CN112958070B - Method for preparing dioxin low-temperature degradation composite catalyst by ball milling method - Google Patents
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- 239000003054 catalyst Substances 0.000 title claims abstract description 88
- 230000015556 catabolic process Effects 0.000 title claims abstract description 46
- 238000006731 degradation reaction Methods 0.000 title claims abstract description 46
- 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 41
- 238000000034 method Methods 0.000 title claims abstract description 39
- 238000000498 ball milling Methods 0.000 title claims abstract description 21
- 239000002131 composite material Substances 0.000 title claims abstract description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 64
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 63
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 63
- 230000003197 catalytic effect Effects 0.000 claims abstract description 34
- 238000000227 grinding Methods 0.000 claims description 24
- 238000005406 washing Methods 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 13
- 239000002243 precursor Substances 0.000 claims description 13
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 11
- 229910017604 nitric acid Inorganic materials 0.000 claims description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 11
- 239000000843 powder Substances 0.000 claims description 10
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
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- 238000001354 calcination Methods 0.000 claims description 5
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- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
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- 239000002048 multi walled nanotube Substances 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 19
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- 238000006555 catalytic reaction Methods 0.000 abstract description 3
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- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 2
- 125000000524 functional group Chemical group 0.000 abstract description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 15
- 238000001179 sorption measurement Methods 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten(VI) oxide Inorganic materials O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 10
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
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- 239000001301 oxygen Substances 0.000 description 5
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 4
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
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- 229910052799 carbon Inorganic materials 0.000 description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- QXYJCZRRLLQGCR-UHFFFAOYSA-N dioxomolybdenum Chemical compound O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 1
- 229910009973 Ti2O3 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 231100000770 Toxic Equivalency Factor Toxicity 0.000 description 1
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- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- MBZLJHHVUVLDSX-UHFFFAOYSA-N cerium hydrochloride Chemical compound Cl.[Ce] MBZLJHHVUVLDSX-UHFFFAOYSA-N 0.000 description 1
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 description 1
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- 235000019441 ethanol Nutrition 0.000 description 1
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- 238000005470 impregnation Methods 0.000 description 1
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
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- -1 permanganate Chemical compound 0.000 description 1
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- 238000000527 sonication Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- GQUJEMVIKWQAEH-UHFFFAOYSA-N titanium(III) oxide Chemical compound O=[Ti]O[Ti]=O GQUJEMVIKWQAEH-UHFFFAOYSA-N 0.000 description 1
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 1
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- 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
- B01J23/20—Vanadium, niobium or tantalum
- B01J23/22—Vanadium
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- 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
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Abstract
The invention discloses a method for preparing a dioxin low-temperature degradation composite catalyst by a ball milling method, and belongs to the technical field of catalyst preparation. The carbon nano tube is used as a carrier, the carbon nano tube is pretreated in a strong acid environment, functional groups such as hydroxyl groups, carboxyl groups and the like are generated on the surface, the transition metal oxide is used as a catalytic component, the transition metal oxide is uniformly loaded on the surface of the carbon nano tube through ball milling, and the large-scale synthesis of the carbon nano tube composite catalyst with high dispersity and stable structure in a room temperature environment is realized through adjusting parameters such as ball milling process parameters, ball-to-material ratio and the like. The preparation method disclosed by the invention is mild in condition, green, environment-friendly and pollution-free, and short in preparation period. Compared with the traditional honeycomb titanium dioxide catalyst, the carbon nano tube composite catalyst prepared by the method has good thermochemical stability, is not easy to inactivate in the reaction process, and has good low-temperature catalytic reaction activity.
Description
Technical Field
The invention belongs to the technical field of catalyst preparation, and particularly relates to a method for preparing a dioxin low-temperature degradation composite catalyst by a ball milling method.
Background
The mechanochemical method is a typical harmless treatment process, and research and development are fast in recent years. The mechanical energy is transferred to the substance through the action of mechanical force, the substance generates physical and chemical reaction when receiving the action of mechanical force, the chemical property and the structure are changed, the reaction activity is improved, and the generated chemical reaction is excited and accelerated. The method consumes less energy, does not produce harmful byproducts in the treatment process, and is green and environment-friendly.
The carbon nanotube is a material with excellent physicochemical properties, and has unique adsorption characteristics, excellent electron mobility and electrical conductivity, excellent mechanical properties and good thermal and chemical stability, so that the carbon nanotube becomes an excellent catalyst carrier. However, carbon nanotubes have significant hydrophobicity, and it is difficult to effectively load the catalyst active component onto the surface of the carbon nanotubes using conventional chemical methods such as impregnation, coprecipitation, hydrothermal method, and the like. The sol-gel method is complicated in process, organic substances such as ethanol are required to be added as a solvent, redundant carbon is additionally introduced, and meanwhile, catalytic components are wrapped in catalytic particles to influence catalytic activity. The chemical method preparation process of the catalyst is complex, the cost is relatively high, and environmental problems such as waste water and the like are easily caused.
It is also a challenge to reduce the reaction temperature while improving the efficiency of catalytic degradation of dioxin. The catalyst nano structure is used as an active substance of a supported catalyst, and the shape and the size of the catalyst nano structure are important factors influencing the catalytic degradation of dioxin. Therefore, the size and the shape of the catalytic component are reasonably and accurately regulated, the catalyst is uniformly loaded on the surface of the carbon nano tube, and the catalytic activity can be improved. Although the carbon nanotube composite catalyst is used for degrading VOCs in the current stage of research, the preparation process has poor stability and high reaction temperature, so that the dioxin low-temperature degradation catalyst with uniform size and stable combination is difficult to obtain.
Disclosure of Invention
In order to solve at least one of the above technical problems, the present invention aims to provide a technical solution for preparing a dioxin low-temperature degradation catalyst in a large scale with a simple process.
In order to achieve the above object, a first aspect of the present invention provides a method for preparing a composite catalyst for low temperature degradation of dioxin by a ball milling method, comprising the steps of:
s1, placing the carbon nano tube in a concentrated acid solution for pretreatment, washing and filtering, washing with water until the pH value of the filtrate is neutral, and drying to obtain the pretreated carbon nano tube;
s2, uniformly mixing the pretreated carbon nanotubes and the catalytic component precursor to form a raw material, placing the raw material into a ball milling tank, and grinding the raw material into powder by using a grinding ball;
s3, calcining the ball-milled mixed powder for 3-6 h to obtain the dioxin low-temperature degradation composite catalyst,
wherein the catalytic component precursor comprises a salt or an oxide of at least one metal selected from V, W, Ti, Mn, Mo and Ce.
In some embodiments of the invention, the concentrated acid solution is a mixture of concentrated sulfuric acid and concentrated nitric acid. In some embodiments of the invention, the concentrated sulfuric acid is 70% to 98% by mass; the mass fraction of the concentrated nitric acid is 68-98 percent; mixing at a ratio of 1:3-3: 1. In some preferred embodiments of the present invention, the mass fraction of the concentrated sulfuric acid is 98%; in some preferred embodiments of the invention, the mass fraction of concentrated nitric acid is 68%; in some embodiments of the invention, the concentrated sulfuric acid and the concentrated nitric acid are mixed in a 1:1 ratio.
In some embodiments of the invention, the pretreatment is ultrasonic treatment for 5-60min, and the treatment is carried out for 1-10 h at 50-160 ℃ under stirring. In some embodiments of the invention, the pretreatment is sonication for 30 min. In some preferred embodiments of the invention, the treatment is carried out at 50 to 160 ℃ for 1 to 10 hours under stirring.
In some embodiments of the invention, the catalytic component precursor is selected from VO, V2O3、VO2、V2O5、WO3、W20O58、TiO、TiO2、Ti2O3、MnO、MnO2、Mn3O4、MoO2、Mo4O11、Mo17O47、Mo5O14、Mo8O23、Mo18O52、Mo9O26、MoO3CeO, vanadate, tungstate, titanate, permanganate, molybdate, cerium hydrochloride, cerium sulfate, cerium nitrate, carbonic acidOne or more of cerium.
In some embodiments of the invention, the catalytic component precursor comprises NH4VO3And TiO2. In some preferred embodiments of the invention, V in the catalyst is prepared2O5And TiO2In a ratio of 4: 91. In other preferred embodiments of the present invention, V2O5And TiO2In a ratio of 4: 86.
In other embodiments of the present invention, the catalytic component precursor comprises NH4VO3、TiO2And (NH)4)10W12O41·xH2O, wherein x is 0-5. Preferably, V in the catalyst prepared2O5、TiO2And WO3In a ratio of 4:72: 14.
In some embodiments of the present invention, the carbon nanotube is a single-walled or multi-walled carbon nanotube having a diameter of 8 to 100nm, a length of 1 to 50 μm, and a specific surface area of 40 to 400m2(ii) in terms of/g. In some embodiments of the present invention, the carbon nanotubes have a diameter of 20 to 30 nm.
In some embodiments of the invention, the mass of the carbon nanotubes is 5% to 95% of the total mass of the feedstock. In some embodiments of the invention, the mass of the carbon nanotubes is 5% or 10% of the total mass of the feedstock.
In some embodiments of the invention, the mass ratio of the grinding balls to the raw material is 5:1 to 30: 1. In some embodiments of the invention, the mass ratio of the grinding balls to the feedstock is 15:1, 20:1, or 25: 1.
In some embodiments of the invention, the rotation speed of the ball milling is 400-800 r/min, and the time of the ball milling is 2-10 h. In some embodiments of the invention, the rotation speed of the ball mill is 400r/min, and the ball milling time is 2h and 4 h.
In some embodiments of the invention, the ball-milled mixed powder is placed in a muffle furnace to be calcined for 2-6 h, wherein the calcination temperature is 400-600 ℃, and in some embodiments of the invention, the ball-milled mixed powder is placed in the muffle furnace to be calcined for 4h, and the calcination temperature is 450 ℃.
The second aspect of the present invention provides a composite catalyst for low-temperature degradation of dioxin prepared by the method of any one of the first aspects of the present invention.
The invention has the advantages of
Compared with the prior art, the invention has the following beneficial effects:
the invention provides a method for preparing a carbon nano tube composite catalyst for degrading dioxin at low temperature by a ball milling method, which comprises the steps of selecting a carbon nano tube as a carrier, pretreating the carbon nano tube in a strong acid environment, generating functional groups such as hydroxyl, carboxyl and the like on the surface, taking a transition metal oxide as a catalytic component, uniformly loading the transition metal oxide on the surface of the carbon nano tube by ball milling, and realizing large-scale synthesis of the carbon nano tube composite catalyst with high dispersity and stable structure in a room temperature environment by adjusting parameters such as ball milling process parameters, ball-to-material ratio and the like. Specifically, the method comprises the following steps:
the preparation method disclosed by the invention is mild in condition, green, environment-friendly and pollution-free, and short in preparation period.
The carbon nano tube composite catalyst prepared by the method is applied to catalytic degradation of dioxin, the carbon nano tube has good adsorption characteristic, excellent electron mobility and electrical conductivity, excellent mechanical property and good thermal and chemical stability, the catalytic components are uniformly loaded on the surface of the carbon nano tube in the form of nano particles, the carbon nano tube provides sufficient adsorption sites, the reaction heat can be directly and effectively transferred, the reaction temperature is reduced, and thus the low-temperature degradation of the dioxin in the carbon nano tube composite catalyst is realized.
Compared with the traditional honeycomb titanium dioxide catalyst, the carbon nano tube composite catalyst prepared by the method has good thermochemical stability, is not easy to inactivate in the reaction process, and has good low-temperature catalytic reaction activity.
Drawings
FIG. 1 shows a scanning electron micrograph of a catalyst prepared in example 1 of the present invention.
FIG. 2 shows a transmission electron micrograph of the catalyst prepared in example 1 of the present invention.
FIG. 3 shows a scanning electron micrograph of a catalyst prepared according to example 6 of the present invention.
FIG. 4 shows the O1s spectra of the catalysts prepared in examples 1, 2, 4 of the present invention.
FIG. 5 shows BET characterization plots of catalysts prepared in examples 1-4 of the present invention.
FIG. 6 is a graph showing the degradation efficiency of dioxin in the presence of catalysts prepared in examples 1 to 6 of the present invention.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects solved by the present invention more apparent, the present invention is further described in detail below with reference to the following embodiments.
Examples
The following examples are used herein to demonstrate preferred embodiments of the invention. It will be appreciated by those of skill in the art that the techniques disclosed in the examples which follow represent techniques discovered by the inventor to function in the invention, and thus can be considered to constitute preferred modes for its practice. Those of skill in the art should, in light of the present disclosure, appreciate that many changes can be made in the specific embodiments which are disclosed and still obtain a like or similar result without departing from the spirit or scope of the invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs and the disclosures and references cited herein and the materials to which they refer are incorporated by reference.
Those skilled in the art will recognize, or be able to ascertain using no more than routine experimentation, many equivalents to the specific embodiments of the invention described herein. Such equivalents are intended to be encompassed by the following claims.
The experimental methods not specifically described in the following examples are conventional methods unless otherwise specified. The instruments used in the following examples are, unless otherwise specified, laboratory-standard instruments; the test materials used in the following examples were purchased from a conventional biochemical reagent store unless otherwise specified.
Example 1 preparation method of Dioxin Low temperature degradation catalyst Cata-1
Placing a carbon nano tube (Jiangsu Xiancheng nano material science and technology ltd., model: XFM34, pipe diameter > 50nm) in a mixed solution of concentrated sulfuric acid (98%) and concentrated nitric acid (68%) at a ratio of 1:1, carrying out ultrasonic treatment for 30min, washing, filtering, washing with water until the pH value of the filtrate is neutral, and drying to obtain the pretreated carbon nano tube. According to the catalyst carbon nano tube: vanadium pentoxide: mixing the precursors according to the proportion of 5:4:91, adding a corresponding matched zirconia grinding ball according to the ball-to-material ratio of 20:1, grinding for 2h under the condition of 400r/min, and then putting the powder into a muffle furnace to calcine for 4h at 450 ℃ to obtain the dioxin low-temperature degradation catalyst Cata-1, wherein the specification of the ball-milling tank is 0.5L.
As can be seen from fig. 1, the catalyst powder is more uniformly dispersed in the mixture with the carbon nanotubes. As can be seen from fig. 2, the catalyst nanoparticles are uniformly dispersed on the surface of the carbon nanotubes.
Example 2 preparation method of Dioxin Low temperature degradation catalyst Cata-2
Placing a carbon nano tube (Jiangsu Xiancheng nano material science and technology ltd., model: XFM34, pipe diameter > 50nm) in a mixed solution of concentrated sulfuric acid (98%) and concentrated nitric acid (68%) at a ratio of 1:1, treating for ultrasonic treatment for 30min, washing, filtering, washing with water until the pH value of the filtrate is neutral, and drying to obtain the pretreated carbon nano tube. According to the catalyst carbon nano tube: vanadium pentoxide: mixing the precursors according to the proportion of 10:4:86, adding a corresponding matched zirconia grinding ball according to the ball-to-material ratio of 20:1, grinding for 2 hours under the condition of 400r/min, and then putting the powder into a muffle furnace to calcine for 4 hours at 450 ℃ to obtain the dioxin low-temperature degradation catalyst Cata-2, wherein the specification of the ball-milling tank is 0.5L.
Example 3 preparation method of Dioxin Low temperature degradation catalyst Cata-3
Placing a carbon nano tube (Jiangsu Xiancheng nano material science and technology ltd., model: XFM34, pipe diameter > 50nm) in a mixed solution of concentrated sulfuric acid (98%) and concentrated nitric acid (68%) at a ratio of 1:1, treating for ultrasonic treatment for 30min, washing, filtering, washing with water until the pH value of the filtrate is neutral, and drying to obtain the pretreated carbon nano tube. According to the catalyst carbon nano tube: vanadium pentoxide: titanium dioxide: mixing the precursor with tungsten trioxide in a ratio of 10:4:72:14, adding a corresponding matched zirconium oxide grinding ball according to a ball-to-material ratio of 20:1, grinding for 2 hours under the condition of 400r/min, and then placing the powder in a muffle furnace to calcine for 4 hours at 450 ℃ to obtain the dioxin low-temperature degradation catalyst Cata-3, wherein the specification of a ball grinding tank is 0.5L.
Example 4 preparation method of Dioxin Low temperature degradation catalyst Cata-4
Preparing the carbon nano tube:
putting the purchased Ni (8%)/C catalyst into a quartz tube, heating to 500 ℃, injecting absolute ethyl alcohol (the flow rate is 0.3mL/H) by using a microsyringe after the reaction temperature is constant, allowing the absolute ethyl alcohol to enter the quartz tube through a vaporizer for reaction, and determining that a gas product in the reaction process contains a large amount of H2Small amount of CO, trace amount of CH4And CO2. The prepared product has the tube diameter of 20-30nm, uniform distribution, unobvious winding phenomenon and better quality of the carbon nano tube.
And (2) placing the prepared carbon nano tube in a mixed solution of concentrated sulfuric acid (98%) and concentrated nitric acid (68%) in a ratio of 1:1 for ultrasonic treatment for 30min, washing and filtering, washing with water until the pH value of the filtrate is neutral, and drying to obtain the pretreated carbon nano tube. According to the catalyst carbon nano tube: vanadium pentoxide: titanium oxide: mixing the precursor with tungsten trioxide in a ratio of 10:4:72:14, adding a corresponding matched zirconium oxide grinding ball according to a ball-to-material ratio of 20:1, grinding for 2 hours under the condition of 400r/min, and then placing the powder in a muffle furnace to calcine for 4 hours at 450 ℃ to obtain the dioxin low-temperature degradation catalyst Cata-4, wherein the specification of a ball grinding tank is 0.5L.
Example 5 preparation method of Dioxin Low temperature degradation catalyst Cata-5
Carbon nanotubes were prepared as described in example 4 without concentrated acid treatment.
According to the catalyst untreated carbon nanotubes: vanadium pentoxide: titanium dioxide: mixing the precursor with tungsten trioxide in a ratio of 10:4:72:14, adding a corresponding matched zirconium oxide grinding ball according to a ball-to-material ratio of 20:1, grinding for 2 hours under the condition of 400r/min, and then placing the powder in a muffle furnace to calcine for 4 hours at 450 ℃ to obtain the dioxin low-temperature degradation catalyst Cata-5, wherein the specification of a ball grinding tank is 0.5L.
Example 6 preparation method of Dioxin Low temperature degradation catalyst Cata-6
Carbon nanotubes were prepared as described in example 4.
And (2) placing the prepared carbon nano tube into a mixed solution of concentrated sulfuric acid (98%) and concentrated nitric acid (65%) in a ratio of 1:1 for ultrasonic treatment for 30min, treating for 1h at 50 ℃ under stirring, washing and filtering, washing with water until the pH value of the filtrate is neutral, and drying to obtain the pretreated carbon nano tube. According to the catalyst vanadium pentoxide: titanium dioxide: mixing the precursor according to the mass ratio of 20:1 of tungsten trioxide to 72:14, adding the corresponding zirconium oxide grinding balls, grinding for 2 hours under the condition of 400r/min, and recently, putting the powder in a muffle furnace and calcining for 4 hours at 450 ℃ to obtain the low-temperature degradation catalyst. According to the carbon nano tube: mixing the catalyst in a ratio of 10:90, adding a corresponding matched zirconia grinding ball according to the mass ratio of 20:1 in a ball-to-material ratio of 0.5L in a ball-milling tank, grinding for 2h under the condition of 400r/min, and then putting the powder in a muffle furnace to calcine for 4h at 450 ℃ to obtain the dioxin low-temperature degradation catalyst Cata-6.
As can be seen from fig. 3, the catalyst prepared by preparing the catalyst first and then mixing the catalyst with the carbon nanotubes is prone to catalyst agglomeration, and reduces the catalytic activity of the catalyst.
Example 7 analysis of valence states of elements on the surface of catalyst by X-ray photoelectron spectroscopy (XPS)
The Cata-1, Cata-2 and Cata-4 prepared above are analyzed for the valence state of surface elements by X-ray photoelectron spectroscopy (XPS), and the instrument model is Thermo ESCALAB 250 Xi.
The results are shown in FIG. 4. Deconvoluting the spectral peak of O1s to obtain two spectral peaks, belonging respectively to two different types of oxygen: the spectral peak between 529.8-530.3eV is attributed to lattice oxygen Oβ(ii) a The spectral peak between 531.5-532.0eV is attributed to the chemical adsorption of oxygen O on the surface of the catalystα. Middle table of three catalystsThe oxygen sequence of the surface chemical adsorption is Cata-4(0.18)>Cata-2(0.13)＝Cata-1(0.13)。
The result shows that the carbon nano tube prepared in the laboratory has more chemisorption oxygen after pretreatment, and the chemisorption oxygen is beneficial to improving the degradation activity of the catalyst.
Example 8N2Determination of specific surface area, pore volume and pore size distribution of catalyst by physical adsorption method
By using N2The information such as the specific surface area, pore volume and pore size distribution of the Cata-1, Cata-2, Cata-3 and Cata-4 catalysts prepared above was measured by physical adsorption method. Before testing, the temperature is raised to 300 ℃ for vacuum desorption for 4h, N2The adsorption temperature was 77K. At p/p0About 0.5 to 0.8, there is a sudden increase in the adsorption capacity. And obtaining the adsorption and desorption isothermal curve of the prepared catalyst.
The results are shown in FIG. 5. N of the prepared catalyst2The adsorption-desorption isotherms are typical type IV isotherms (IUPAC classification), indicating that the four catalysts studied are all mesoporous materials and that the N of the catalyst is2The adsorption-desorption isotherm curve has an H3 hysteresis loop, indicating that the pore structure of the catalyst is a wedge-shaped pore formed by a loose packing of plate-like particles. Through comparison, the Cata-4 prepared by using the carbon nano tube with the tube diameter of 20-30nm has the largest specific surface area and can provide the largest catalytic active sites for pollutant degradation.
Example 9 application of Dioxin Low temperature degradation catalyst prepared in examples 1-6
The dioxin low-temperature degradation catalysts Cata-1, Cata-2, Cata-3, Cata-4, Cata-5 and Cata-6 prepared in the examples 1 to 6 are used for the catalytic degradation of dioxin, and the reaction formula is as follows:
C12HnCl8-nO2+O2→H2O+CO2+HCl
C12HnCl8-nO+O2→H2O+CO2+HCl
wherein n is 0 to 7.
The reaction conditions are as follows: the catalyst is placed in a fixed bed reactor, the loading of the catalyst is 2mL, and the catalyst is dioxaneEnglish origin concentration 4.7ng I-TEQ/Nm3Introduction of N2(450mL/min) with O2(50mL/min) at 160 ℃ or 180 ℃.
The catalytic degradation efficiency of each catalyst for dioxin 1 hour after the catalytic reaction is shown in fig. 6, and it can be seen from fig. 6 that:
at the temperature of 160 ℃, the catalytic degradation efficiency of the Cata-1, the Cata-2, the Cata-3, the Cata-4, the Cata-5 and the Cata-6 to the dioxin is 46 percent, 52 percent, 56 percent, 72 percent, 50 percent and 48 percent respectively.
The catalytic degradation efficiency of the Cata-1, Cata-2, Cata-3, Cata-4, Cata-5 and Cata-6 to dioxin at 180 ℃ is 66%, 74%, 77%, 87%, 67% and 65%, respectively.
Therefore, when the reaction temperature is 180 ℃, the catalytic degradation efficiency of each catalyst to dioxin is obviously higher than that when the reaction temperature is 160 ℃.
In addition, the catalytic degradation efficiency of Cata-2 to dioxin is higher than that of Cata-1 at the same temperature, which shows that the catalytic degradation efficiency can be improved by improving the content of the carbon nano tube. The catalytic degradation efficiency of Cata-3 to dioxin is higher than that of Cata-2, which shows that the catalytic degradation efficiency can be improved by adding the components of the cocatalyst. The catalytic degradation efficiency of Cata-4 to dioxin is higher than that of Cata-3, which shows that the catalytic degradation efficiency can be improved by adjusting the pipe diameter of the carbon nano tube. The catalytic degradation efficiency of Cata-5 to dioxin is obviously lower than that of Cata-3, which shows that the catalytic activity of the catalyst is reduced by adopting the carbon nano tube which is not pretreated. The catalyst Cata-6 prepared by preparing the catalyst first and then mixing the catalyst with the carbon nano tube also shows lower catalytic activity.
All documents referred to herein are incorporated by reference into this application as if each were individually incorporated by reference. Furthermore, it should be understood that various changes and modifications of the present invention can be made by those skilled in the art after reading the above teachings of the present invention, and these equivalents also fall within the scope of the present invention as defined by the appended claims.
Claims (8)
1. A method for preparing a composite catalyst for low-temperature degradation of dioxin by a ball milling method is characterized by comprising the following steps:
s1, placing the carbon nano tube in a mixed solution of concentrated sulfuric acid and concentrated nitric acid for ultrasonic treatment for 5-60min, washing and filtering, washing with water until the pH value of the filtrate is neutral, and drying to obtain the pretreated carbon nano tube;
s2, uniformly mixing the pretreated carbon nanotubes and the catalytic component precursor to form a raw material, placing the raw material in a ball milling tank, and grinding the raw material into powder by using a grinding ball;
s3, calcining the ball-milled mixed powder for 3-6 h to obtain the dioxin low-temperature degradation composite catalyst,
wherein the catalytic component precursor comprises a salt or an oxide of at least one metal selected from V, W, Ti, Mn, Mo and Ce.
2. The method according to claim 1, characterized in that the mass fraction of the concentrated sulfuric acid is 70-98%; the mass fraction of the concentrated nitric acid is 68-98 percent; mixing at a ratio of 1:3-3: 1.
3. The method of claim 1, wherein the carbon nanotubes are single-walled or multi-walled carbon nanotubes having a diameter of 8 to 100nm, a length of 1 to 50 μm, and a specific surface area of 40 to 400m2/g。
4. The method of claim 1, wherein the mass of the carbon nanotubes is 5% to 95% of the total mass of the feedstock.
5. The method according to claim 1, wherein the mass ratio of the grinding balls to the raw material is 5:1 to 30: 1.
6. The method of claim 5, wherein the rotation speed of the ball mill is 400-800 rpm, and the ball milling time is 2-10 h.
7. The method as claimed in claim 1, wherein the mixed powder after ball milling is calcined in a muffle furnace at a temperature of 400-600 ℃.
8. The dioxin low-temperature degradation composite catalyst prepared by the method of any one of claims 1 to 7.
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