CN104248948A - Ti pillared clay supported catalyst, preparation method and application thereof - Google Patents
Ti pillared clay supported catalyst, preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a Ti pillared clay supported catalyst, a preparation method and application thereof. The catalyst employs Ti pillared clay as a carrier, the Ti pillared clay has mesoporous structure, layer spacing of 1.77 nm, specific surface area of 224.7 m<2> / g, total pore volume of 0.170 cm<3> / g, and the mass fraction of the total load amount accounts for 10%. The invention uses Ti pillared clay to support Ce and Cr or only support Cr as the catalyst, and the Ti pillared clay has large specific surface area and pore size. The invention as the advantages of simple preparation process, and low equipment requirements. The Ti pillared clay supported Cr or CrCe catalyst is used in the catalytic degradation of low concentration of chlorobenzene, and shows excellent activity of catalytic degradation of chlorobenzene.
Description
Technical field
The invention belongs to chemical catalyst and fabricating technology field thereof, particularly relate to a kind of Ti column clay loaded catalyst, preparation method and application thereof.
Background technology
Column clay ((Pillared Clays, be called for short PILC) be utilize the expansiveness of clay and the interchangeability of interlayer ion, be inserted between argillic horizon as intercalator, through heating, roasting obtain further by introducing polymerization hydroxyl cation.With organic-pillared clay-phase ratio, inorganic column clay, as common Al-PILC, Fe-PILC and Ti-PILC etc., has better heat endurance, and under pyroreaction condition, its pore structure keeps stable, therefore can be applicable to gas-solid catalysis.
For Ti-PILC, it has following features: (1) specific area is large, uniform pore diameter; (2) titanium dioxide of interlayer mainly nano particle, is not easy to assemble; (3) there is stronger, more solid acid performance etc.Therefore, Ti-PILC shows wide application prospect as selective solid catalyst and adsorbent in fields such as petrochemical industry, fine chemistry industry and environmental protection.If Ti-PILC is at the lower NO of temperature requirement
xexcellent performance is shown in SCR.The catalytic activity relatively utilizing Ti-PILC and Y-82 zeolite to react at 1-phenylethanol selectively dewatering, result shows that Ti-PILC is selective and is better than zeolite.Existing Ti crosslinking agent synthesis needs concentrated hydrochloric acid (being generally 6mol/L), and smell is pungent, not easy to operate.Butyl Phthalate and concentrated hydrochloric acid need to stir 24 hours continuously usually, and preparation process is long, and energy resource consumption is large.
Chloride volatile organism (Chlorinated Volatile Organic Compounds, be called for short CVOCS), obtains application widely as common are machine solvent and chemical industry semi-finished product.But this compounds has great harm to health and environment.China has carried out strict regulation for the discharge of industrial discharge CVOCs class organic pollution, and therefore efficiently, Energy Saving Control CVOCs draining technology has very large demand and market.
Production by Catalytic Combustion Process is removed CVOCs and is had the advantages such as startup energy consumption is low, clearance is high, and secondary pollution is little, and the Cl element that crucial part controls wherein changes into the less HCl of toxicity as far as possible, thus reaches the object of purification.The key of Production by Catalytic Combustion Process is catalyst, catalyst normally utilizes the material of bigger serface as carrier, and the structures and characteristics of carrier can affect dispersiveness and the redox property of activity over catalysts component, thus affect the catalytic degradation performance of catalyst to CVOCs.
Traditional catalyst, as Al
2o
3, SiO
2carried noble metal is selective lower to the catalytic activity of CVOCs and end product.Molecular sieve is owing to having abundanter acid centre, and be conducive to absorption and the activation of CVOCs, therefore its supported precious metal catalyst is to CVOC
scatalytic degradation activity is higher.But this kind of catalyst ratio is easier to inactivation.Mainly containing following two reasons: one, easily there is carbon deposition phenomenon in molecular sieve, causes that duct blocks, active sites is capped, thus the activity of catalyst is reduced; Two, the molecular sieve of molecular sieve especially low silica-alumina ratio, its anti-HCl poor-performing, the HCl of the Al in skeleton easily with product in is combined the volatile AlCl of generation
3, cause framework of molecular sieve destruction, acid centre minimizing, thus make catalysqt deactivation.Non-noble metal supported catalyst mainly contains V, the single metal oxides such as Mn and Cu, and composite metal oxide.Compared with noble metal catalyst, the activity that most of non-noble metal oxide is degraded to CVOCs is lower, but its low price and anti-fluorine poisoning performance are apparently higher than noble metal catalyst.
In addition, also have the important oxide of a class, as rare earth oxide, what research was at present more mainly contains pure rare earth oxide, complex rare-earth oxidate containing valuable metal and perovskite LaBO for CVOCs catalytic degradation
3composite oxides.As added Ce and La to MnO
xthe impact of catalytic degradation chlorobenzene, result shows, the interpolation of Ce defines MnCeO
xsolid solution, forms a large amount of active oxygen species and substantially increases the activity be oxidized chlorobenzene.And add La and improve MnCeO
xthe heat endurance of solid solution.Non-loading type terres rares catalyst, active particle is easily assembled, and rare-earth usage is comparatively large, somewhat expensive.Specific area and the pore volume of such catalyst are less, are unfavorable for the mass transfer effect of large-size CVOCs, as chlorobenzene, thus affect the effect of its catalytic degradation.
Summary of the invention
The object of this invention is to provide a kind of Ti column clay loaded catalyst being obtained bigger serface, large aperture, high thermal stability by ion-exchange, and the preparation method of this catalyst and the application on the catalytic degradation of low concentration chlorobenzene are provided.
In order to realize an object of the present invention, the invention provides a kind of Ti column clay loaded catalyst, catalyst is using Ti column clay as carrier, and Ti column clay is meso-hole structure, and interlamellar spacing is 1.77nm, and specific area is 224.7m
2/ g, total pore volume is 0.170cm
3/ g, the mass fraction of total load amount accounts for 10%.
In order to realize another object of the present invention, the present invention also provides a kind of preparation method of Ti column clay loaded catalyst, comprises the steps.The preparation of Ti crosslinking agent: get under 25.5mL Butyl Phthalate stirs and add in 60mL absolute ethyl alcohol, continue to be stirred to light yellow transparent liquid, be added drop-wise to 60mL1.0mol/L HNO by under liquid vigorous stirring
3in solution, fully stir into clear solution, stand-by.The preparation of Ti column clay: utilize the sodium form imvite Na-mmt of purity >98% as initiation material, the 6g Na-mmt aqueous dispersions of the 10wt.% infiltrating 0.5h is joined stirring reaction 3h in above-mentioned clear solution, centrifugal, with distilled water washing precipitation to without Cl-, 50 DEG C of vacuumizing and drying, roasting 4h at 550 DEG C in Muffle furnace, sieve particle is 40 ~ 60 orders, obtain Ti column clay.The preparation of Ti column clay load C rCe catalyst: with Ti column clay for carrier, the nitrate solution of Cr and Ce is presoma, adds deionized water and adopts equi-volume impregnating dipping Cr (NO
3)
39H
2o and Ce (NO
3)
36H
2o, the total load amount regulating Cr and Ce is 10wt.%, and dipping places 12h, and dry 3h at 110 DEG C, 500 DEG C of roasting 2h in Muffle furnace, obtain CrCe/Ti column clay catalyst.
In one embodiment of the invention, the mol ratio regulating Cr and Ce is 6:1.
In one embodiment of the invention, centrifugal, with distilled water washing precipitation to being first with distilled water cleaning then centrifugal each 5 times without the step of Cl-, check with liquor argenti nitratis ophthalmicus and determine that supernatant liquid is without Cl-.
In one embodiment of the invention, at 550 DEG C roasting 4h step in Muffle furnace be rise to 550 DEG C with the heating rate of 10 DEG C/min from room temperature.
In one embodiment of the invention, the ion exchange capacity CEC of the sodium form imvite Na-mmt of employing is 145meq/100g ± 10%, and specific area is 2.81m
2/ g, interlamellar spacing is 1.18nm.
In order to realize another object of the present invention, the present invention also provides a kind of preparation method of Ti column clay loaded catalyst, comprises the steps.The preparation of Ti crosslinking agent: get under 25.5mL Butyl Phthalate stirs and add in 60mL absolute ethyl alcohol, continue to be stirred to light yellow transparent liquid, be added drop-wise to 60mL1.0mol/L HNO by under liquid vigorous stirring
3in solution, fully stir into clear solution, stand-by.The preparation of Ti column clay: utilize the sodium form imvite Na-mmt of purity >98% as initiation material, the 6g Na-mmt aqueous dispersions of the 10wt.% infiltrating 0.5h is joined stirring reaction 3h in above-mentioned clear solution, centrifugal, with distilled water washing precipitation to without Cl-, 50 DEG C of vacuumizing and drying, roasting 4h at 550 DEG C in Muffle furnace, sieve particle is 40 ~ 60 orders, obtain Ti column clay.The preparation of Ti column clay load C r catalyst: with Ti column clay for carrier, the nitrate solution of Cr is presoma, adds deionized water and adopts equi-volume impregnating dipping Cr (NO
3)
39H
2o, the total load amount regulating Cr is 10wt.%, and dipping places 12h, and dry 3h at 110 DEG C, 500 DEG C of roasting 2h in Muffle furnace, obtain Cr/Ti column clay catalyst.
In one embodiment of the invention, centrifugal, with distilled water washing precipitation to being first with distilled water cleaning then centrifugal each 5 times without the step of Cl-, check with liquor argenti nitratis ophthalmicus and determine that supernatant liquid is without Cl-.
In one embodiment of the invention, at 550 DEG C roasting 4h step in Muffle furnace be rise to 550 DEG C with the heating rate of 10 DEG C/min from room temperature.
In one embodiment of the invention, the ion exchange capacity CEC of the sodium form imvite Na-mmt of employing is 145meq/100g ± 10%, and specific area is 2.81m
2/ g, interlamellar spacing is 1.18nm.
In order to realize another object of the present invention, the present invention also provides the application of a kind of Ti column clay loaded catalyst on the catalytic degradation of low concentration chlorobenzene.
In sum, the following beneficial effect that has of preparation method provided by the invention and the Ti column clay loaded catalyst that utilizes this preparation method to prepare:
(1) preparation technology is simple, and equipment requirement is low.Have employed 1.0mol/L HNO
3solution, more easy to operate, synthesis condition is easy, and follow-up need be continued stirring 2.5 hours, namely obtains required Ti crosslinking agent.Therefore the method has the advantages such as easy to operate, expense is few.
(2) the method prepare after 550 DEG C of roasting 4h, specific area and the pore volume of Ti-PILC still reach 224.7m
2/ g and 0.170cm
3/ g, much larger than the 2.81m of original soil
2/ g and 0.00786cm
3/ g.
(3) Ti column clay load C r or CrCe catalyst are in the catalytic degradation for low concentration chlorobenzene, show the activity of excellent catalytic degradation chlorobenzene, wherein when CrCe mol ratio is 6:1, and just can degradable chlorobenzene at 250 DEG C.
The present invention prepares clay-like material low price, is optimized through its structure modified, and the bigger serface that Ti-PILC has and aperture structure are conducive to the mass transfer of CVOCs, and the active component consumption of load is few and scattered, not easily reunites.Main active component transition metal Cr with low cost and catalytic activity is higher.Auxiliary agent ceria and cerium-based composite oxides have good oxygen mobility, and cost is low, environmental friendliness.Result shows the catalytic degradation of this catalyst for chlorobenzene, shows very excellent catalytic activity.
For above and other objects of the present invention, feature and advantage can be become apparent, preferred embodiment cited below particularly, and coordinate accompanying drawing, be described in detail below.
Accompanying drawing explanation
Fig. 1 is preparation technology's outline flowchart of Ti column clay loaded catalyst provided by the invention.
Fig. 2 is the XRD spectra of Na-mmt and Ti-PILC.
Fig. 3 is the XRD spectra of Na-mmt and Ti-PILC loaded catalyst.
Fig. 4 is the high resolution electron microscopy figure of Na-mmt and Ti-PILC carrier and Na-mmt and Ti-PILC loaded catalyst.
Fig. 5 indicates in Fig. 4 partly to measure the EDS spectrogram obtained.
Fig. 6 is the conversion rate curve of each catalyst for chlorobenzene catalytic degradation.
Detailed description of the invention
Fig. 1 is preparation technology's outline flowchart of Ti column clay loaded catalyst provided by the invention.The present invention is further illustrated below in conjunction with Fig. 1 and embodiment.
The preparation of Ti crosslinking agent: measure 25.5mL Butyl Phthalate with pipette, adds in 60mL absolute ethyl alcohol, continues to stir 20min to light yellow transparent liquid (overall process is anhydrous), is added drop-wise to 60mL1.0mol/L HNO by under liquid vigorous stirring
3in solution, fully stir 2.5h and become clear solution, stand-by.
The preparation of Ti column clay: utilize the sodium form imvite Na-mmt of purity >98% as initiation material.In the present embodiment, utilize the inorganic level imvite of the G-105 of NANOCOR company (Na-mmt, purity >98%) as initiation material.Ion exchange capacity CEC is 145meq/100g ± 10%, and its specific area is 2.81m
2/ g, interlamellar spacing is 1.18nm.The 6g Na-mmt aqueous dispersions of the 10wt.% infiltrating 0.5h is joined stirring reaction 3h in above-mentioned clear solution, centrifugal, with distilled water washing precipitation to without Cl-(in the present embodiment, first by washed with de-ionized water then centrifugal each 5 times, determine that supernatant liquid is without Cl-with liquor argenti nitratis ophthalmicus inspection).50 DEG C of vacuumizing and drying, in Muffle furnace, 550 DEG C of roasting 4h (in the present embodiment, Muffle furnace rises to 550 DEG C with the heating rate of 10 DEG C/min from room temperature), sieve particle is 40 ~ 60 orders, obtain Ti-PILC.
The preparation of Ti column clay load C rCe catalyst: take Ti-PILC as carrier, the nitrate solution of Cr and Ce is presoma, adds deionized water and adopts equi-volume impregnating dipping Cr (NO
3)
39H
2o and Ce (NO
3)
36H
2o, the total load amount regulating Cr and Ce is 10wt.%, and dipping places 12h (spending the night), and dry 3h at 110 DEG C, in Muffle furnace, 500 DEG C of roasting 2h, obtain CrCe/Ti-PILC.
In the preparation method of Ti column clay load C r catalyst, the first two step (preparation of Ti crosslinking agent and the preparation of Ti column clay) is the same with the preparation method of Ti column clay load C rCe catalyst, difference is only that, in last step, presoma only has one.Specifically, add deionized water and adopt equi-volume impregnating dipping Cr (NO
3)
39H
2o, the total load amount regulating Cr is 10wt.%, and dipping places 12h, and dry 3h at 110 DEG C, 500 DEG C of roasting 2h in Muffle furnace, obtain Cr/Ti column clay catalyst.
To the Mn comprising Cr, Fe, Co, the activity that the components such as Ni and Cu are used for chlorobenzene catalytic degradation is studied, result shows, taking Ti-PILC as carrier loaded above-mentioned transition metal, best with Cr base catalytic activity, therefore the present invention uses Cr base to be obtained catalyst as active component by load.Ce be auxiliary agent by load, be conducive to Cr
2o
3dispersion, substantially increase to chlorobenzene oxidation activity.
In the present embodiment, adjustable Cr/Ce mol ratio is 3:1,6:1 and 9:1, prepares different Ti column clay load C rCe catalyst.In order to investigate the difference of carrier structure to catalytic degradation chlorobenzene, being that carrier has prepared two catalyst with Na-mmt, being respectively Ce/Na-mmt and Cr/Na-mmt.Preparation method and load capacity the same.
Ti-PILC obtained by above-mentioned enforcement is carried out to the experiments such as X-ray diffraction, specific area and pore volume, high resolution electron microscopy mensuration and determination of activity, as described below:
1, X-ray diffraction measurement result:
Testing conditions: the phase structure of clay and loaded catalyst thereof adopts X-ray diffraction (XRD) method to measure, experiment is carried out on Rigaku D/max2550PC type X-ray powder diffractometer, Cu K alpha ray, tube voltage 40kV, tube current 40mA, sweep speed 0.02degree/s.See Fig. 2 and Fig. 3.
Fig. 2 is X-ray diffraction (XRD) spectrogram of Na-mmt and Ti-PILC.Wherein (a) Na-mmt; (b) Ti-PILC.As we can see from the figure, the interlamellar spacing d of Na-mmt
001for 1.18nm (2 θ=7.51 °), and the d of Ti-PILC
001increase to about 1.77nm, this shows to define TiO between argillic horizon
2pillar, makes soil layer be strutted by permanent, and create the intercalation space of larger molecular dimension, therefore its interlamellar spacing increases greatly.2 θ should be attributed to cristobalite and quartzy characteristic peak in the diffraction maximum of 19.8 ° and 26.7 °.
Fig. 3 is the XRD spectra of Na-mmt and Ti-PILC loaded catalyst.Wherein, (a) Ce/Na-mmt; (b) Cr/Na-mmt; (c) Cr/Ti-PILC; (d) CrCe (6:1)/Ti-PILC (mol ratio of Cr and Ce is 6:1).There is CeO in Ce/Na-mmt catalyst
2thing phase diffraction maximum, containing Cr is all appearring in Cr catalyst
2o
3thing phase diffraction maximum.Compared with Cr/Na-mmt, the Cr of Ti-PILC load C r catalyst
2o
3thing phase diffraction peak intensity obviously reduce, this illustrates the Cr of Ti-PILC load after pillared modification
2o
3decentralization increase, and particle size reduce.And add the CrCe after Rare-Earth Ce (6:1)/Ti-PILC catalyst, Cr
2o
3thing phase diffraction peak intensity reduce further, be on the one hand be conducive to Cr owing to adding Rare-Earth Ce
2o
3dispersion, may be on the other hand Cr
2o
3load capacity reduction causes.It should be noted that and not find CeO on CrCe (6:1)/Ti-PILC
2thing phase diffraction maximum, this is by CeO
2load capacity less and on carrier high dispersive to cause.Above-mentioned phenomenon is consistent with the dispersity of the active component in HRTEM (high-resolution transmission electron microscope).
2, specific area and pore volume measurement result:
Testing conditions: the specific area of clay material and loaded catalyst thereof and pore volume measure on the full-automatic adsorption instrument of Tristar II 3020 (Micromeritics Company, USA).Adopt liquid nitrogen temperature (77K), sample all vacuumizes pretreatment 4h at 250 DEG C.With Brunauer-Emmett-Teller (BET) method measurement the specific area, pore specific surface area during t-plot method measures, Barrett-Joyner-Halenda (BJH) method calculates mesopore pore size distribution.In table 1..
The specific area S of table 1 organic pillared interlayered clay material
bET, middle pore specific surface area A
mes(being calculated by BJH method), pore volume data V
p(total pore volume is at specific pressure P/P
0calculate for=0.99 time).
As can be seen from Table 1, the Ti-PILC prepared by ion-exchange, its specific area S
bETfor 224.7m
2/ g, much larger than the 2.81m of Na-mmt
2/ g.Its pore volume data V
pat 0.170cm
3/ g, much larger than the 0.00786cm of Na-mmt
3/ g.The middle pore specific surface area A of Ti-PILC
mesreach 222.2m
2/ g, accounts for 98.9% of total specific area, illustrates that this material is typical mesoporous material.As everyone knows, mesoporous material has good mass transfer effect for larger molecular organics, as the chlorobenzene in this research, greatly can improve rate of catalysis reaction.After Ti-PILC load active component, the S of catalyst
bET, A
mesand V
preduce all to some extent, this phenomenon illustrates, part Cr and Ce enters the mesoporous interior of carrier thus aperture is reduced slightly, also in duct, defines new active sites simultaneously, make its surface and body all there is active sites mutually, greatly can improve the catalytic activity of its catalytic degradation chlorobenzene.
3, high resolution electron microscopy figure result:
Testing conditions: high resolution electron microscopy analysis (HRTEM), utilize JEOL-2010F (HR) type transmission electron microscope to obtain the pattern of Na-mmt and Ti-PILC, operating voltage is 200KV.Cut into slices after sample epoxy resin embedding, then measure.Sample powder is scattered in absolute ethyl alcohol, and vibrate under putting ultrasonic wave 5min, fishes for suspended sample with the copper mesh being coated with carbon film, and rear loading Electronic Speculum pretreatment chamber to be dried, proceeds to measuring chamber after finding time.Observe pattern, picked-up photo.The pattern of Na-mmt and Ti-PILC loaded catalyst utilizes JEOL-2100F (HR), and processing method is the same.Energy dispersive X-ray spectroscopy (EDS) experiment is the chemical composition utilizing OXFORD INCA to carry out working sample.
Fig. 4 is the high resolution electron microscopy figure of Na-mmt and Ti-PILC carrier and Na-mmt and Ti-PILC loaded catalyst.The Electronic Speculum figure that Fig. 4 (a) is Na-mmt, as can be seen from the figure, this material has two-dimensional layered structure, but its interlamellar spacing is less, and interlamellar spacing is greatly about about 1.18nm, consistent with XRD result.Fig. 4 (b) is through the Electronic Speculum figure of pillared obtained Ti-PILC, its pattern also presents the two-dimensional channel structure of rule, compared with Na-mmt, its soil layer is strutted greatly, interlamellar spacing is greatly about 1.75nm, illustrate that Ti-PILC that we prepare is after high-temperature roasting, still keeps the meso-hole structure of rule.Fig. 4 (c) is the Electronic Speculum figure of Na-mmt load C r catalyst, Cr
2o
3granular composite is on the surface of Na-mmt, and more serious agglomeration has appearred in part.Fig. 4 (d) is that the Electronic Speculum figure of Ti-PILC load C rCe catalyst, CrCe (6:1)/Ti-PILC and Cr/Na-mmt compares, and the decentralization of its active component improves greatly, and distribution is relatively more even, and does not occur obvious agglomeration.
Fig. 5 indicates the EDS spectrogram (energy spectrogram) partly measured and obtain in Fig. 4, wherein abscissa is energy, and ordinate is the photoelectron number received in the unit interval.EDS spectrogram has found the elements such as Ti, Cr, Ce and O, and TiO is described
2pillar is present in clay, and also successfully load is at Ti-PILC on the surface for active component Cr and Ce.High resolution electron microscopy figure gives the change of soil layer before and after clay alteration clearly, and the improvement of decentralization and agglomeration after load active component, the above results illustrates that the Ti-PILC after pillared modification is a kind of excellent carrier, its activity over catalysts component disperses degree prepared is high, soilless sticking phenomenon, these are all conducive to catalytic degradation chlorobenzene.
4, to the application experiment of the Ti column clay load C rCe catalyst degradation low concentration chlorobenzene obtained by above-described embodiment, its process and result as described below:
Catalyst activity is evaluated in (WFS-3010) type catalyst activity evaluating apparatus (production of Tianjin Xian Quan Instrument Ltd.), and air speed is 20000h
-1the concentration of CVOCs (concentration of chlorobenzene is 200ppm) in being imported and exported by GC1690 type gas-chromatography (FID) detection reaction device, testing conditions is temperature of vaporization chamber 170 DEG C, column temperature 120 DEG C, and records in N2000 chromatographic work station and analyze data.Catalytic degradation product all adopts gaseous mass spectrum (QIC-20, HIDEN) to detect, except H
2o, CO
2other accessory substance is not detected with HCl.
Fig. 5 is the conversion rate curve of each catalyst for chlorobenzene catalytic degradation.As can be seen from the figure, the activity of Na-mmt load C e catalyst is very poor, only has the conversion ratio of about 50% 500 DEG C time.The activity of Na-mmt load C r catalyst is also poor, the degradable chlorobenzene of ability 450 DEG C time.The Ti-PILC load C r obtained after pillared is catalyst based, when the temperature of its degradable chlorobenzene is 350 DEG C, reduces about 100 DEG C than Cr/Na-mmt.After Cr/Ti-PILC catalyst adds different content Ce, its catalytic activity all significantly improves, especially best with the activity of CrCe (6:1)/Ti-PILC, just can the chlorobenzene of degradable low concentration at about 250 DEG C.And in the product except H
2o, CO
2and HCl, do not detect Cl
2 etc.other accessory substance.Illustrating that this catalyst has selective to Cl preferably, do not produce secondary pollution, is the catalyst for chlorobenzene degraded that a class is more excellent.
In sum, the present invention utilize Ti-PILC simultaneously supported rare earth Ce and base metal Cr or only carried noble metal Cr as catalyst, the advantage of this catalyst is, 1. clay-like material low price, be optimized through its structure modified, be suitable as very much the carrier of gas-solid phase reaction catalyst; The bigger serface that 2.Ti-PILC has and aperture structure are conducive to the mass transfer of CVOCs, and the active component consumption of load is few and scattered, not easily reunites; 3. main active component transition metal Cr with low cost and catalytic activity is higher; 4. auxiliary agent ceria and cerium-based composite oxides have good oxygen mobility, and cost is low, environmental friendliness.Result shows the catalytic degradation of this catalyst for chlorobenzene, shows very excellent catalytic activity.This means that this kind of Ti column clay new catalytic material can be applied to CVOCs pollutant catalytic degradation aspect in process atmosphere pollution.Preparation method have employed 1.0mol/L HNO
3solution, more easy to operate, synthesis condition is easy, and follow-up need be continued stirring 2.5 hours, namely obtains required Ti crosslinking agent.Therefore the method has the advantages such as easy to operate, expense is few.
Although the present invention discloses as above by preferred embodiment; but and be not used to limit the present invention, anyly know this those skilled in the art, without departing from the spirit and scope of the present invention; can do a little change and retouching, therefore protection scope of the present invention is when being as the criterion depending on claims scope required for protection.
Claims (10)
1. a Ti column clay loaded catalyst, is characterized in that, described catalyst is using Ti column clay as carrier, and Ti column clay is meso-hole structure, and interlamellar spacing is 1.77 nm, and specific area is 224.7 m
2/ g, total pore volume is 0.170 cm
3/ g, the mass fraction of total load amount accounts for 10%.
2. a preparation method for the Ti column clay loaded catalyst described in manufacturing claims 1, is characterized in that, comprise the steps:
The preparation of Ti crosslinking agent: get under 25.5 mL Butyl Phthalates stir and add in 60 mL absolute ethyl alcohols, continue to be stirred to light yellow transparent liquid, 60 mL 1.0 mol/L HNO will be added drop-wise under liquid vigorous stirring
3in solution, fully stir into clear solution, stand-by;
The preparation of Ti column clay: utilize the sodium form imvite Na-mmt of purity >98% as initiation material, the 6 g Na-mmt aqueous dispersions having infiltrated the 10 wt. % of 0.5 h are joined stirring reaction 3 h in above-mentioned clear solution, centrifugal, with distilled water washing precipitation to without Cl
-, 50 ° of C vacuumizing and drying, roasting 4 h under 550 ° of C in Muffle furnace, sieves particle is 40 ~ 60 orders, obtains Ti column clay;
The preparation of Ti column clay load C rCe catalyst: with Ti column clay for carrier, the nitrate solution of Cr and Ce is presoma, adds deionized water and adopts equi-volume impregnating dipping Cr (NO
3)
39H
2o and Ce (NO
3)
36H
2o, the total load amount regulating Cr and Ce is 10wt.%, and dipping placement 12 h, dry 3h at 110 DEG C, in Muffle furnace, 500 ° of C roasting 2 h, obtain CrCe/Ti column clay catalyst.
3. the preparation method of Ti column clay loaded catalyst according to claim 2, is characterized in that, the mol ratio regulating Cr and Ce is 6:1.
4. the preparation method of Ti column clay loaded catalyst according to claim 2, is characterized in that, centrifugal, with distilled water washing precipitation to without Cl
-step be first with distilled water cleaning then centrifugal each 5 times, determine that supernatant liquid is without Cl with liquor argenti nitratis ophthalmicus inspection
-.
5. the preparation method of Ti column clay loaded catalyst according to claim 2, is characterized in that, under 550 ° of C roasting 4 h step in Muffle furnace be with 10
othe heating rate of C/min rises to 550 from room temperature
oc.
6. the preparation method of Ti column clay loaded catalyst according to claim 2, is characterized in that, the ion exchange capacity CEC of the sodium form imvite Na-mmt of employing is 145meq/100g ± 10%, and specific area is 2.81m
2/ g, interlamellar spacing is 1.18 nm.
7. a preparation method for the Ti column clay loaded catalyst described in manufacturing claims 1, is characterized in that, comprise the steps:
The preparation of Ti crosslinking agent: get under 25.5 mL Butyl Phthalates stir and add in 60 mL absolute ethyl alcohols, continue to be stirred to light yellow transparent liquid, 60 mL 1.0 mol/L HNO will be added drop-wise under liquid vigorous stirring
3in solution, fully stir into clear solution, stand-by;
The preparation of Ti column clay: utilize the sodium form imvite Na-mmt of purity >98% as initiation material, the 6 g Na-mmt aqueous dispersions having infiltrated the 10 wt. % of 0.5 h are joined stirring reaction 3 h in above-mentioned clear solution, centrifugal, with distilled water washing precipitation to without Cl
-, 50 ° of C vacuumizing and drying, roasting 4 h under 550 ° of C in Muffle furnace, sieves particle is 40 ~ 60 orders, obtains Ti column clay;
The preparation of Ti column clay load C r catalyst: with Ti column clay for carrier, the nitrate solution of Cr is presoma, adds deionized water and adopts equi-volume impregnating dipping Cr (NO
3)
39H
2o, the total load amount regulating Cr is 10wt.%, and dipping placement 12 h, dry 3h at 110 DEG C, in Muffle furnace, 500 ° of C roasting 2 h, obtain Cr/Ti column clay catalyst.
8. the preparation method of Ti column clay loaded catalyst according to claim 7, is characterized in that, under 550 ° of C roasting 4 h step in Muffle furnace be with 10
othe heating rate of C/min rises to 550 from room temperature
oc.
9. the preparation method of Ti column clay loaded catalyst according to claim 7, is characterized in that, the ion exchange capacity CEC of the sodium form imvite Na-mmt of employing is 145meq/100g ± 10%, and specific area is 2.81m
2/ g, interlamellar spacing is 1.18 nm.
10. the application of a Ti column clay loaded catalyst according to claim 1 on the catalytic degradation of low concentration chlorobenzene.
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Cited By (4)
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| CN106914247A (en) * | 2017-03-16 | 2017-07-04 | 广西大学 | The preparation and application of a kind of nickel-base catalyst for carbon dioxide methanation |
| CN108786824A (en) * | 2018-05-21 | 2018-11-13 | 绍兴文理学院 | Si column clays load high dispersive Co3O4-CeO2The preparation method and application of catalyst |
| CN109772433A (en) * | 2019-01-29 | 2019-05-21 | 绍兴文理学院 | The kaolinite soil matrix Cr of rare earth modification2O3The preparation method and application of catalyst |
| CN115301243A (en) * | 2022-07-15 | 2022-11-08 | 西北大学 | Supported perovskite catalyst, preparation method and application thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106914247A (en) * | 2017-03-16 | 2017-07-04 | 广西大学 | The preparation and application of a kind of nickel-base catalyst for carbon dioxide methanation |
| CN108786824A (en) * | 2018-05-21 | 2018-11-13 | 绍兴文理学院 | Si column clays load high dispersive Co3O4-CeO2The preparation method and application of catalyst |
| CN109772433A (en) * | 2019-01-29 | 2019-05-21 | 绍兴文理学院 | The kaolinite soil matrix Cr of rare earth modification2O3The preparation method and application of catalyst |
| CN115301243A (en) * | 2022-07-15 | 2022-11-08 | 西北大学 | Supported perovskite catalyst, preparation method and application thereof |
| CN115301243B (en) * | 2022-07-15 | 2024-01-05 | 浙江聚泰新能源材料有限公司 | Supported perovskite catalyst, preparation method and application thereof |
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