CN104525274A - Preparation method of modified carbon-covered titania-diatomite carrier - Google Patents
Preparation method of modified carbon-covered titania-diatomite carrier Download PDFInfo
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- CN104525274A CN104525274A CN201410619081.3A CN201410619081A CN104525274A CN 104525274 A CN104525274 A CN 104525274A CN 201410619081 A CN201410619081 A CN 201410619081A CN 104525274 A CN104525274 A CN 104525274A
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Abstract
The invention discloses a preparation method of a modified carbon-covered titania-diatomite carrier. The carrier is core-shell-structured particles. The shell of the core-shell structure is titania with uniformly deposited carbon. The core of the core-shell structure is a diatomite carrier. According to the invention, proper amounts of a transition metal salt and an organic compound of titanium are dissolved in an organic solvent; a proper amount of water is added, such that alumina hydrate colloid containing transition metal is obtained; the colloid is loaded onto the particulate diatomite carrier with an impregnation or spray dip manner; the carrier is dried and and is placed into a reaction furnace where the carrier contacts mixed gas of argon and hydrogen; the temperature is increased to 700 DEG C, and the delivering of argon and hydrogen is stopped; mixed gas of a carbon source and hydrogen is delivered in; and finally argon is delivered for cooling, such that the core-shell-structured modified carbon-covered alumina carrier is obtained. The transition metal salt is nitrate of Ni. The organic solvent is isopropanol or ethanol. The carbon source is carbon monoxide.
Description
Technical field
The present invention relates to the preparation method that char combustion titanium-diatomite support is covered in a kind of modification.
Background technology
The catalyst carrier that existing petrochemical industry is commonly used is usually using aluminium oxide as carrier, be easy to control and the feature such as cheap and easy to get owing to having good mechanical stability, specific area and pore structure, be all the time be most widely used, catalyst carrier that consumption is maximum, especially hydrotreating catalyst be nearly all utilize aluminium oxide or through the aluminium oxide of modification, compound as carrier.Therefore, about the preparation of alumina support and modification technology research are one of important contents of scientific worker and each catalyst Co. research always.Show for the research of aluminium oxide as catalyst carrier, aluminium oxide not only plays the effect of inert carrier, and it also has facilitation to the formation of active phase in hydrotreating catalyst.Interaction between Al2O3 and active component is comparatively strong, is conducive to the stable of active component in the dispersion of active component and course of reaction.But then, the strong interaction between the highly acid position on Al2O3 surface and active component often causes nickel, cobalt isoreactivity component generating nickel (or cobalt) aluminate, and the latter is difficult to the active phase that sulfuration generates sulphided state, thus reduces catalytic activity.Therefore, in order to improve activity and the catalytic efficiency of catalyst, much research adopts new material as carrier or takes to modify to improve the dispersion of active phase, the interaction between the active phase of change and carrier to alumina support, thus change the reproducibility of oxidation state predecessor, reduce the generation of spinelle thus the activity of raising catalyst.The patent No. is the preparation method that patent discloses a kind of silicon-containing alumina of 96120987.9.What it was prepared is a kind of is the alumina globule of 5% ~ 15wt% containing silica, and the character of the aluminium oxide obtained has certain improvement.But because globulation is complicated, and need to carry out low temperature drying in containing the atmosphere of ammonia, cause product yield low, preparation cost is high.The patent No. be 98114347.4 patent discloses alumina support of a kind of macropore high strength and preparation method thereof.One or more of the boehmite dry glue powder prepared by different material route mix mutually with carbon black powder and surfactant, are obtained by peptization, shaping, dry and calcination process.The existing higher intensity of the alumina support obtained, has again larger aperture and double hole channel distribution, but due to the carbon black that adds and surfactant after calcination process with amorphous existence, therefore its heat endurance and anticoking capability have much room for improvement.
On the other hand, research in recent years finds, the hydrodesulfurization activity of Co-Mo and the Ni-Mo catalyst of charcoal load is higher than Co-Mo and Ni-Mo catalyst (the Sano Y of traditional alumina load, Choi K H, Korai Y, et al., Appl.Catal.B, 49:219-225,2004; Farag H, Mochida I, Sakanishi K, Appl.Catal.A, 194/195:147-157,2000).Also there is the Co-Mo catalyst of bibliographical information Carbon Materials load to have lower coking tendency simultaneously, can further improve service life (Vissers J P R, Scheffer B, J.Catal., 105:227-284,1987 of catalyst; He S B, Sun C L, Du H Zh, et al., Chem.Eng.J, 141:284-289,2008).The high activity of the catalyst of Carbon Materials load is because the high-specific surface area of Carbon Materials ensure that the high degree of dispersion of active component on the one hand, also be because the interaction of active component and high-area carbon is more weak on the other hand, make the oxide species of its load be easy to sulfuration formation and there is the active phase of highly active Co-Mo-SII.But disadvantageously, although active carbon has very high specific area, its pore structure is abundant micropore, for the hydrodesulfurization (HDS) of larger molecule as dibenzothiophenes (DBT), resistance to mass tranfer is very large, and these micropores are difficult to be utilized.For some mesoporous carbon material, then due to bad mechanical strength, the reasons such as specific surface is little are also difficult to be applied
Since rising of Tokyo Univ Japan in 1972 has been led since the strong professor of clear and tutor Duo Ben finds photocatalysis principle and effect for the first time, the research of optically catalytic TiO 2 is always very active, be widely used in the exploitation of solar cell, gas sensor, solar energy preparing hydrogen by decomposing, the photocatalytic degradation of sewage and waste water, photo-catalyst, self-cleaning and antifog etc.But the forbidden band of TiO2 wider (Eg=3.2eV), only can only be accounted in sunshine about 5% (λ≤387.5nm) ultraviolet light excite.Thus, improve its quantum yield, widen TiO2 to the response of visible ray accounting for solar radiation 46%, thus full range utilizes solar energy, is the developing direction of TiO2 catalysis material.The spectral sensitization of organic dyestuff, noble metal support and transient metal doped, although can improve the utilization rate to sunshine, also make photocatalytic titania film ultraviolet light light reaction reduce, photo-catalysis capability is weak, photo and thermal stability be deteriorated, cost improve.Asahi etc. calculate the state density (DDSs) of the rear TiO2 of C, N, F, P or S doping respectively, after showing that TiO2 is anion doped, its light absorption edge can be made to be shifted to lower level, exciting light threshold values can be expanded to visible region (Science2001,293,269).Because carbon has suitable electrical conductivity, density is very low, and carbon can enter in titanium dioxide by the organic carbon of preference temperature, changes the absorption of visible ray, thus obtains good photocatalysis effect.Khan etc., by controlling methane and oxygen flow, the flame calcination titanium sheet of 850 degree, obtain the titanium dioxide (Science 2002,297,2243) of carbon doping.But mainly the form of rutile exists after the titanium dioxide high-temperature roasting of carbon doping, and the reunion of TiO2 nanocrystal may be caused to grow up.Irie etc. to TiC 600 degree of oxidizing annealings in oxygen stream, the Carbou doped titanium-oxide obtained.
Therefore the study hotspot that titanium oxide progressively becomes new is added in the carrier, CN101024168A discloses with titanate esters (comprising other various alkoxide etc.), lauryl amine (DDA), vitamin B6s etc. are raw material, the titanium-oxide graded Porous materials of one-step synthesis method carbon doping.This preparation method comprises the following two kinds scheme: at (1) 80 DEG C by titanate esters and carbon source (as lauryl amine DDA, the ratio 0.05 ~ 1 of DDA/TiO2 material amount) mix in conical flask, the mixed liquor (volume ratio is 10: 1 ~ 5: 1) of ethanol and deionized water is joined in reactant liquor fast, stir, aging, washing, suction filtration, drying, obtains white powder.White powder solid in tube furnace under nitrogen protection at 300 ~ 600 DEG C roasting 2-8h namely obtain the porous oxidation titanium powder of yellowish carbon doping.(2) under room temperature, 5.8 ~ 8.0g titanate esters, 15 ~ 30ml deionized water, 4.0 ~ 8.0g carbon source (as vitamin B6) are mixed; stir; aging; dry at 60 DEG C; white powder, white powder under the condition of nitrogen protection at 300 ~ 600 DEG C roasting 2-8h namely obtain the porous oxidation titanium powder of yellowish carbon doping.Described titanate esters can be tetraethyl titanate [Ti (OC2H5) 4], metatitanic acid n-propyl [Ti (OC3H7) 4], isopropyl titanate [Ti (iso-OC3H7) 4] or butyl titanate [Ti (OC4H9) 4].Described carbon source can be lauryl amine, urea, tetrabutylammonium, cyclohexylamine, vitamin B6.Adopt above formula and reaction condition, through above-mentioned processing step, can prepare and have foramen magnum-mesoporous hierarchical porous structure, single anatase phase, absorption spectrum expansion is wide, has the titania meterial of ultraviolet and the highly active carbon doping of visible light catalytic.
Summary of the invention
The object of the invention is to propose the preparation method that char combustion titanium-diatomite support is covered in a kind of modification.
For reaching this object, the present invention by the following technical solutions:
The preparation method of char combustion titanium-diatomite support is covered in a kind of modification, described carrier is the particle of nucleocapsid structure, the shell of described nucleocapsid structure is the titanium oxide of uniform deposition charcoal, the kernel of described nucleocapsid structure is-diatomite support, it is characterized in that comprising the following steps: by the organic compound of appropriate transition metal salt and titanium, dissolve in organic solvent, add suitable quantity of water, pH is regulated to be 1 ~ 5, 0.5 ~ 4 hour is hydrolyzed in 40 ~ 80 DEG C of water-baths, obtain the hydrated alumina colloid containing transition metal, the organic compound of titanium is butyl titanate, the mixture mixed with 1:1:1 of tetraisopropyl titanate and tetraethyl titanate, colloid is loaded on granular diatomite support, in 100 ~ 120 DEG C of dryings 4 ~ 10 hours by the mode of flooding or spray, after dry, carrier is placed in reacting furnace, contact with the mist of hydrogen with argon gas, be warming up to 700 DEG C of stoppings and pass into argon gas and hydrogen, change the mist passing into carbon source and hydrogen into, finally pass into argon gas cooling, char combustion alumina supporter is covered in the modification must with nucleocapsid structure, and transition metal salt is the nitrate of Ni, organic solvent is isopropyl alcohol or ethanol, carbon source carbon monoxide.
Detailed description of the invention
Embodiment 1
The preparation method of char combustion titanium-diatomite support is covered in a kind of modification, described carrier is the particle of nucleocapsid structure, the shell of described nucleocapsid structure is the titanium oxide of uniform deposition charcoal, the kernel of described nucleocapsid structure is-diatomite support, it is characterized in that comprising the following steps: by the organic compound of appropriate transition metal salt and titanium, dissolve in organic solvent, add suitable quantity of water, pH is regulated to be 1, 0.5 hour is hydrolyzed in 40 DEG C of water-baths, obtain the hydrated alumina colloid containing transition metal, the organic compound of titanium is butyl titanate, the mixture mixed with 1:1:1 of tetraisopropyl titanate and tetraethyl titanate, colloid is loaded on granular diatomite support, in 100 ~ 120 DEG C of dryings 4 ~ 10 hours by the mode of flooding or spray, after dry, carrier is placed in reacting furnace, contact with the mist of hydrogen with argon gas, be warming up to 700 DEG C of stoppings and pass into argon gas and hydrogen, change the mist passing into carbon source and hydrogen into, finally pass into argon gas cooling, char combustion alumina supporter is covered in the modification must with nucleocapsid structure, and transition metal salt is the nitrate of Ni, organic solvent is isopropyl alcohol or ethanol, carbon source carbon monoxide.
Embodiment 2
The preparation method of char combustion titanium-diatomite support is covered in a kind of modification, described carrier is the particle of nucleocapsid structure, the shell of described nucleocapsid structure is the titanium oxide of uniform deposition charcoal, the kernel of described nucleocapsid structure is-diatomite support, it is characterized in that comprising the following steps: by the organic compound of appropriate transition metal salt and titanium, dissolve in organic solvent, add suitable quantity of water, pH is regulated to be 2, 2 hours are hydrolyzed in 50 DEG C of water-baths, obtain the hydrated alumina colloid containing transition metal, the organic compound of titanium is butyl titanate, the mixture mixed with 1:1:1 of tetraisopropyl titanate and tetraethyl titanate, colloid is loaded on granular diatomite support, in 100 ~ 120 DEG C of dryings 4 ~ 10 hours by the mode of flooding or spray, after dry, carrier is placed in reacting furnace, contact with the mist of hydrogen with argon gas, be warming up to 700 DEG C of stoppings and pass into argon gas and hydrogen, change the mist passing into carbon source and hydrogen into, finally pass into argon gas cooling, char combustion alumina supporter is covered in the modification must with nucleocapsid structure, and transition metal salt is the nitrate of Ni, organic solvent is isopropyl alcohol or ethanol, carbon source carbon monoxide.
Embodiment 3
The preparation method of char combustion titanium-diatomite support is covered in a kind of modification, described carrier is the particle of nucleocapsid structure, the shell of described nucleocapsid structure is the titanium oxide of uniform deposition charcoal, the kernel of described nucleocapsid structure is-diatomite support, to it is characterized in that comprising the following steps after stirring by the organic compound solubilization of appropriate transition metal salt and titanium in organic solvent, add suitable quantity of water, pH is regulated to be 5, 4 hours are hydrolyzed in 80 DEG C of water-baths, obtain the hydrated alumina colloid containing transition metal, the organic compound of titanium is butyl titanate, the mixture mixed with 1:1:1 of tetraisopropyl titanate and tetraethyl titanate, colloid is loaded on granular diatomite support, in 100 ~ 120 DEG C of dryings 4 ~ 10 hours by the mode of flooding or spray, after dry, carrier is placed in reacting furnace, contact with the mist of hydrogen with argon gas, be warming up to 700 DEG C of stoppings and pass into argon gas and hydrogen, change the mist passing into carbon source and hydrogen into, finally pass into argon gas cooling, char combustion alumina supporter is covered in the modification must with nucleocapsid structure, and transition metal salt is the nitrate of Ni, organic solvent is isopropyl alcohol or ethanol, carbon source carbon monoxide.
Obviously, the above embodiment of the present invention is only for example of the present invention is clearly described, and is not the restriction to embodiments of the present invention.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here exhaustive without the need to also giving all embodiments.And these belong to spirit institute's apparent change of extending out of the present invention or change and are still among protection scope of the present invention.
Claims (1)
1. the preparation method of char combustion titanium-diatomite support is covered in a modification, described carrier is the nucleocapsid structure comprising shell and kernel, shell is titanium oxide, uniform deposition charcoal on it, kernel is-diatomite support, it is characterized in that comprising the following steps: by the organic compound of transition metal salt and titanium and organic solvent phased soln, then in this solution, deionized water is added, pH is regulated to be 1 ~ 5, hydrolysis obtains the hydrated alumina colloid containing transition metal, described hydrolysising condition is react 0.5 ~ 4 hour in 40 ~ 80 DEG C of water-baths, the organic compound of titanium is butyl titanate, the mixture mixed with 1:1:1 of tetraisopropyl titanate and tetraethyl titanate, to load on granular diatomite support, in 100 ~ 120 DEG C of dryings 4 ~ 10 hours, described load was undertaken by the mode of flooding or spray with colloid, dried carrier is sent into reactor, the gaseous mixture of argon gas and hydrogen is passed in phase reactor, thus and carrier contact, then heat up, until 700 DEG C of stoppings pass into described gaseous mixture, then the gaseous mixture of Small molecular alkane or alkene and hydrogen is passed into, finally pass into argon gas, char combustion alumina supporter is covered in the modification obtaining having nucleocapsid structure, and transition metal salt is the nitrate of Ni, organic solvent is isopropyl alcohol or ethanol, carbon source carbon monoxide.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109652192A (en) * | 2019-01-11 | 2019-04-19 | 西安凯丰铁路机电设备有限公司 | A kind of aqua type coefficient of friction modifiers for rail tread |
| CN116282348A (en) * | 2023-03-31 | 2023-06-23 | 万思得新材料科技(中山)有限公司 | Photoresist dye wastewater treatment process |
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| CN101804338A (en) * | 2009-05-19 | 2010-08-18 | 王秀宝 | Process for producing nano titanium dioxide/diatomite composite photocatalytic material |
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| CN1078921A (en) * | 1992-05-18 | 1993-12-01 | 美国环球油品公司 | The catalyst that contains homogeneous layered clay/inorganic oxide |
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| CN109652192A (en) * | 2019-01-11 | 2019-04-19 | 西安凯丰铁路机电设备有限公司 | A kind of aqua type coefficient of friction modifiers for rail tread |
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| CN116282348B (en) * | 2023-03-31 | 2024-01-02 | 万思得新材料科技(中山)有限公司 | Photoresist dye wastewater treatment process |
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