CN104475170A - Aluminum silicon alloy catalyst carrier as well as preparation method and application thereof - Google Patents
Aluminum silicon alloy catalyst carrier as well as preparation method and application thereof Download PDFInfo
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- CN104475170A CN104475170A CN201410772917.3A CN201410772917A CN104475170A CN 104475170 A CN104475170 A CN 104475170A CN 201410772917 A CN201410772917 A CN 201410772917A CN 104475170 A CN104475170 A CN 104475170A
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Abstract
The invention discloses a method for preparing a catalyst carrier which takes an aluminum-silicon alloy as a core and flaky aluminum oxide as a shell. The method is mainly characterized by comprising the following steps: by taking aluminum-silicon alloy powder (the mass content of silicon is 10-50%) which is prepared by using an atomization method as a raw material, performing hydro-thermal treatment, washing, drying and roasting, thereby forming a porous structure consisting of flaky aluminum oxide on the surface of the aluminum-silicon alloy powder, wherein the average aperture of the porous structure is 3-40nm, the flake layer thickness of the porous structure is 10-30nm, and the specific surface area of the porous structure is up to 70-500m<2>/g. The carrier has high activity in hydrogenation reaction of styrene and low-temperature catalysis combustion of VOCs when used for carrying a noble metal palladium catalyst.
Description
Technical field
The present invention relates to a kind of catalyst carrier field, and preparation method and application, be further also specifically related to a kind of application of catalyst carrier of the catalyst combustion reaction for styrene hydrogenation reaction or VOCs.
Background technology
Carrier surface due to flaking structure is conducive to the mass transport process of reactant at catalyst surface, thus is conducive to carrying out fast of reaction, improves the catalytic activity of catalyst.But the catalyst carrier of current sheet surface structure, adopts interpolation structure directing agent (template) to utilize solvent-thermal method to prepare usually.As CN201310670278.5 discloses flake nano SAPO-34 molecular sieve, preparation method and application thereof.Employing tetraethyl ammonium hydroxide is template, and conventional hydrothermal or solvent process for thermosynthesizing synthesis, synthesized nanometer SAPO-34 sample is platelet morphology.This synthetic method is simple, and efficiently, solvent-oil ratio is little, and Methanol has very high selectivity of light olefin in alkene (MTO) reaction, and especially the total recovery of ethene and propylene can reach more than 83%.But the method needs to add template.CN201310234194.7 discloses a kind of laminar chromium oxide/aluminum oxide catalyst and preparation method thereof.Under the condition adding template, alcohol thermal response is carried out in aluminium source, chromium source, gained solid is dried, calcining, and cooling grinding is shaping both obtained catalyst.Catalyst prepared by this method has flake structure, is conducive to reaction mass transfer, is applied to preparing propylene by dehydrogenating propane and has excellent conversion ratio and selective.But above preparation method all inevitably introduces template.
On the other hand, the catalyst carrier that in fixed bed reactors, thermal conductivity is bad, often easily causes the difficulty that heat transfer and temperature control.Especially high exothermic reaction, very easily causes beds hot-spot, even occurs " temperature runaway " phenomenon time serious, and catalyst activity component is sintered, and catalytic performance declines.In order to address this problem, the material that at present conventional method useful inertia highly heat-conductive material dilute catalyst bed or use have a high-termal conductivity as catalyst carrier to improve fixed bed reactors heat transfer efficiency, to maintain the stability of catalyst.CN102020525A discloses the application of a kind of Ni/SiC catalyst in preparing methane by synthetic gas.Utilize the SiC of high thermal conductivity as catalyst carrier load active component metallic nickel, found that catalyst catalytic performance is excellent, methane selectively is more than 85%, and bed temperature is evenly distributed, and catalyst does not have carbon deposit to generate.But SiC carrier specific area prepared is at present less, and its surface too inertia, be unfavorable for the load of active component.
Therefore, the anxious a kind of catalyst carrier to be developed of those skilled in the art, can develop a kind of preparation process simple, be easy to control, there is higher catalytic activity and high thermal conductivity, and environmental protection, favourable large-scale industrial production catalyst support structures and preparation method thereof.
Summary of the invention
The present invention successfully develops alusil alloy catalyst nucleocapsid carrier structure first, while can having high thermal conductivity, also helps the mass transport process of reactant at catalyst surface, improves catalytic activity.
The object of the invention is to, provide a kind of preparation process simple, be easy to control, when without the need to template, also can obtain environmental protection, be applicable to large-scale industrial production, there is the preparation method of the alusil alloy catalyst carrier of flaking surface texture.
The present invention also aims to, the application of above-mentioned alusil alloy catalyst carrier is provided, can efficient for styrene hydrogenation reaction or the catalyst combustion reaction of VOCs.
Alusil alloy catalyst carrier of the present invention is the spherical nuclei shell structure prepared for raw material with alusil alloy powder, kernel is alusil alloy, shell is the loose structure of surface scale shape aluminium oxide composition, and its average pore size is 3-40nm, lamellar spacing 10nm-30nm.
With alusil alloy powder for stock preparation process is: alusil alloy powder is carried out at 40-200 DEG C after hydro-thermal reaction forms flaking surface texture, filter, washing, dry, by dried powder in atmosphere 300-600 DEG C of roasting obtain.
The preparation method of alusil alloy catalyst carrier of the present invention is after by alusil alloy powder, at 40-200 DEG C, hydro-thermal reaction forms flaking surface texture, filter, washing, dry, by the 300-600 DEG C of roasting in atmosphere of dried powder, obtaining kernel is uncorroded alusil alloy, and shell is the catalyst carrier of flaky alumina.
The hydro-thermal reaction time described in the present invention is preferably 10min-12h; Particularly preferably 2-6h.
Roasting time described in the present invention is preferably 2-10h.
Drying of the present invention is dry 2-10h at 60-100 DEG C preferably.
Described alusil alloy powder average particle size range 3 ~ 40 microns of the present invention.
The mass content of described silicon from aluminum-silicon alloy is 10 ~ 50%; Be preferably 10 ~ 40%; Most preferably be 30 ~ 40%.
The application of described catalyst carrier of the present invention is catalyst combustion reaction active noble metals palladium and described catalyst carrier composition catalyst being used for styrene hydrogenation reaction or VOCs.
Inventor by repeatedly studying trial, finds unexpectedly, and when without the need to adopting template, alusil alloy powder can the flaking structure of formation rule under the control of hydrothermal condition.Inventor thinks by further studying, why can be formed said structure be due to the present invention have employed alusil alloy powder especially when, aluminium under hydrothermal conditions facile hydrolysis generates while aluminium hydroxide, along with the carrying out of reaction, aluminium hydroxide degree of supersaturation increases, and is easy to nucleating growth on a silicon substrate and forms the regular flaking body structure surface of crystalline form at the alusil alloy rough surface be corroded.By to alusil alloy composition, hydro-thermal time, temperature can the size structure of effective control surface lamella further.Therefore, the present invention is by carrying out hydrothermal treatment consists by alusil alloy surface, and mild corrosion obtains stable aluminium oxide lamella further through calcination process after obtaining aluminium hydroxide schistose surface.Catalyst activity component is loaded in carrier sheet of the present invention, the equally distributed catalyst of active component can be obtained.Now, active component is easy to load to aluminium oxide sheet surfaces, and inside is uncorroded alusil alloy material, the catalyst that method of the present invention is obtained, is conducive to reactant in the mass transport process of catalyst surface thus carrying out fast of being conducive to reacting.Meanwhile, due to only surperficial mild corrosion, kernel is solid alusil alloy, and this carrier has higher mechanical strength.And alusil alloy material also has the good feature of thermal conductivity, the catalyst utilizing alusil alloy powder to prepare is conducive to the heat conduction of beds, avoids being emerged of bed " focus ".In addition, alusil alloy powder has the advantage such as its cheap market price, sufficient raw.Therefore, with alusil alloy powder for this carrier prepared by raw material has great actual application value and great commercial promise.
Catalyst carrier of the present invention, its raw material prepared is the preferred average particle size range of alusil alloy powder 3 ~ 40 microns.
The mass content of described silicon from aluminum-silicon alloy is preferably 10 ~ 50%; Be more preferably 10 ~ 40%; More preferably 30-40%.
Catalyst carrier specific area of the present invention can reach 70-500m
2/ g.
Preparation method's detailed process of catalyst carrier of the present invention is as follows:
(1) alusil alloy powder (average particle size range 3-40 micron, silicone content is 10 ~ 40%) is put into hydrothermal reaction kettle, add distilled water wherein;
(2) hydro-thermal reaction 10min-12h at 40-200 DEG C of temperature;
(3) filter, add deionized water washing, dry 2-10h at filter cake puts into baking oven 60-100 DEG C;
(4) by gained powder 300-600 DEG C of roasting 2-10h in atmosphere, this carrier is obtained.
Carrier of the present invention adopts infusion process supported precious metal palladium, and probes into the activity of catalyst prepared by this carrier by styrene hydrogenation reaction and VOCs catalyst combustion reaction.
Infusion process is adopted to be dissolved in deionized water by active noble metals palladium soluble-salt, flood with the carrier obtained at ambient temperature, dip time is 0.5-2h, after dipping at 60-100 DEG C dry 1-2h, carry out roasting in air atmosphere after drying, sintering temperature is 200-600 DEG C, and roasting time is 1-3h, pass into hydrogen atmosphere reduction after roasting, obtain catalyst.
Compared with prior art, tool has the following advantages in the present invention: the present invention is by adopting simple hydro-thermal method without the need to adding template, and can obtain kernel is uncorroded alusil alloy, and shell is the catalyst carrier of flaky alumina; Preparation process of the present invention is simple, environmental protection.This carrier that is kernel with the alusil alloy of high heat conduction, is conducive to the heat conduction improving beds, thus effectively prevents being emerged and the generation of " temperature runaway " of fixed bed reactors bed " focus ".This carrier also has good mechanical strength and larger specific area simultaneously.Catalyst preparation process is simple, and catalytic performance is excellent.
Accompanying drawing explanation
Fig. 1 is this carrier (raw material is the alusil alloy of silicone content 40%) ESEM (SEM) photo figure before calcination of gained of the present invention, and the carrier before roasting is the spherical structure of surface scale shape.
Fig. 2 is ESEM (SEM) the photo figure of this carrier (raw material is the alusil alloy of silicone content 40%) of gained of the present invention, and this carrier prepared after roasting still well maintains the spherical structure of surface scale shape.
Fig. 3 is carried palladium catalyst transmission electron microscope (TEM) photo figure prepared by this carrier (raw material is the alusil alloy of silicone content 40%) of gained of the present invention, prepared catalyst is sheet surfaces, the nucleocapsid structure of solid kernel, and palladium particle load is on lamella.
Fig. 4 is ESEM (SEM) the photo figure of this carrier (raw material is the alusil alloy of silicone content 10%) of gained of the present invention, and the carrier prepared by this raw material also presents the spherical structure of surface scale shape.
Fig. 5 is ESEM (SEM) the photo figure of the aluminium powder processed under the hydrothermal condition in comparative example 1.Aluminium powder after process not only defines strip cube structure on its surface, and defines many larger rectangular structure around.
Fig. 6 is ESEM (SEM) the photo figure of the alusil alloy powder (alusil alloy of silicone content 40%) processing 6h in the thermostat in comparative example 2 under 90 DEG C of water bath condition, alusil alloy surface also form sclay texture, but at ball the many larger uneven assorted sheets of outer and Surface Creation.
Fig. 7 is ESEM (SEM) the photo figure of the alusil alloy powder after the HCl treatment in comparative example 3.Alusil alloy spheroid after peracid treatment defines the porous surface structure of dendritic crystalline.
Detailed description of the invention
The present invention will be further described for embodiment below, and protection scope of the present invention is not by the restriction of these embodiments.
Embodiment 1:
(average grain diameter is 6.11 μm to take alusil alloy powder, silicone content is 40%) 6g puts into hydrothermal reaction kettle, add distilled water wherein, at 150 DEG C of hydro-thermal reaction 6h, filter, add deionized water washing, dry 2h at 60 DEG C, baking oven put into by filter cake, and the powder of acquisition uses SEM electron microscopic observation as shown in Figure 1, and dried powder is continued 450 DEG C of roasting 2h in atmosphere, this carrier obtained, the result that use SEM electron microscopic observation arrives as shown in Figure 2.
The soluble salt solution 0.01mol/L of preparation palladium, measure four parts of 23.5mL, respectively to wherein adding this carrier of 2.5g, silica, cocoanut active charcoal, activated alumina four kinds of carriers, dipping absorption under normal temperature condition, dip time 0.5h, after dipping at 60 DEG C dry 1h, carry out roasting in air atmosphere after drying, sintering temperature is 350 DEG C, and roasting time is 2h, pass into hydrogen atmosphere reduction after roasting, finally obtain four kinds and carry the catalyst that palladium content is 1 (wt) %.The TEM result of the catalyst prepared by this carrier as shown in Figure 3.
Get 1mL styrene and 100uL n-decane (marking as in gas chromatographic detection) in 100mL ethanolic solution, and add four kinds of fine catalysts, pass into hydrogen reaction, maintenance hydrogen flowing quantity is 40mL/min, reaction temperature is 20 DEG C, reaction timing sampling, sample detection adopts Shimadzu GC-2010 chromatographic, using reaction rate constant as evaluation of catalyst activity index.Reaction result shows, the styrene hydrogenation reactivity of this carrier, silica, cocoanut active charcoal, activated alumina four kinds of carrier carried palladium catalysts is respectively 264.8mmolmin
-1g
-1, 99.9mmolmin
-1g
-1, 110.1mmolmin
-1g
-1, 212.4mmolmin
-1g
-1.
Embodiment 2:
(average grain diameter is 6.11 μm to take alusil alloy powder, silicone content is 40%) 6g puts into hydrothermal reaction kettle, add distilled water wherein, at 150 DEG C of hydro-thermal reaction 6h, filter, add deionized water washing, dry 2h at 60 DEG C, baking oven put into by filter cake, by the 450 DEG C of roasting 2h in atmosphere of powder after drying, this carrier obtained.
The soluble salt solution 0.01mol/L of preparation palladium, measure two parts of 23.5mL, respectively to the alusil alloy wherein added handled by 2.5g, activated alumina two kinds of carriers, dipping absorption under normal temperature condition, dip time 0.5h, after dipping at 60 DEG C dry 1h, carry out roasting in air atmosphere after drying, sintering temperature is 350 DEG C, and roasting time is 2h, pass into hydrogen atmosphere reduction after roasting, finally obtain two kinds and carry the catalyst that palladium content is 1 (wt) %.
With fixed bed reactors, VOCs is as target contaminant in toluene simulation, carries out toluene catalytic combustion experiment respectively to this carrier and activated alumina loaded palladium catalyst.At 25000h
-1high-speed and toluene concentration 21.29g/m
3carry out catalyst combustion reaction under reaction condition, reaction adopts open tubular furnace and temperature controller temperature programming, and temperature range is by 80 DEG C to 360 DEG C, and toluene concentration is by chromatographic.Experimental result shows: the initiation temperature (T10) of activated alumina carried palladium catalyst is 195 DEG C, and complete ignition temperature (T99) is 345 DEG C; Alusil alloy carried palladium catalyst initiation temperature is (T10) 170 DEG C, and complete ignition temperature (T99) is 265 DEG C.
Embodiment 3:
(average grain diameter is 6.11 μm to take alusil alloy powder, silicone content is 10%) 6g puts into hydrothermal reaction kettle, add distilled water wherein, at 150 DEG C of hydro-thermal reaction 6h, filter, add deionized water washing, dry 2h at 60 DEG C, baking oven put into by filter cake, by the 450 DEG C of roasting 2h in atmosphere of powder after drying, obtained silicone content is the alusil alloy carrier of 10%, and the result that use SEM electron microscopic observation arrives as shown in Figure 4.
The soluble salt solution 0.01mol/L of preparation palladium, measure 23.5mL, add the alusil alloy carrier handled by 2.5g wherein, dipping absorption under normal temperature condition, dip time 0.5h, after dipping at 60 DEG C dry 1h, carry out roasting in air atmosphere after drying, sintering temperature is 350 DEG C, and roasting time is 2h, pass into hydrogen atmosphere reduction after roasting, finally obtain the catalyst that palladium load capacity is 1 (wt) %.
Toluene catalytic combustion experiment is carried out to prepared catalyst.At 25000h
-1high-speed and toluene concentration 21.29g/m
3carry out catalyst combustion reaction under reaction condition, reaction adopts open tubular furnace and temperature controller temperature programming, and temperature range is by 80 DEG C to 360 DEG C, and toluene concentration is by chromatographic.Experimental result shows: alusil alloy (silicone content is 10%) carried palladium catalyst initiation temperature is (T10) 188 DEG C, and complete ignition temperature (T99) is 325 DEG C.
Comparative example 1:
Take aluminium powder (average grain diameter is about 6 μm) 6g and put into hydrothermal reaction kettle, add distilled water wherein, at 150 DEG C of hydro-thermal reaction 6h, filter, add deionized water washing, dry 2h at 60 DEG C, baking oven put into by filter cake, by the 450 DEG C of roasting 2h in atmosphere of powder after drying, aluminium powder under obtained the same terms after hydrothermal treatment consists, the result that use SEM electron microscopic observation arrives as shown in Figure 5.
Comparative example 2:
(average grain diameter is 6.11 μm to take alusil alloy powder, silicone content is 40%) 6g puts into 500mL beaker, add 300mL distilled water, in constant temperature water bath, 90 DEG C of reaction 6h, filter, and add deionized water washing, dry 2h at 60 DEG C, baking oven put into by filter cake, by the 450 DEG C of roasting 2h in atmosphere of powder after drying, obtained powder, the result that use SEM electron microscopic observation arrives as shown in Figure 6.
Comparative example 3:
(average grain diameter is 6.11 μm to take alusil alloy powder, silicone content is 40%) 6g, the hydrochloric acid solution 300mL of preparation 1mol/L, the 6g alusil alloy powder taken is joined in the hydrochloric acid solution prepared and reacts 2h, rear filtration, washing is to neutrality and by filter cake dry 10h at 60 DEG C, and the alusil alloy powder after obtained acid treatment, uses the result of SEM electron microscopic observation as shown in Figure 7.
Claims (10)
1. an alusil alloy catalyst carrier, is characterized in that, the spherical nuclei shell structure prepared for raw material with alusil alloy powder, kernel is alusil alloy, shell is the loose structure of surface scale shape aluminium oxide composition, and its average pore size is 3-40nm, lamellar spacing 10nm-30nm.
2. catalyst carrier as claimed in claim 1, it is characterized in that, in described alusil alloy powder, the mass content of silicon is 10 ~ 50%.
3. catalyst carrier as claimed in claim 1, it is characterized in that, in described alusil alloy powder, the mass content of silicon is 10 ~ 40%.
4. catalyst carrier as claimed in claim 1 or 2: it is characterized in that, the preparation process being raw material with alusil alloy powder is: after alusil alloy powder being carried out at 40-200 DEG C hydro-thermal reaction formation flaking surface texture, filter, washing, drying, by dried powder in atmosphere 300-600 DEG C of roasting obtain.
5. catalyst carrier as claimed in claim 3, it is characterized in that, the described hydro-thermal reaction time is 10min-12h.
6. the preparation method of an alusil alloy catalyst carrier, it is characterized in that, after by alusil alloy powder, at 40-200 DEG C, hydro-thermal reaction forms flaking surface texture, filter, washing, dry, by the 300-600 DEG C of roasting in atmosphere of dried powder, obtaining kernel is uncorroded alusil alloy, and shell is the catalyst carrier of flaky alumina.
7. preparation method as claimed in claim 5, it is characterized in that, the described hydro-thermal reaction time is 10min-12h.
8. preparation method as claimed in claim 6, it is characterized in that, in described alusil alloy powder, the mass content of silicon is 10 ~ 50%.
9. the preparation method as described in claim 6-8, is characterized in that, in described alusil alloy powder, the mass content of silicon is 10 ~ 40%.
10. the application of the catalyst carrier as described in any one of claim 1-4, is characterized in that, active noble metals palladium and described catalyst carrier composition catalyst is used for the catalyst combustion reaction of styrene hydrogenation reaction or VOCs.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109603797A (en) * | 2019-01-04 | 2019-04-12 | 武汉科技大学 | A kind of catalyst with core-casing structure carrier and preparation method thereof |
| CN110586061A (en) * | 2019-09-24 | 2019-12-20 | 浙江工业大学 | Catalyst carrier with temperature adjusting function and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61254250A (en) * | 1985-05-02 | 1986-11-12 | Cataler Kogyo Kk | Preparation of catalyst carrier |
| JP4552098B2 (en) * | 2001-01-29 | 2010-09-29 | 株式会社豊田中央研究所 | Exhaust gas purification catalyst carrier, production method thereof and catalyst |
-
2014
- 2014-12-15 CN CN201410772917.3A patent/CN104475170B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61254250A (en) * | 1985-05-02 | 1986-11-12 | Cataler Kogyo Kk | Preparation of catalyst carrier |
| JP4552098B2 (en) * | 2001-01-29 | 2010-09-29 | 株式会社豊田中央研究所 | Exhaust gas purification catalyst carrier, production method thereof and catalyst |
Non-Patent Citations (1)
| Title |
|---|
| 郭军: "Al-Si/Al2O3核壳结构粒子的制备及其相变特性研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》, no. 6, 15 June 2014 (2014-06-15) * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109603797A (en) * | 2019-01-04 | 2019-04-12 | 武汉科技大学 | A kind of catalyst with core-casing structure carrier and preparation method thereof |
| CN110586061A (en) * | 2019-09-24 | 2019-12-20 | 浙江工业大学 | Catalyst carrier with temperature adjusting function and preparation method thereof |
| CN110586061B (en) * | 2019-09-24 | 2022-04-01 | 浙江工业大学 | Catalyst carrier with temperature adjusting function and preparation method thereof |
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