CN107321349A - A kind of fento coated carbon nano-tube composite material of carried metal active component and its preparation and application - Google Patents
A kind of fento coated carbon nano-tube composite material of carried metal active component and its preparation and application Download PDFInfo
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- CN107321349A CN107321349A CN201710494729.2A CN201710494729A CN107321349A CN 107321349 A CN107321349 A CN 107321349A CN 201710494729 A CN201710494729 A CN 201710494729A CN 107321349 A CN107321349 A CN 107321349A
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- fento
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- carbon nano
- active component
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- 239000002131 composite material Substances 0.000 title claims abstract description 75
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 58
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 55
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 40
- 239000002184 metal Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000002243 precursor Substances 0.000 claims abstract description 20
- 239000003054 catalyst Substances 0.000 claims abstract description 19
- 238000010438 heat treatment Methods 0.000 claims abstract description 18
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 15
- 150000003624 transition metals Chemical class 0.000 claims abstract description 15
- 239000000835 fiber Substances 0.000 claims abstract description 14
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 13
- 239000010935 stainless steel Substances 0.000 claims abstract description 13
- 238000010792 warming Methods 0.000 claims abstract description 10
- 239000012298 atmosphere Substances 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 8
- 238000004519 manufacturing process Methods 0.000 claims abstract description 7
- 230000001681 protective effect Effects 0.000 claims abstract description 7
- 239000007789 gas Substances 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 238000005245 sintering Methods 0.000 claims description 13
- 238000004062 sedimentation Methods 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 230000001590 oxidative effect Effects 0.000 claims description 7
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 229920002522 Wood fibre Polymers 0.000 claims description 4
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 claims description 3
- QNZRVYCYEMYQMD-UHFFFAOYSA-N copper;pentane-2,4-dione Chemical compound [Cu].CC(=O)CC(C)=O QNZRVYCYEMYQMD-UHFFFAOYSA-N 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- HYZQBNDRDQEWAN-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;manganese(3+) Chemical compound [Mn+3].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O HYZQBNDRDQEWAN-LNTINUHCSA-N 0.000 claims description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 2
- -1 acetylacetone copper Chemical class 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- BKFAZDGHFACXKY-UHFFFAOYSA-N cobalt(II) bis(acetylacetonate) Chemical compound [Co+2].CC(=O)[CH-]C(C)=O.CC(=O)[CH-]C(C)=O BKFAZDGHFACXKY-UHFFFAOYSA-N 0.000 claims description 2
- 230000000593 degrading effect Effects 0.000 claims description 2
- 239000005416 organic matter Substances 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 239000002025 wood fiber Substances 0.000 claims description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims 2
- 125000002252 acyl group Chemical group 0.000 claims 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
- 229910052737 gold Inorganic materials 0.000 claims 1
- 239000010931 gold Substances 0.000 claims 1
- 230000007704 transition Effects 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 14
- 238000000034 method Methods 0.000 abstract description 5
- 238000001035 drying Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 10
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 8
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 6
- 239000007800 oxidant agent Substances 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 230000003247 decreasing effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000002048 multi walled nanotube Substances 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000000969 carrier Substances 0.000 description 3
- 239000007857 degradation product Substances 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 238000010494 dissociation reaction Methods 0.000 description 3
- 230000005593 dissociations Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 238000007493 shaping process Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 238000005253 cladding Methods 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 238000010009 beating Methods 0.000 description 1
- RRTCFFFUTAGOSG-UHFFFAOYSA-N benzene;phenol Chemical compound C1=CC=CC=C1.OC1=CC=CC=C1 RRTCFFFUTAGOSG-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000002717 carbon nanostructure Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- WQPDQJCBHQPNCZ-UHFFFAOYSA-N cyclohexa-2,4-dien-1-one Chemical compound O=C1CC=CC=C1 WQPDQJCBHQPNCZ-UHFFFAOYSA-N 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052752 metalloid Inorganic materials 0.000 description 1
- 150000002738 metalloids Chemical class 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000002109 single walled nanotube Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000009279 wet oxidation reaction Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
- A62D3/30—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents
- A62D3/38—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents by oxidation; by combustion
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
- B01J35/397—Egg shell like
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Toxicology (AREA)
- General Chemical & Material Sciences (AREA)
- Business, Economics & Management (AREA)
- Emergency Management (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to the technical field of fixed bed catalyst, fento coated carbon nano-tube composite material and its preparation and application of a kind of carried metal active component are disclosed.Methods described is：(1) fento composite material precursor and drying is made by wet paper manufacturing method in stainless steel fibre, wood-fibred and CNT, is then sintered in protective gas, obtains carrier；(2) transition metal precursor and carrier are placed in reaction unit, in protective gas, are warming up to the temperature that transition metal precursor can gasify or distil, constant temperature；The temperature that being continuously heating to transition metal precursor can decompose is deposited, cooling, obtains deposit；(3) in the atmosphere of air, deposit is calcined, cools down, obtains composite.The method of the present invention is simple, and prepared composite has preferable catalytic effect, and Stability Analysis of Structures can effectively reduce bed pressure drop, and mass transfer enhancement heat transfer lifts catalytic efficiency.
Description
Technical field
Wet paper manufacturing method is utilized the present invention relates to one kind, prepared by temperature programming sintering technology and chemical vapour deposition technique technology
The fento coated carbon nano-tube composite material of carried metal active component and preparation method and application.
Background technology
CNT is found to be 1991 first, and Sumio Iijima are found that depositing for multi-walled carbon nanotube by Electronic Speculum
Attracting increasing concern from this CNT.CNT has an excellent mechanical strength, electric conductivity, and
Chemical stability.Compared to other carbon materials such as activated carbon etc., CNT can be applied to more areas, because it has
High selectivity and the diversity of structure.In addition, CNT is also a kind of preferable adsorbent, can be employed with it is organic
In the processing of waste water.CNT can also be used as catalyst, and it avoids the high cost easy in inactivation of noble metal catalyst
Shortcoming, sometimes even can reach more preferable effect.Yang et al. (S.Yang, X.Wang, H.Yang, et al.Influence
of the different oxidation treatment on the performance of multi-walled
carbon nanotubes in the catalytic wet air oxidation of phenol[J].Journal of
Hazardous Materials.233-234 (3) (2012) 18-24) multi-walled carbon nanotube is applied to catalytic wet oxidation benzene
Phenol, it is found that it has activity well.Soria-S á nchez et al. (Soria-S á nchez, M., et al., Carbon
nanostrutured materials as direct catalysts for phenol oxidation in aqueous
phase.Applied Catalysis B Environmental,2011.104(1–2):P.101-109.) also obtained identical
Result.While many research ((1) Y.X.Yang, R.K.Singh, P.A.Webley.Hydrogen adsorption in
transition metal carbon nano-structures[J].Adsorption.14(2)(2008)265-274.(2)
C.K.Yang,J.Z.And,J.P.Lu.Complete Spin Polarization for a Carbon Nanotube with
an Adsorbed Atomic Transition-Metal Chain[J].Nano Letters.4(4)(2004)561-563.)
It has also been found that CNT can be used in treatment of Organic Wastewater as carrier, carried metal as catalyst.But CNT
Particle diameter is smaller, if directly applied in fixed bed reactors, bed resistance can be caused excessive, and the uneven grade of heat and mass transport lacks
Point.The fixed bed reactors that can be operated continuously application industrially and its extensively, and CNT these shortcomings are limited
Its application on fixed bed reactors, so that its industrial applicibility is substantially reduced.
In order to solve the above problems, CNT is combined by the present invention with fento composite first, can kept
In the case of CNT activity, reduce its bed resistance in fixed bed reactors, so that mass transfer enhancement conducts heat, improve
The practical value of catalyst.
The content of the invention
It is an object of the invention to provide a kind of fento coated carbon nano-tube composite material of carried metal active component and its
Preparation method, high to change existing covering material catalyst cost of manufacture, manufacturing conditions are harsh, unstable product quality, living
Property component load it is uneven, the shortcomings of poor practicability.The product that the present invention is prepared is provided simultaneously with the electric conductivity of CNT,
The heat endurance of chemical stability and stainless steel fibre, ductility and corrosion resistance, are applied in fixed bed catalyst
Bed pressure drop and increase contacting efficiency can effectively be reduced.The active component loaded simultaneously using vapour deposition process can be uniform
Ground is distributed in carrier surface, and particle diameter is smaller, lifts catalytic efficiency.
The thickness of the fento coated carbon nano-tube composite material of carried metal active component prepared by the present invention is 1-2mm,
The present invention composite be used as fixed bed catalyst when, compared to traditional fixed bed catalyst, can be made using this product
Fixed bed bed pressure drop reduction by more than 50%, catalytic efficiency lifting 20%-100%, during for liquid phase reactor, the leaching of active component
Extracting rate can decrease below 1mg/L, and pollutants removal rate reaches as high as 100%.In view of above advantage, the present invention is for other
The preparation of cladding metalloid support materials has reference.
The purpose of the present invention is achieved through the following technical solutions：
A kind of preparation method of the fento coated carbon nano-tube composite material of carried metal active component, including following step
Suddenly：
(1) fento composite material precursor is made by wet paper manufacturing method in stainless steel fibre, wood-fibred and CNT
And dry；
(2) it will be sintered by dry fento composite material precursor in protective gas, obtain fento cladding
Carbon nano tube compound material carrier；
(3) transition metal precursor and fento coated carbon nano-tube composite material carrier are placed in reaction unit, protected
In shield property gas, the temperature that transition metal precursor can gasify or distil is warming up to, constant temperature is for a period of time；It was continuously heating to
The temperature that crossing metal precursor can decompose is deposited, and natural cooling obtains deposit；
(4) in the atmosphere of air, deposit is calcined 120~360min in 400-500 DEG C, cooling obtains gold-supported
Belong to the fento coated carbon nano-tube composite material of active component.
Wood-fibred described in step (1) is needle-leaved wood fibre and/or broad-leaved wood fiber.
Stainless steel fibre described in step (1)：Wood-fibred：The mass ratio of CNT is (3~8)：10：(1~6)；
The condition dried described in step (1) is 100 DEG C~110 DEG C dry 30~120min.
The temperature sintered described in step (2) is 950-1100 DEG C of 15~30min of constant temperature；The condition of the sintering is preferably
480 DEG C, 480 DEG C of 10~30min of constant temperature, then with 3~7 DEG C/min speed liter are risen to from room temperature with 3~7 DEG C/min speed
Temperature is to 950~1100 DEG C, then at 950-1100 DEG C of 15~30min of constant temperature.
The time of constant temperature described in step (3) is 30~120min, the heating rate of continuation heating for 1~3 DEG C/
Min, the sedimentation time is 30~60min, and the consumption of the transition metal precursor is fento enveloped carbon nanometer tube composite wood
Expect the 1%~30% of carrier quality；
Stainless steel fibre model SS-316L described in step (1), length is 1-5mm, a diameter of 6.5 μm.Wood-fibred is beaten
The degree of beating is 25 °, and water content is 90%；CNT is multi-walled carbon nanotube or single-walled carbon nanotube.
Protective gas described in step (2), (3) is nitrogen, helium or argon gas.Described protective gas atmosphere passes through multiple
Lead to the operation of protection gas after vacuumizing repeatedly again to realize.
Transition metal precursor described in step (3) is transition metal organic salt, including acetylacetone copper, acetylacetone,2,4-pentanedione
In iron, acetylacetone,2,4-pentanedione ferrous (II), acetylacetone cobalt (II), manganese acetylacetonate (II) it is a kind of and more than.
The fento coated carbon nano-tube composite material of the carried metal active component is prepared by the above method.
The fento coated carbon nano-tube composite material of the carried metal active component is used as fixed bed catalyst.It is described solid
Bed catalyst catalyzing oxidizing degrading organism.The organic matter is phenol and its derivatives.
The pore size of the composite of the application is adjustable, even structure, and load capacity is high, easily prepares, with preferable machine
Tool intensity, applied to fixed bed reactors, can significantly reduce bed resistance, increase contacting efficiency, while tridimensional network
Channel, air-teturning mixed phenomenon and radial diffusion limitation etc., lifting absorption and catalytic efficiency can greatly be eliminated.
The Active components distribution loaded in the composite of the application is uniform, and composite structure is stable, with preferable
Catalytic activity.
The present invention has the following advantages that compared with prior art：
(1) catalyst carrier low manufacture cost, preparation method is simple, and product quality is stable, works well.
(2) active component Load Balanced in the composite of the application, grain diameter is smaller, and catalytic effect is improved；
(3) electric conductivity of CNT is maintained as carrier using stainless steel fibre, chemical stability and stainless
The heat endurance of steel fibre, ductility and corrosion resistance.
(4) stainless steel fibre carrier can effectively reduce bed pressure drop, mass transfer enhancement heat transfer, lifting as large pore material
Catalytic efficiency.
Brief description of the drawings
Fig. 1 is the microstructure (a) and carried metal of fento coated carbon nano-tube composite material carrier prepared by embodiment 1
The microstructure (b) of fento coated carbon nano-tube composite material after active component；
Fig. 2 is the XRD of the fento coated carbon nano-tube composite material of carried metal active component prepared by embodiment 1；
Fig. 3 is the TPR figures of the fento coated carbon nano-tube composite material of carried metal active component prepared by embodiment 1；
Fig. 4 is the fento coated carbon nano-tube composite material catalysis oxidation of carried metal active component prepared by embodiment 1
The activity curve figure of m-methyl phenol.
Embodiment
With reference to specific embodiment and accompanying drawing, the invention will be further described, but embodiments of the present invention are not
It is limited to this.
The thickness of the fento coated carbon nano-tube composite material of the carried metal active component prepared in the embodiment of the present invention
For 1-2mm, compared to traditional fixed bed catalyst, can make the reduction of fixed bed bed pressure drop using the composite of the present invention
More than 50%, catalytic efficiency lifting 20%-100%, during for liquid phase reactor, the leaching rate of active component can be decreased below
1mg/L, pollutants removal rate reaches as high as 100%.
Embodiment 1
A kind of preparation method of the fento coated carbon nano-tube composite material of carried metal active component, including following step
Suddenly：
(1) preparation of fento coated carbon nano-tube composite material carrier：
(1-1) weighs 7g stainless steel fibres (model SS-316L, length is 1-5mm, a diameter of 6.5 μm), 10g needles
Wood-fibred and 2g CNTs, are added in 2L water, are dissociated in standard fibre dissociation device after 10min, the mistake on manual handsheet machine
Filter shaping, 110 DEG C of heating press, which are dried, is made fento composite material precursor；
Presoma is placed in the high temperature shell and tube sintering furnace of protection gas (nitrogen or helium) protection by (1-2) enters line program
Heating sintering；Before sintering, sintering furnace is first vacuumized, and is then led to protection gas, is repeated three times, then by following temperature programming：
With 5 DEG C/min speed from room temperature to 480 DEG C, in 480 DEG C of constant temperature 20min, then 1050 are warming up to 4.7 DEG C/min
DEG C, 20min is sintered in 1050 DEG C, room temperature is then naturally cooling to, obtains fento coated carbon nano-tube composite material carrier；
(2) preparation of the fento coated carbon nano-tube composite material of carried metal active component
(2-1) weighs 1.5g fento coated carbon nano-tube composite material carriers and 0.426g ferric acetyl acetonades are placed in reaction dress
In putting, under protection gas nitrogen atmosphere, 120 DEG C, constant temperature 60min are risen to from room temperature with 3 DEG C/min heating rate；Again with 3 DEG C/
Min is warming up to 310 DEG C, keeps 60min, naturally cools to room temperature, obtain sedimentation products；
Sedimentation products are calcined 360min in 400 DEG C, heating rate is 1 DEG C/min, natural by (2-2) under air atmosphere
Room temperature is cooled to, the fento coated carbon nano-tube composite material of carried metal active component is obtained.Gold-supported prepared by the application
The thickness for belonging to the fento coated carbon nano-tube composite material of active component is that the grain diameter of 1-2mm active components is 15nm.
The SEM figures of fento coated carbon nano-tube composite material carrier manufactured in the present embodiment are as shown in Fig. 1 (a), gold-supported
Belong to the SEM figures of fento coated carbon nano-tube composite material of active component as shown in Fig. 1 (b).Gold-supported manufactured in the present embodiment
Belong to the XRD of fento coated carbon nano-tube composite material of active component as shown in Fig. 2 temperature programmed reduction curve map (TPR
Figure) as shown in Figure 3.The three-dimensional netted knot of stainless steel fibre formation is successfully coated on from SEM it can be seen from the figure thats CNT
In structure, and successfully active component is equably loaded on carrier by chemical vapour deposition technique.It can confirm that from XRD
Active component is successfully loaded on carrier, and can calculate by Scherrer formula the particle size of active component.TPR figures can be with
Obtain the reduction temperature of active component, it was demonstrated that active component has the ability of oxidation organic pollution.
Catalyst performance is tested：
The fento coated carbon nano-tube composite material of obtained carried metal active component is used for consolidating for m-methyl phenol
Fixed bed catalytic degradation reaction, bed height is 2cm, and reaction temperature is 80 DEG C, and feed flow rate is 2ml/min.Oxidant is H2O2,
M-methyl phenol concentration is 1000mg/L, and oxidant is with treating that the ratio between input concentration of degradation product is stoichiometric proportion：C7H8O+
17H2O2→7CO2+21H2O, reactivity curve are as shown in figure 4, methylphenol conversion ratio reaches 97%, and passes through 6 hours instead
Active should it not be decreased obviously.
Embodiment 2
A kind of preparation method of the fento coated carbon nano-tube composite material of carried metal active component, including following step
Suddenly：
(1) preparation of fento coated carbon nano-tube composite material carrier：
(1-1) weighs 6g stainless steel fibres (model SS-316L, length is 1-5mm, a diameter of 6.5 μm), 10g needles
Wood-fibred and 3g CNTs, are added in 2L water, are dissociated in standard fibre dissociation device after 10min, the mistake on manual handsheet machine
Filter shaping, 110 DEG C of heating press, which are dried, is made fento composite material precursor；
Presoma is placed in the high temperature shell and tube sintering furnace of protection gas (nitrogen) protection and carries out temperature programming burning by (1-2)
Knot；Before sintering, sintering furnace is first vacuumized, and is then led to protection gas, is repeated three times, then by following temperature programming：With 5 DEG C/
Min speed, in 480 DEG C of constant temperature 20min, is then warming up to 1050 DEG C from room temperature to 480 DEG C with 4.7 DEG C/min, in
1050 DEG C of constant temperature 20min, are then naturally cooling to room temperature, obtain fento coated carbon nano-tube composite material carrier；
(2) preparation of the fento coated carbon nano-tube composite material of carried metal active component
(2-1) weighs 1g fento composite material carriers, then weighs 0.172g acetylacetone coppers, and protection gas (nitrogen is placed in together
Gas) temperature programming under atmosphere, heating schedule is：180 DEG C first are risen to from room temperature with 3 DEG C/min heating rate, is protected in the temperature
Hold 60min；350 DEG C are warming up to 3 DEG C/min again, 60min is kept, naturally cools to room temperature, obtain sedimentation products；
Sedimentation products are calcined 360min in 400 DEG C, heating rate is 1 DEG C/min, natural by (2-2) under air atmosphere
Room temperature is cooled to, the fento coated carbon nano-tube composite material of carried metal active component is obtained.
Catalyst performance is tested：
The fento coated carbon nano-tube composite material of obtained carried metal active component is used for consolidating for m-methyl phenol
Fixed bed catalytic degradation reaction, bed height is 3cm, and reaction temperature is 80 DEG C, and feed flow rate is 2ml/min.Oxidant is H2O2,
Phenol concentration is 1000mg/L, and oxidant is with treating that the ratio between input concentration of degradation product is stoichiometric proportion：C6H6O+14H2O2→
6CO2+17H2O, phenol conversion reaches 99%, and is not decreased obviously by 6 hours reactivities.
Embodiment 3
A kind of preparation method of the fento coated carbon nano-tube composite material of carried metal active component, including following step
Suddenly：
(1) preparation of fento coated carbon nano-tube composite material carrier：
(1-1) weighs 7g stainless steel fibres (model SS-316L, length is 1-5mm, a diameter of 6.5 μm), 10g needles
Wood-fibred and 2g CNTs, are added in 2L water, are dissociated in standard fibre dissociation device after 10min, the mistake on manual handsheet machine
Filter shaping, 110 DEG C of heating press, which are dried, is made fento composite material precursor；
Presoma is placed in the high temperature shell and tube sintering furnace of protection gas (nitrogen) protection and carries out temperature programming burning by (1-2)
Knot；Before sintering, sintering furnace is first vacuumized, and is then led to protection gas, is repeated three times, then by following temperature programming：With 5 DEG C/
Min speed, in 480 DEG C of constant temperature 20min, is then warming up to 1050 DEG C from room temperature to 480 DEG C with 4.7 DEG C/min, in
1050 DEG C of constant temperature 20min, are then naturally cooling to room temperature, obtain fento coated carbon nano-tube composite material carrier；
(2) preparation of the fento coated carbon nano-tube composite material of carried metal active component
(2-1) weighs 1g fento composite material carriers, then weighs 0.139g ferric acetyl acetonades, and protection gas (nitrogen is placed in together
Gas) temperature programming under atmosphere, heating schedule is：120 DEG C first are risen to from room temperature with 3 DEG C/min heating rate, is protected in the temperature
Hold 60min；310 DEG C are warming up to 3 DEG C/min again, 60min is kept, naturally cools to room temperature, obtain sedimentation products；
Sedimentation products are calcined 360min in 400 DEG C, heating rate is 1 DEG C/min, natural by (2-2) under air atmosphere
Room temperature is cooled to, the fento coated carbon nano-tube composite material of carried metal active component is obtained.
Catalyst performance is tested：
The fento coated carbon nano-tube composite material of obtained carried metal active component is used for consolidating for m-methyl phenol
Fixed bed catalytic degradation reaction, bed height is 3cm, and m-methyl phenol concentration is 1000mg/L, and oxidant is with treating entering for degradation product
It is stoichiometric proportion to expect the ratio between concentration：C7H8O+17H2O2→7CO2+21H2O, methylphenol conversion ratio reaches 99%, and passes through 6
Hour reactivity is not decreased obviously.
Claims (10)
1. a kind of preparation method of the fento coated carbon nano-tube composite material of carried metal active component, it is characterised in that：Bag
Include following steps：
(1) fento composite material precursor is made by wet paper manufacturing method in stainless steel fibre, wood-fibred and CNT and done
It is dry；
(2) it will be sintered by dry fento composite material precursor in protective gas, obtain fento carbon coated and receive
Mitron composite material carrier；
(3) transition metal precursor and fento coated carbon nano-tube composite material carrier are placed in reaction unit, in protectiveness
In gas, the temperature that transition metal precursor can gasify or distil is warming up to, constant temperature is for a period of time；It is continuously heating to transition gold
The temperature that category presoma can be decomposed is deposited, and natural cooling obtains deposit；
(4) in the atmosphere of air, deposit is calcined 120~360min in 400~500 DEG C, cooling obtains carried metal work
The fento coated carbon nano-tube composite material of property component.
2. the preparation method of the fento coated carbon nano-tube composite material of carried metal active component according to claim 1,
It is characterized in that：Wood-fibred described in step (1) is needle-leaved wood fibre and/or broad-leaved wood fiber；
Transition metal precursor described in step (3) is transition metal organic salt, including acetylacetone copper, ferric acetyl acetonade, second
Acyl acetone ferrous iron (II), acetylacetone cobalt (II), it is a kind of in manganese acetylacetonate (II) and more than.
3. the preparation method of the fento coated carbon nano-tube composite material of carried metal active component according to claim 1,
It is characterized in that：Stainless steel fibre described in step (1)：Wood-fibred：The mass ratio of CNT is (3~8)：10：(1~6).
4. the preparation method of the fento coated carbon nano-tube composite material of carried metal active component according to claim 1,
It is characterized in that：The consumption of transition metal precursor described in step (3) is fento coated carbon nano-tube composite material carrier matter
The 1%~30% of amount.
5. the preparation method of the fento coated carbon nano-tube composite material of carried metal active component according to claim 1,
It is characterized in that：The temperature sintered described in step (2) is 950-1100 DEG C of 15~30min of constant temperature；Constant temperature described in step (3)
Time be 30~120min, the heating rate of continuation heating is 1~3 DEG C/min, the sedimentation time is 30~
60min。
6. the preparation method of the fento coated carbon nano-tube composite material of carried metal active component according to claim 5,
It is characterized in that：The condition of the sintering is to rise to 480 DEG C from room temperature with 3~7 DEG C/min speed, 480 DEG C of constant temperature 10~
30min, is then warming up to 950~1100 DEG C with 3~7 DEG C/min speed, then at 950~1100 DEG C of 15~30min of constant temperature.
7. the preparation method of the fento coated carbon nano-tube composite material of carried metal active component according to claim 1,
It is characterized in that：The condition dried described in step (1) is 100 DEG C~110 DEG C dry 30~120min；
Protective gas described in step (2), (3) is nitrogen, helium or argon gas.
8. a kind of fento carbon coated of the carried metal active component obtained by any one of claim 1~7 preparation method
Nanometer tube composite materials.
9. the application of the fento coated carbon nano-tube composite material of carried metal active component according to claim 8, it is special
Levy and be：The fento coated carbon nano-tube composite material of the carried metal active component is used as fixed bed catalyst, described solid
Bed catalyst catalyzing oxidizing degrading organism.
10. the application of the fento coated carbon nano-tube composite material of carried metal active component according to claim 9, it is special
Levy and be：The organic matter is phenol and/or the derivative of its phenol.
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Application publication date: 20171107 |