 Ammonium metavanadate: ammonium molybdate tetrahydrate = 6:0.429:0.409.
(3) Pulverizing the dried block material, sieving with 60 mesh sieve, calcining at 450deg.C in air atmosphere for 3 hr to obtain VO x -MoO x /TiO 2 A powder catalyst; the temperature rising rate is controlled to be 5 ℃/min during calcination, and standard air with the flow rate of 750mL/min is introduced.
In the following application examples 1 to 3, the production of the dioxin stock solution was achieved by the dioxin generating source device, the speed of injecting the dioxin stock solution with the microinjection pump was 1 μl/min, and the initial concentration of dioxin was 5.4ng I-TEQ Nm -3 The stability time of the dioxin generating device is 6-8 hours, after the dioxin generating device is stabilized, one sample is taken every 1 hour, and the catalytic reaction temperature is sequentially 150 ℃,170 ℃ and 190 ℃.
Application example 4 and comparative examples 1 to 2 were realized by a VOCs generating apparatus, toluene was bubbled by bubbling, the initial toluene concentration was 650ppm, and the carrier gas was N 2 ∶O 2 11% simulated smoke, flow rate of 100mL/min and air speed ratio of 10000h -1 。
Application example 1
Firstly, a small amount of quartz wool is arranged in a reaction tube, and after a dioxin generating source device is air-transported for 8 hours, a dioxin catalytic experiment is started. After the 3 samples before sampling are stabilized, 3mL of 5% VO is added into the reaction tube x -5％MoO x /TiO 2 The catalyst (powder) and 3mL quartz sand are mixed into particles, and a small amount of quartz cotton is plugged at both ends. The temperature of the combustion tube is 200 ℃, the temperature of the reaction tube is 150 ℃, the carrier gas flow is 500mL/min, and the air speed ratio is 10000h -1 . The tail of the reaction tube is connected with 2 gas washing cylinders for loading toluene to absorb tail gas, the gas washing cylinders adopt ice-water bath, and the sampling time of a stable sample and a catalytic sample is 1h. After sample changing, the tail part of the reaction tube and a silica gel tube connected with a gas washing bottle and the reaction tube are washed for 2 times and are transferred into the gas washing bottle for absorbing tail gas together, and the tail gas is stabilizedAnd (3) taking difference between the sample and the dioxin absorbed in the gas washing bottle to calculate the removal efficiency of the dioxin.
After pretreatment, detection and analysis of dioxin, the removal efficiency of dioxin at 150 ℃ reaches more than 86%.
Application example 2
Firstly, a small amount of quartz wool is arranged in a reaction tube, and after a dioxin generating source device is air-transported for 8 hours, a dioxin catalytic experiment is started. After the 3 samples before sampling are stabilized, 3mL of 5% VO is added into the reaction tube x -5％MoO x /TiO 2 The catalyst (powder) and 3mL quartz sand are mixed into particles, and a small amount of quartz cotton is plugged at both ends. The temperature of the combustion tube is 200 ℃, the temperature of the reaction tube is 170 ℃, the carrier gas flow is 500mL/min, and the air speed ratio is 10000h -1 . The tail of the reaction tube is connected with 2 gas washing cylinders for loading toluene to absorb tail gas, the gas washing cylinders adopt ice-water bath, and the sampling time of a stable sample and a catalytic sample is 1h. After sample replacement, the tail part of the reaction tube and a silica gel tube connected with the gas washing bottle and the reaction tube are washed for 2 times and are transferred to the gas washing bottle for absorbing tail gas, and the removal efficiency of dioxin is calculated by stabilizing the difference between dioxin absorbed in the sample and the gas washing bottle.
After pretreatment, detection and analysis of dioxin, the removal efficiency of dioxin reaches 90% at 170 ℃.
Application example 3
Firstly, a small amount of quartz wool is arranged in a reaction tube, and after a dioxin generating source device is air-transported for 8 hours, a dioxin catalytic experiment is started. After the 3 samples before sampling are stabilized, 3mL of 5% VO is added into the reaction tube x -5％MoO x /TiO 2 The catalyst (powder) and 3mL quartz sand are mixed into particles, and a small amount of quartz cotton is plugged at both ends. The temperature of the combustion tube is 200 ℃, the temperature of the reaction tube is 190 ℃, the flow rate of carrier gas is 500mL/min, and the air speed ratio is 10000h -1 . The tail of the reaction tube is connected with 2 gas washing cylinders for loading toluene to absorb tail gas, the gas washing cylinders adopt ice-water bath, and the sampling time of a stable sample and a catalytic sample is 1h. After sample replacement, the tail part of the reaction tube and a silica gel tube connected with a gas washing bottle and the reaction tube are washed for 2 times and are transferred into the gas washing bottle for absorbing tail gas, and difference is obtained by stabilizing the sample and absorbing dioxin in the gas washing bottleTo calculate the removal efficiency of dioxin.
After pretreatment, detection and analysis of dioxin, the removal efficiency of dioxin at 190 ℃ is close to 91%.
Application example 4
Firstly, 1.2mL of quartz sand is filled in a quartz tube, the quartz tube is heated by a vertical tube furnace and is stabilized for a period of time at 150 ℃ until the toluene concentration is stabilized at about 650 ppm. The carrier gas is N 2 :O 2 11% simulated smoke, flow rate of 100mL/min and air speed ratio of 10000h -1 . Then, the quartz tube was filled with 0.6mL of weighed quartz sand and 0.6mL of 5% VO x -5％MoO x /TiO 2 The catalyst (powder) mixed particles are prepared by taking 25 ℃ as a temperature gradient from 150 ℃ to 9 temperature points which are 150 ℃, 175 ℃, 200 ℃, 225 ℃,250 ℃,275 ℃,300 ℃, 325 ℃ and 350 ℃ respectively, preserving heat for 30min at each temperature point, and controlling the temperature rising rate to be 5 ℃/min.
Through the detection and analysis of a portable organic gas online detection system Thermo Trace 1300, 5% VO at 250℃ is found x -5％MoO x /TiO 2 The conversion rate of the catalyst to toluene reaches more than 90%, and the conversion rate is close to 100% at 275 ℃.
Comparative example 1
Firstly, 1.2mL of quartz sand is filled in a quartz tube, the quartz tube is heated by a vertical tube furnace and is stabilized for a period of time at 150 ℃ until the toluene concentration is stabilized at about 650 ppm. The carrier gas is N 2 :O 2 11% simulated smoke, flow rate of 100mL/min and air speed ratio of 10000h -1 . Then, the quartz tube was filled with 0.6mL of weighed quartz sand and 0.6mL of 5% VO x /TiO 2 The catalyst mixed particles are prepared by taking 25 ℃ as a temperature gradient from 150 ℃ to 9 temperature points which are 150 ℃, 175 ℃, 200 ℃, 225 ℃,250 ℃,275 ℃,300 ℃, 325 ℃ and 350 ℃ respectively, and preserving heat for 30min at each temperature point, wherein the temperature rising rate is controlled to be 5 ℃/min.
Through the detection and analysis of a portable organic gas online detection system Thermo Trace 1300, 5% VO at 250℃ is found x /TiO 2 The conversion rate of the catalyst to toluene is less than 80%, and the conversion rate is only close to 100% at the temperature of 300 ℃.
Comparative example 2
Firstly, 1.2mL of quartz sand is filled in a quartz tube, the quartz tube is heated by a vertical tube furnace and is stabilized for a period of time at 150 ℃ until the toluene concentration is stabilized at about 650 ppm. The carrier gas is N 2 :O 2 11% simulated smoke, flow rate of 100mL/min and air speed ratio of 10000h -1 . Then, the quartz tube was filled with 0.6mL of weighed quartz sand and 0.6mL of 5% VO x -5％CeO x /TiO 2 The catalyst mixed particles are prepared by taking 25 ℃ as a temperature gradient from 150 ℃ to 9 temperature points which are 150 ℃, 175 ℃, 200 ℃, 225 ℃,250 ℃,275 ℃,300 ℃, 325 ℃ and 350 ℃ respectively, and preserving heat for 30min at each temperature point, wherein the temperature rising rate is controlled to be 5 ℃/min.
Through the detection and analysis of a portable organic gas online detection system Thermo Trace 1300, 5% VO at 250℃ is found x -5％CeO x /TiO 2 The conversion rate of the catalyst to toluene is only about 70%, and the conversion rate is close to 100% at the temperature of 350 ℃.
Table 1 VO x -MoO x /TiO 2 Catalyst and other catalysts to catalyze comparison of dioxin and toluene performance
VO of the invention x -MoO x /TiO 2 The removal efficiency of the catalyst to dioxin at the low temperature of 150 ℃ can reach more than 86 percent, which is far superior to most catalysts; from the above data, it can be seen that the conversion of toluene at 250 ℃ can reach more than 90%, and is better than most transition metal oxide catalysts. In addition, the catalyst raw material nano titanium dioxide used in the invention has low price, simple preparation process, and wide application prospect, and is beneficial to industrial large-scale use.
Claims (4)
1.VO x -MoO x /TiO 2 The application method of the catalyst in the reaction of degrading dioxin at low temperature is characterized in that VO is adopted x -MoO x /TiO 2 Mixing the powder catalyst and quartz sand according to the volume ratio of 1:1, and filling the mixture into a reaction tube; introducing carrier gas containing dioxin as simulated flue gas, and realizing the degradation of the dioxin through catalytic oxidation reaction; the flow rate of simulated flue gas in the reaction tube is controlled to be 500mL/min, and the air-speed ratio is 10000h -1 The reaction temperature is 150-190 ℃;
the VO is x -MoO x /TiO 2 The catalyst is prepared by the following steps:
(1) Dissolving ammonium metavanadate in ethanolamine to prepare ammonium metavanadate solution, and dissolving ammonium molybdate tetrahydrate in deionized water to prepare ammonium molybdate solution; then mixing the two to prepare a precursor solution;
(2) Precursor solution and nano TiO 2 Mixing and stirring the carriers to obtain a viscous paste; after leaving the paste to stand 36h, it is dried 24h at 105 ℃;
(3) Pulverizing the dried block material, sieving with 60 mesh sieve, calcining at 450deg.C in air atmosphere for 3h to obtain VO x -MoO x /TiO 2 A powder catalyst;
the mass ratio of the raw material components is as follows: nanometer TiO 2 Ammonium metavanadate: ammonium molybdate tetrahydrate = 6:0.429:0.409.
2. The method according to claim 1, wherein in the step (1), the solution is prepared by heating in a water bath at 50 ℃ and stirring sufficiently by magnetic force to promote dissolution.
3. The method according to claim 1, wherein in the step (3), the temperature rising rate is controlled to be 5 ℃/min during the calcination, and the standard air with the flow rate of 750mL/min is introduced.
4. The method of claim 1, wherein, in the carrier gas,N 2 ∶O 2 the mass ratio of (2) is 89% to 11%.
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