CN101327933A - Silicon based mesoporous composite material loaded with transient metal and preparation thereof - Google Patents
Silicon based mesoporous composite material loaded with transient metal and preparation thereof Download PDFInfo
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- CN101327933A CN101327933A CNA2007101176627A CN200710117662A CN101327933A CN 101327933 A CN101327933 A CN 101327933A CN A2007101176627 A CNA2007101176627 A CN A2007101176627A CN 200710117662 A CN200710117662 A CN 200710117662A CN 101327933 A CN101327933 A CN 101327933A
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Abstract
The invention provides a preparation method of silicon-based mesoporous composites supported with transition metal comprising: reacting and aging alkali-soluble or water-soluble transition metal salts and silicon sources under alkaline condition using quaternary ammonium cation surfactants as a template and acetylacetone as an auxiliary template, washing, drying and calcining the solid products after reaction, controlling the material mol ratio of reacting system in the reaction to: quaternary ammonium cation surfactants/SiO2=0.0625-0.125, acetylacetone/SiO2=1-10, Me/SiO2=0.1-1, H2O/SiO2=60-200, wherein Me represents transition metal, and preparing mesoporous composites with high transition metal loading. The mesoporous composites have advantages of high surface area, larger aperture and adjustable pore volume. The bimetallic catalyst is prepared using the composites as carrier and gamma-Al2O3 as binder and introducing auxiliary active metal, which has more excellent diesel oil HDS activity and stability.
Description
Technical field
The present invention relates to mesoporous composite material (molecular sieve) and synthetic method thereof, especially about a kind of silicon based mesoporous composite material and preparation method thereof with high capacity amount transition metal, this mesoporous composite material can be used as sorbing material and is used to prepare diesel oil HDS catalyzer, the invention belongs to inorganic materials, functional materials and catalytic material field.
Background technology
Nineteen nineties Mobil Beck of company and Kresge etc. use cats product (C first in alkaline medium
nH
2n+1Me
3N
+, n=8-16) make template, hydrothermal crystallizing (373-423K) silicate or aluminate gel one-step synthesis go out to have the serial mesopore material of regular pore passage structure and narrow pore size distribution, note is made M41S, comprise MCM-41 (six sides), MCM-48 (cube), stratified material and cube octamer.The prominent feature of such mesoporous material is to have very big specific surface area, has nano level aperture and aperture yardstick height unanimity.
Molecular screen material research in the past, direction mainly concentrates on aspects such as the synthetic and acidity, optimizing stability, functionalization of micro porous molecular sieve, but because the limited aperture of micro porous molecular sieve, make field macromole processing such as carrying out petrochemical industry with micro porous molecular sieve as carrier have significant limitation.The birth of mesopore molecular sieve has been opened up new direction for the development in this field.Since mesopore molecular sieve was in the news, synthetic, the performance optimization of mesopore molecular sieve, property representation and functionalization research enjoyed material science experts and scholars' concern.
Silicon-based mesoporous material generally acidity is very weak, thereby causes when this type of material is used for catalytic process catalytic activity very poor.Majority is reacted, usually need to introduce the metal active center, the introducing of metal component can become the active centre of catalytic reaction process on the one hand, on the other hand, because heteroatomic existence, can form new acid site, therefore, need make material can satisfy the needs of specific reaction process by in mesoporous material, introducing metal heteroatom.Introduce heteroatomic method and mainly contain three kinds: at first, can adopt dipping technique, metal refining component in pure silicon base mesopore molecular sieve structure, problem such as there is metal component skewness in material in this kind method more, and the activity that the too low grade of degree of scatter causes is too low; Secondly, can adopt engrafting method, its possible mechanism is in the pure silicon based mesoporous material, there is 26～30% Siliciumatom to link to each other, heteroatomic grafting point is provided, therefore can in the pure silicon based mesoporous material, introduce the heteroatoms composition by the back synthetic method with hydroxyl, the result is, form the layer of metal active centre at material surface, but this method has strict requirement to the precursor structure of assorted metal species, and process is very complicated; At last; can in synthesising mesoporous molecular sieve, introduce heteroatoms; like this; the heteroatoms composition just can enter into molecular sieve structure; can realize that by this method the heteroatoms composition disperses at the molecular sieve structure camber; but shortcoming is heteroatomic existence and can causes the regularity of mesopore molecular sieve to reduce usually, the specific surface area character of synthetic materials compared with the pure silicon sill with porous all had very big difference, even can't synthesize the solid material with meso-hole structure.
Mainly concentrate on the Alization to pure silicon based mesoporous material study on the modification at present, its possible starting point is, synthetic experience according to micro porous molecular sieve, Si, Al are many in the synthetic solid phase prod exists with oxide compound tetrahedron form, therefore and Si-O key bond distance and Al-O key bond distance difference are little, can realize Si-O tetrahedron and the tetrahedral isomorphous substitution of Al-O and do not cause the obvious change of order degree in building-up process.
Pure silicon based mesoporous material study on the modification also is distributed in transition metal component and introduces; generally concentrate on and in mesoporous material, introduce Ti, the Zr etc. that have isomorphous structure with silicon-oxy tetrahedron; introduce non-isomorphous species; especially the higher non-isomorphous species of valence state can cause the meso-hole structure order degree to reduce even completely destroy usually.Though it is very extensive that transition metal species such as Mo, W is used in catalytic reaction process, but in mesoporous material, introduce transition metal species such as Mo, W, present studies show that, acidic conditions adopts original position " peroxidation " method can prepare the mesoporous composite material of high transition metal M o charge capacity down, realizes that the Si/Mo ratio reaches 25.On the other hand, introduce the Mo species by in-situ compounding process and but can't overcome following obstacle under alkaline medium condition: the original position recombination process is difficult to realize the high-content load in material of Mo transition metal, the compound Mo transition metal carrying capacity that can realize of original position is no more than 1wt% usually under the alkaline condition, and the utilization ratio in Mo source has only about 1/100 usually.Above problem makes the research for preparing the mesoporous composite material that contains transition metal under the alkaline condition lose realistic meaning and supports, and therefore, the research of original position introducing transition metal species is not had an optimistic view of by people under the alkaline medium condition.
Applied research at this class functional materials shows that ambient condition difference certainly will impact the physical and chemical performance of material, and therefore, people still wait in expectation can successfully synthesize the mesoporous composite material of high capacity amount transition metal under the alkaline condition.
Summary of the invention
The technical problem underlying that desire of the present invention solves is to research and propose a kind of method that load has the silicon based mesoporous composite material of transition metal for preparing, by screening to reaction system, be implemented in synthesizing such matrix material under the slight alkali environment, and the matrix material that obtains has the transition metal charge capacity that significantly improves, and has high-specific surface area, large pore volume and the adjustable feature of aperture homogeneous.
The diesel oil HDS catalyzer that the present invention also provides the silicon based mesoporous composite material that utilizes this high capacity transition metal to prepare on the other hand, this catalyzer can have excellent catalytic activity and stability.
The present invention at first provides a kind of method that load has the silicon based mesoporous composite material of transition metal for preparing, comprise: the employing quaternary ammonium salt cationic surfactant is a template, methyl ethyl diketone is the auxiliary template agent, caustic solubility or water-soluble transition metal salt and silicon source are reacted and ageing under neutrality or alkaline environment, to reacted solid product wash, drying and roasting; The molar ratio of material example of control reaction system is in the reaction: quaternary ammonium salt cationic surfactant/SiO
2=0.0625-0.125, methyl ethyl diketone/SiO
2=1-10, Me/SiO
2=0.1-1, H
2O/SiO
2=60-200, Me wherein represents transition metal.
According to contriver's research, the essence factor of the mesoporous material of the synthetic high transition species content of influence original position under alkaline condition is that under alkaline condition, transition metal species for example Mo reacts with alkali, generation single-unit [MoO
4]
2-, this reaction trend is difficult in the building-up process and the silica common deposited Mo species, therefore, must be difficult to obtain the mesoporous composite material of transition metal M o high level.
Therefore the contriver thinks, realize that for example the Mo transition metal species deposits in material, at first need to change the single-unit existence of Mo species, and when realizing the change of existence, also expectation can realize that novel Mo species existence can have very high reactive behavior with silicon species, therefore, can be anchored in the material by reaction.If can realize the above change of transition metal species, not only can improve the charge capacity of transition metal species in material, improve the availability of transition metal source in reaction process, and the grappling response feature can make species transition disperse at the mesoporous material camber.
Transition metal species has unoccupied orbital more, therefore, has good coordination effect usually.And can realize several carbonyl containing compounds of working as of fine coordination effect with these transition metal species, therefore, the applicant studies show that, in the time of changing the existence of transition metal species under the alkaline condition, at first ought be to introduce carbonyl containing compound.In containing the compound of carbonyl, methyl ethyl diketone especially will generate the high reactivity species under the strong alkaline condition under the meta-alkalescence condition, and therefore, transition metal and methyl ethyl diketone can react under the meta-alkalescence condition, and the reactive behavior of reaction product is very high.
Based on such result, the present invention proposes a kind of silicon based mesoporous composite material that under neutrality or alkaline medium condition, synthesizes high transition metal carrying capacity, for example the method for MoSiOx mesoporous composite material.It is template that the core of this method is to adopt quaternary ammonium salt cationic surfactant, methyl ethyl diketone (HAcac) is the use of auxiliary template agent, and the application meeting of HAcac exerts an influence to duct size, duct alignment degree, Mo transition metal carrying capacity and Mo source utilization ratio etc.Method of the present invention is by tensio-active agent and auxiliary template agent HAcac and the effect of Mo species, then, the Mo species again with the hydrolysate silicon hydroxyl effect of silicon source, prepare transition metal M o high dispersing, the mesoporous composite material that transition metal M o charge capacity is very high.This MoSiOx mesoporous composite material also has the mesoporous aperture of homogeneous, bigger specific surface area; The Mo species transition has in duct internal surface enrichment and high dispersing trend.The matrix material of the inventive method preparation is the charge capacity of the 1wt%Mo transition metal of the compound realization of original position and 1/100 Mo source utilization ratio under the alkaline condition in the past head and shoulders above.
The transition metal species that the inventive method is suitable for comprises and can the transition metal that coordination reaction forms covalent linkage take place with HAcac that for example described transition metal can comprise molybdenum, tungsten, vanadium or titanium etc.
The method according to this invention, described reaction process comprises: reaction system under alkaline environment stirring reaction 1-30 hour sealed ageing 1 hour-30 days then.According to the alkaline state of reaction system, preferred reaction 3-10 hour, ageing 5-10 days.
One of feature of the synthetic method of the silicon based mesoporous composite material that the present invention proposes is to adopt quaternary ammonium salt cationic surfactant.That relatively more commonly used is the alkyl trimethyl ammonium salt (C of C10-24
mTMA
+), or the alkyl triethyl ammonium salt (C of C10-24
mTEA
+), quaternary ammonium salt cationic surfactant forms micella when concentration reaches certain limit, for the self-assembly of oxide precursor provides template; And the pore properties of prepared material and specific surface area character etc. exerted an influence.In the above tensio-active agent that the present invention preferably uses, m=10-24.
Neutrality or alkali systems are that synthetic environment is another feature of the present invention, preferably control the alkaline environment system, and promptly the alkali systems of pH＞7 can be NaOH, also can be KOH, ammoniacal liquor etc.Under alkaline medium condition, the silicon species that the hydrolysis of silicon source obtains has negative electricity, and there is electrostatic interaction each other in silicon species, therefore is difficult to assemble; Even silicon species can be at quaternary ammonium salt micella template (C for example
mTMAB) assemble the periphery, and resulting electronegative micelle also can make solution stable existence in synthetic system, can not get the solid phase product, more can not get having the mesoporous of orderly pore passage structure.And, be example with Mo, under strong alkaline condition, there is the very big single-unit [MoO of concentration in the Mo source with liquid phase
4]
2-Exist, assemble being suppressed between electronegative Mo particle and the electronegative silicon species, therefore under alkaline medium condition, be difficult to realize the compound of transition metal M o and mesoporous material by in-situ synthetic method.The invention provides a kind of new synthetic system, not only have solid phase prod to generate, and the Mo species content in the solid phase prod is higher, solid phase prod also has the pore properties and the very big specific surface area of excellent mesoporous scope.
The adding of methyl ethyl diketone (HAcac) also is one of feature of the present invention.HAcac has keto-acid and ketone-two kinds of structures of hydroxyl formula, and in the especially dense strongly basic medium of meta-alkalescence, HAcac exists with the ketone-carbonyl structure with conjugate character.The contriver discovers, does not add the Mo source when reacting synthetic system, and when promptly the pure silicon sill under the strong alkaline condition being synthesized, under the situation that does not add HAcac, synthetic system stirs and even the heating promotion through long-time, all can't obtain solid product; Add an amount of HAcac, then can obtain having the silicon-based mesoporous material of vermiform pore passage structure.Study on the synthesis to MoSiOx finds that under the fewer situation of Mo source add-on, do not add HAcac, synthetic system can't obtain solid phase prod; After adding an amount of HAcac, can prepare MoSiOx mesoporous composite material with high transition metal M o load.All there is influence in the use of HAcac to pore properties and specific surface area character.Add HAcac, can improve prepared mesoporous material pore passage structure order degree, hole diameter enlargement size, increase pore volume, and change and porous changes the size that influences specific surface area because of the order degree of material.Each side function Characteristics according to HAcac, the contriver proposes the mechanism of action of HAcac: the lone-pair electron on the HAcac ketonic oxygen are connected the peripheral stretching, extension of CTMAB micella by the N+ effect with quaternary micella template, form the novel micella template of CTMAB-HAcac.Under the situation that does not add the Mo source, silicon species obtains mesoporous material by the HAcac effect in intermolecular hydrogen bonding and the novel micella template thereby be implemented in the peripheral gathering of micella template and assemble; For synthesizing of MoSiOx, the Mo species by with the HAcac ketonic oxygen on lone-pair electron or the lone-pair electron effect on the constitutional isomer carboxyl oxygen form title complex, silicon species interacts with Mo under the effect of CTMAB-HAcac micella and assembles, form the Si-O-Mo key, thereby realize the introducing of Mo species.This mechanism model can also have same mechanism with the transition metal species that lone-pair electron on the HAcac ketonic oxygen or the lone-pair electron effect on the constitutional isomer carboxyl oxygen form title complex for other, so can explain that transition metal species is in the enrichment and make the species high dispersing in mesopore orbit of the load of material middle and high concentration and transition metal species; Can explain the duct characteristic of prepared material and the silica-based species depositional phenomenon of in material is synthetic, finding of promotion.
Contriver's research finds that also under strong alkaline condition, the solubility property of Mo source in synthetic system is very good, and can form single-unit Mo species [MoO
4]
2-, for the high dispersing of Mo species in material laid a good foundation.Contain [NH in this Mo source
4]
+Component can be destroyed the steady state of electronegative micelle at sol system, promotes the micelle deposition.
So the synthetic method of MeSiOx mesoporous composite material provided by the present invention comprises: with quaternary ammonium salt cationic surfactant C
mTMA
+(for example, C
14TMABr, C
14TMACl, C
16TMABr or C
16TMACl) be template, with the methyl ethyl diketone is auxiliary template, with white carbon black, water glass, tetraethoxy, water glass or silicon sol etc. is the silicon source, with alkaloid substances such as NaOH or KOH, ammoniacal liquor is base matter, for example four hydration Ammonium Heptamolybdates, ammonium metawolframate, ammonium meta-vanadate etc. are transition metal M e source with caustic solubility or water-soluble transition metal salt, the anabolic reaction system, wherein, tensio-active agent/SiO
2=0.0625～0.125, HAcac/SiO
2=1～10, Me/SiO
2=0.1～1, H
2O/SiO
2=60～200, according to such proportioning reactant is mixed, fully stir 1～30hr after, vessel port is sealed ageing 1 hour to 30 days under envrionment conditions then with mould material.After ageing finishes, product through separate, behind washing and the 100 ℃ of dry about 6hr.After 500-600 ℃ of following roasting 5-8 hour, characterize.
Above-mentioned reaction process can be to make template elder generation and transition metal species effect, then make transition metal species and silicon source hydrolysate-silicon hydroxyl effect again, product is through the sealing ageing under the envrionment conditions, this process is by the consumption of control alkali lye, and the add-on in optimization Me source, can prepare Me content greater than 10wt%, Me source utilization ratio reaches 60% MeSiOx mesoporous composite material.By the use of HAcac, this matrix material has more high-specific surface area (can reach 966m
2/ g), bigger and adjustable mesoporous aperture (reaching 4.7nm) and pore volume (1.5cm
3/ characteristics such as g).
Another aspect of the present invention utilizes institute's synthetic mesoporous composite material further to prepare diesel oil catalytic desulfurhydrogenation (HDS) catalyzer, is carrier for described load the silicon based mesoporous composite material of transition metal being arranged, with γ-Al
2O
3For binding agent be combined with the product that the auxiliary activity metal obtains.The method for preparing catalyst that proposes comprises that the supernatant liquor with this synthetic system is that dissolution with solvents auxiliary activity metal component is made solution, and with described matrix material and γ-Al
2O
3The binding agent thorough mixing, dry roasting removed template method and auxiliary template agent; Described auxiliary activity metal comprises transiting metal nickel, cobalt or tungsten etc., but with carrier in the compound transition metal should be inequality, better be transiting metal nickel or cobalt.In this Preparation of Catalyst, caking agent is the amount of being routinely added to, instead mend introducing assistant metal component method in fresh MeSiOx powder by wetting hybrid system of supernatant liquor and supernatant liquor, because solution system that is adopted and solid phase reach molecular balance substantially and balance each other, therefore, the utilization of this solvent is save energy not only, alleviates environmental pollution, and helps keeping the original meso-hole structure of material not to be damaged.Medium diesel oil with sulphur content 320ppm is that raw material carries out the hydrogenation reaction test, through tracking and measuring, sulphur content in the hydrogenated diesel oil product is controlled in about 8ppm, can realize that desulfurization degree is 97.5%, and can reach the good result that the maintenance of the sulphur content in the product diesel oil can't detect in 300 hours.
Description of drawings
Fig. 1 is the XRD figure according to embodiment 1 prepared MoSiOx provided by the invention.
Fig. 2 is the N according to embodiment 1 obtained MoSiOx
2Adsorption isothermal line.
Fig. 3 is according to the pyridine infrared spectrum of embodiment 1 obtained MoSiOx material (Py-FT-IR spectrogram).
Fig. 4 is the SEM figure according to embodiment 4 prepared MoSiOx provided by the invention, and as seen from the figure, the MoSiOx matrix material has regular spherical appearance, and particle diameter is in 200～500nm scope.
Fig. 5 is the HRTEM figure according to the embodiment of the invention 4 prepared MoSiOx materials, as seen from the figure, be covered with the duct on the particle of prepared MoSiOx matrix material, and pore passage structure is based on vermiform.
Fig. 6 is the XRD figure according to embodiment 4 provided by the invention prepared MoSiOx under weak basic condition.
Fig. 7 is the N according to embodiment 4 obtained MoSiOx
2Adsorption isothermal line.
Fig. 8 is the Py-FT-IR spectrogram according to embodiment 4 obtained MoSiOx materials.
Fig. 9 is the HRTEM result who presses the VSiOx of embodiment 5 preparations.
Figure 10 is the SEM result who presses the WSiOx of embodiment 6 preparations.
Figure 11 is the Py-IR result of the NiMoSiOx of embodiment 7 preparations.
Specific embodiments
Below further specify technical scheme of the present invention by specific embodiment and realize and beneficial effect, understand essence of the present invention better to help the reader, but practical range of the present invention do not constituted any restriction.
Add deionized water 25ml in beaker, add 1g NaOH, dissolving becomes alkali lye fully; 0.6g four hydration Ammonium Heptamolybdates are directly joined in this alkali lye, make it dissolving fully under vigorous stirring; Add methyl ethyl diketone 3ml, stir 10min; Add quaternary ammonium salt cationic surfactant C
16TMABr 0.6g, vigorous stirring makes the solution system transparent and homogeneous; Add organosilicon source TEOS (tetraethoxy) 3ml at last, stir 3hr and make oxide precursor thing assembling polycondensation.With preservative film rim of a cup is sealed, placed ageing under the room temperature; After 7 days, also use the vacuum pump suction filtration, wash 3～5 times, with the powder dry 6hr in about 100 ℃ that reclaims with deionized water wash; Powder transfer in crucible, is put into 550 ℃ of roasting 6hr in the retort furnace, can obtains the MoSiOx mesoporous composite material of the about 6.3wt% of Mo content.
The BET specific surface area that adopts the BET Model Calculation to obtain this matrix material is 966m
2/ g, adopting the BJH method to calculate the material pore volume is 1.5cm
3/ g, the pore size distribution homogeneous of material, aperture size is 4.68nm.These information have proved that further the experiment product has good structurally ordered degree and good porous.
Fig. 1 is the XRD figure of this matrix material, can see, at low angle, the diffraction peak of 2 distinctive mesoporous materials occurs, proves that the degree of order of MoSiOx product is higher, better heat stability.The diffraction peak that does not occur the body phase oxide in the high angle XRD spectra, the Mo species high dispersing in the testimonial material does not form MoO
3Crystal.(a) arrow indication and illustration (b) show the diffraction spectrogram of 2 θ=3.5 and 5-80 respectively among the figure.
Fig. 2 is the N of this MoSiOx matrix material
2Adsorption isothermal line, the illustration among the figure are the pore distribution curve of this matrix material.
The pyridine meleic acid property representation of this material is referring to Fig. 3, from the absorption spectrogram of 200 ℃ and 350 ℃ (the figure: ℃ absorption spectrum a.200; B.350 ℃ absorption spectrum) as can be seen, the acidity of material mainly comes from the L acid site, and B acid site amount is then very low.It is less demanding that weak acid can be used for to acidity material to middle strong acid acidity, is the reaction of active ingredient with the Mo species.
Embodiment 2
0.5g NaOH is dissolved in the 25ml deionized water, 2.5g four hydration Ammonium Heptamolybdates are directly joined in the alkali lye, dissolving fully under vigorous stirring; Add methyl ethyl diketone 3ml, stir 10min; Add quaternary ammonium salt cationic surfactant C
16TMABr 0.6g, vigorous stirring makes the solution system transparent and homogeneous; Add organosilicon source TEOS 3ml, stir 3hr and make oxide precursor thing assembling polycondensation.With preservative film rim of a cup is sealed, placed ageing under the room temperature; After 7 days, also use the vacuum pump suction filtration, wash 3～5 times, with the powder dry 6hr in about 100 ℃ that reclaims with deionized water wash; Powder transfer in crucible, is put into 550 ℃ of roasting 6hr in the retort furnace, can obtains the MoSiOx mesoporous composite material, molybdenum charge capacity wherein is higher than 6.7wt% after measured.Its pore structure feature is similar to the material of embodiment 1, and the BET specific surface area is 921m
2/ g, adopting the BJH method to calculate the material pore volume is 1.5cm
3/ g, and the pore size distribution homogeneous of material, aperture size is 4.86nm.
0.5g NaOH is dissolved in the 25ml deionized water, adds 0.17g ammonium vanadate dissolving back and add methyl ethyl diketone 3ml, stir 10min; Continue to add quaternary ammonium salt cationic surfactant C
16TMABr 0.6g, vigorous stirring makes the solution system transparent and homogeneous; Add organosilicon source TEOS 3ml, stir 3hr and make oxide precursor thing assembling polycondensation.With preservative film rim of a cup is sealed, placed ageing under the room temperature; After 7 days, also use the vacuum pump suction filtration, wash 3～5 times, with the powder dry 6hr in about 100 ℃ that reclaims with deionized water wash; Powder transfer in crucible, is put into 550 ℃ of roasting 6hr in the retort furnace, can obtains the VSiOx mesoporous composite material.The charge capacity 10.1wt% of V wherein, the BJH aperture of synthetic materials is 5.2nm, BJH desorption pore volume is 0.69cm
3/ g.
In beaker, add deionized water and each 25ml of dehydrated alcohol, add 0.6g template C
16TMAB after the dissolving, adds HAcac fully; After stirring 10min, add medium and regulate actual ammoniacal liquor, it is the yellow (pH is about 8) of transparent and homogeneous that vigorous stirring makes solution system; Add organosilicon source TEOS 3ml, after stirring makes and presents muddiness, add the aqueous solution of 5ml four hydration Ammonium Heptamolybdates (0.35g).Vigorous stirring 3hr makes the oxide precursor thing fully assemble polycondensation.With preservative film rim of a cup is sealed, placed ageing under the room temperature; After 7 days, also use the vacuum pump suction filtration, wash 3～5 times, with the powder dry 6hr in about 100 ℃ that reclaims with deionized water wash; Powder transfer in crucible, is put into 550 ℃ of roasting 6hr in the retort furnace, can obtains the about 14.6wt% of Mo content, Mo source utilization ratio is about 60% MoSiOx mesoporous composite material (the present invention also is designated as MoSiOx-w).
Fig. 4 is the SEM figure of prepared MoSiOx, and as seen from the figure, the MoSiOx matrix material has regular spherical appearance, and particle diameter is in 200～500nm scope.
Fig. 5 is the HRTEM figure of prepared MoSiOx material, as seen from the figure, be covered with the duct on the particle of prepared MoSiOx matrix material, and pore passage structure is based on vermiform.
The XRD figure of this material is referring to Fig. 6, and the diffraction peak at 2 distinctive mesoporous materials of low angle appearance proves that the degree of order of MoSiOx product is higher, better heat stability.The diffraction peak that does not occur the body phase oxide in the high angle XRD spectra, the Mo species high dispersing in the testimonial material does not form MoO
3Crystal.
Fig. 7 is the N of obtained MoSiOx
2Adsorption isothermal line.The BET specific surface area that adopts the BET Model Calculation to obtain material is 891m
2/ g, adopting the BJH method to calculate the material pore volume is 0.6cm
3/ g, and the pore size distribution homogeneous of matrix material, aperture size is 2.9nm.These information have proved that further the experiment product has good structurally ordered degree and good porous.
Fig. 8 is the Py-FT-IR spectrogram of obtained MoSiOx material, and a is 200 ℃ of absorption spectrums among the figure, and b is 350 ℃ of absorption spectrums, and from the absorption spectrogram of 200 ℃ and 350 ℃ as can be seen, the acidity of material mainly comes from the L acid site, and B acid site amount is then very low.It is less demanding that weak acid can be used for to acidity material to middle strong acid acidity, is the reaction of active ingredient with the Mo species.
In beaker, add deionized water 10ml and dehydrated alcohol 25ml, add 0.6g template C
16TMAB (cetyl trimethylammonium bromide) after the dissolving, adds Hacac fully; After stirring 10min, add medium and regulate reagent ammoniacal liquor, it is the yellow (pH is about 8) of transparent and homogeneous that vigorous stirring makes solution system; Add organosilicon source TEOS 3ml; After stirring makes the preliminary muddiness of system, dropwise add the aqueous solution of ammonium vanadate.Through vigorous stirring 3hr, make the oxide precursor thing fully assemble polycondensation reaction mixture.With preservative film rim of a cup is sealed, placed ageing under the room temperature; After 7-10 days, also use the vacuum pump suction filtration, wash 3～5 times, with the powder dry 6hr in about 100 ℃ that reclaims with deionized water wash; Powder transfer in crucible, is put into 550 ℃ of roasting 6-8hr in the retort furnace, can obtains the VSiOx mesoporous composite material.The charge capacity 10.2wt% of V wherein.
Fig. 9 is the HRTEM result of the VSiOx of preparation.The VSiOx matrix material has special macropore yardstick pore size distribution as can be seen, and N
2The adsorption-desorption analytical results shows that material has the two mesoporous distributions of characteristic, and the aperture is adjustable by the change of material proportion.
Embodiment 6
In beaker, add deionized water 10ml and dehydrated alcohol 25ml, add 0.6g template C
14TMAB after the dissolving, adds Hacac fully; After stirring 10min, add medium and regulate reagent ammoniacal liquor, it is the yellow of transparent and homogeneous that vigorous stirring makes solution system; Add organosilicon source TEOS 3ml; After stirring makes the preliminary muddiness of system, dropwise add the aqueous solution of ammonium metawolframate.Through vigorous stirring 3hr, make the oxide precursor thing fully assemble polycondensation reaction mixture.With preservative film rim of a cup is sealed, placed ageing under the room temperature; After 7 days, also use the vacuum pump suction filtration, wash 3～5 times, with the powder dry 6hr in about 100 ℃ that reclaims with deionized water wash; Powder transfer in crucible, is put into 550-600 ℃ of roasting 5-6hr in the retort furnace, can obtains the WSiOx mesoporous composite material.The charge capacity of W can reach 15wt% among the WSiOx.
Figure 10 is the SEM result of the WSiOx of preparation.As can be seen, WSiOx has very regular spherical appearance.XRD analysis shows that material has the characteristic diffraction peak of mesoporous material.
Embodiment 7
The supernatant liquor of synthetic system among the embodiment 4 is inclined to,, will contain Ni solution and pour into and fill fresh MoSiOx powder and binding agent γ-Al as the solvent of dissolving Ni source nickelous nitrate
2O
3System, the binding agent consumption accounts for the 15-30wt% (in the catalyzer total amount) of catalyzer total amount, after fully mixing or adopting the ultrasonic wave aid dispersion, in about 70 ℃ of cryodryings, 100 ℃ continue dry 6hr after, transfer to retort furnace, by the temperature programming setting, to remove quaternary ammonium template and the agent of HAcac auxiliary template, obtain bimetallic catalyst NiMoSiOx 550 ℃ of following roastings, wherein, the Ni/Mo atomic ratio is 1/2.The gained material can be used as good diesel oil HDS catalyzer after compressing tablet, screening.
Figure 11 is the Py-IR result of the NiMoSiOx of preparation, has shown that the acidity of NiMoSiOx distributes.Among the figure, curve a shows that 200 ℃ total acid distributes; Curve b shows that 350 ℃ strong acid distributes.The acidity that this catalyzer can be described still only comes from L acid.
The catalytic cracking diesel oil of Shengli Oil Field is mixed with the straight-run diesel oil of Daqing oil field, and obtaining sulphur content is the Medium diesel oil raw material of 320ppm; With this NiMoSiOx is catalyzer, is 1.0hr in air speed
-1, hydrogen-oil ratio is 600, pressure 5MPa, and temperature is under 350 ℃ of conditions, and the diesel oil HDS that investigates NiMoSiOx is active and stable, and the result shows that the sulphur content in 300hr in the product diesel oil keeps detecting the result.
Claims (11)
1, the preparation load has the method for the silicon based mesoporous composite material of transition metal, comprise: the employing quaternary ammonium salt cationic surfactant is a template, methyl ethyl diketone is the auxiliary template agent, caustic solubility or water-soluble transition metal salt and silicon source are reacted and ageing under neutrality or alkaline environment, to reacted solid product wash, drying and roasting; The molar ratio of material example of control reaction system is in the reaction: quaternary ammonium salt cationic surfactant/SiO
2=0.0625-0.125, methyl ethyl diketone/SiO
2=1-10, Me/SiO
2=0.1-1, H
2O/SiO
2=60-200, Me wherein represents transition metal.
2, method according to claim 1, wherein, described reaction process comprises: reaction system under neutrality or alkaline environment stirring reaction 1-30 hour sealed ageing 1 hour-30 days then.
3, method according to claim 1, wherein, described transition metal comprises molybdenum, tungsten, vanadium or titanium.
4, according to claim 1 or 3 described methods, wherein, described caustic solubility or water-soluble transition metal salt are the ammonium salt of transition metal.
5, method according to claim 1 and 2, wherein, described reaction system is reacted containing under the alkaline environment of inorganic alkali solution, the pH of described alkaline environment＞7, this inorganic alkali solution comprises sodium hydroxide, potassium hydroxide or ammoniacal liquor.
6, method according to claim 1, wherein, described quaternary ammonium salt cationic surfactant is selected from C
mTMA
+Or C
mTEA
+, and m=10-24.
7, method according to claim 1, wherein, described silicon source comprises white carbon black, water glass, tetraethoxy, water glass or silicon sol.
8, method according to claim 1 and 2 wherein, is washed, after the drying, in 500-600 roasting 5-8 hour, is obtained described matrix material reacted solid product.
9, a kind of load has the silicon based mesoporous composite material of transition metal, and it prepares according to each described method of claim 1-8.
10, a kind of diesel oil catalytic desulfurhydrogenation catalyzer that is used for is that with the described load of claim 9 silicon based mesoporous composite material of transition metal to be arranged be carrier, with γ-Al
2O
3For binding agent be combined with the product that the auxiliary activity metal obtains, described auxiliary activity metal comprises transiting metal nickel or cobalt.
11, the described diesel oil catalytic desulfurhydrogenation of claim 10 Preparation of catalysts method, it comprises, prepare the silicon based mesoporous composite material that load has transition metal according to each described method of claim 1-8, supernatant liquor with this synthetic system is that dissolution with solvents auxiliary activity metal component is made solution, and with described matrix material and γ-Al
2O
3Binding agent thorough mixing, dry roasting removed template method and auxiliary template agent.
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