CN1169621C - Preparation method of transition metal carbide catalyst and its catalytic performance - Google Patents
Preparation method of transition metal carbide catalyst and its catalytic performance Download PDFInfo
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- CN1169621C CN1169621C CNB021094586A CN02109458A CN1169621C CN 1169621 C CN1169621 C CN 1169621C CN B021094586 A CNB021094586 A CN B021094586A CN 02109458 A CN02109458 A CN 02109458A CN 1169621 C CN1169621 C CN 1169621C
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Abstract
The present invention discloses a preparation method of a catalyst of transition metal carbide, a precursor of the catalyst is composed of carbon material and transition metal compounds. The transition metal compounds are supported on carbon material by an immersion or mechanical mixed method, the supported weight percentage of the transition metal compounds is in the range of 1 to 200%. The temperature of the obtained sample is raised to 500 to 1000 DEG C at a temperature rise rate of 1 to 20 DEG C /min in a hydrogen atmosphere, and the obtained sample is reduced for 0.1 to 10 hours at constant temperature; the temperature of the hydrogen atmosphere drops to the room temperature, the reduced sample is inactivated with 1% oxygen, or the temperature drops to the room temperature in an inert atmosphere, and the corresponding transition metal carbide or the transition metal carbide supported on the carbon material is obtained. The prepared transition metal carbide can be used for various reactions relating to hydrogen and can be particularly used for the hydrogenation refining reaction and the selective hydrogenation reaction.
Description
Technical field
The present invention relates to the preparation method of a kind of transition metal list constituent element and double elements carbide.Specifically, adopt the hot hydrogen reduction method of carbon to make transistion metal compound be converted into transition metal carbide and prepared transition metal carbide as Application of Catalyst.
Background technology
Transition metal carbide is to be embedded between the class that the transition metal lattice produces by carbon atom to fill the type compound, has the characteristic of covalency solid, ionic crystal and transition metal concurrently.Since nineteen seventies it is found that transition metal carbide has class precious metal character, transition metal carbide had received very big concern at catalytic field.Transition metal carbide has unique reactivity worth to reactions such as ammonia synthesis and decomposition, hydrofining, selection hydrogenation and isomerization.The temperature programming carbonization method of development such as Boudart can be prepared the transition metal carbide (L.Leclercq than high-ratio surface, M.Boudart, et al., U.S.Pat.No.4107282,1978), but,, and be difficult to remove so the gained carbide contains carbon distribution owing to adopt hydrocarbon compound; In addition, carbide is very active, must careful control carbonization and passivating process.The method that carbothermic reduction prepares carbide is widely used in fields such as pottery and superhard material, but gained carbide specific surface is low, is unsuitable for using at catalytic field.Ledoux etc. utilize the carbothermic reduction method to make metallic compound steam and carbon material reaction (M.J.Ledoux, et al., U.S.Pat.No.4914070,1990), have prepared the carbide of high-ratio surface, but temperature of reaction higher (more than 1000 ℃).
Summary of the invention
The object of the invention has been to provide a kind of method for preparing single constituent element and multicomponent transition metal carbide under mild conditions, the transition metal carbide of preparation has shown preferable activity and selectivity to hydrogen-involved reaction, especially hydrogenating desulfurization and selective hydrogenation reaction has been shown higher activity.
In the preparation transition metal carbide method provided by the invention, precursor is made up of carbon material and transition metal (comprising Mo, V, W, Nb, Cr, Ta, Co, Fe, Ni etc.) compound.Carbon material in the precursor comprises various gacs, carbon black and carbon nanotube, carbon fiber etc.; Transistion metal compound comprises oxide compound, sulfide, halogenide or transition metal mixtures and their mixture etc.The multicomponent transition metal carbide also can adopt this method preparation in addition.The multicomponent transition metal carbide can be expressed as follows MxM ' yC, and wherein M is Co, Fe, and Ni grade in an imperial examination VIII family element, M ' is Mo, V, W, Nb, Cr, Ta grade in an imperial examination IVB, VB, VIB, VIIB subgroup element; Wherein 0＜X＜2,0＜Y＜2, preferred X=1, Y=1.
The transition metal carbide method for preparing provided by the invention is: the method that adopts dipping or mechanically mixing with transition metal compound loaded to carbon material, under nitrogen atmosphere, rise to 500-1000 ℃ with 0.1-20 ℃ of/minute intensification speed, constant temperature reduction 0.1-10 hour, drop to room temperature in nitrogen atmosphere and drop to room temperature, promptly obtain corresponding transition metal carbide or be carried on transition metal carbide on the carbon material with (in the mixed volume of oxygen and the nitrogen) passivation of 1% oxygen or at inert atmosphere.
For the multicomponent carbide, can adopt step impregnation, be total to steep water solution or ammonia soln method.
Above-mentioned hydrogen flowing quantity is the 10-500 ml/min, best 150 ml/min; Optimum temperature rise speed is 1-5 ℃/minute; The hot hydrogen reduction temperature of best carbon is 600-800 ℃; The best recovery time is 1-5 hour.
The preparation of above-mentioned precursor is to adopt the aqueous solution or ammonia soln dipping method that transistion metal compound or mixture are loaded on the raw material of wood-charcoal material, and the weight percent of transistion metal compound loading is in the 1-200% scope; Flooded 2-10 hour, and boiled off solution under stirring, 100-120 ℃ of baking 10-24 hour, promptly get the carbide precursor again at 200-400 ℃ of inert atmosphere or vacuum-treat.
The transition metal carbide of above-mentioned preparation can be used for various hydrogen-involved reactions, especially hydrofining and two key or triple bond selective hydrogenation reaction.
The invention provides a kind of under mild conditions the method for preparation single constituent element and multicomponent transition metal carbide, its reaction atmosphere, temperature of reaction, reaction times, temperature rise rate and second component have very important influence to the formation of transition metal carbide, granularity etc.Of the present invention preparation is simple, pollution-free, and its temperature of reaction can be controlled in below 1000 ℃, and at 700 ℃ of carbide that can obtain cleaning surfaces, the gained carbide surface does not have carbon distribution, high dispersive or high surface.The transition metal carbide of preparation hydrogen-involved reaction has been shown preferable activity and selectivity, especially hydrogenating desulfurization and selective hydrogenation reaction have been shown higher activity, can be applicable to hydrofining and two key and triple bond selective hydrogenation reaction as catalyzer, improve catalytic process efficient.
Description of drawings
Fig. 1 is the X-ray diffractogram of the molybdenum carbide of different loadings;
Fig. 2 is the variation diagram of the BET specific surface of molybdenum carbide with the molybdenum loading;
Fig. 3 is the X-ray diffractogram of the molybdenum carbide on the different carbon materials;
Fig. 4 is the X-ray diffractogram of the molybdenum carbide under the different reduction temperature;
Fig. 5 is the photos of 700 ℃ of gained molybdenum carbides under transmission electron microscope;
Fig. 6 is the photos of 800 ℃ of gained molybdenum carbides under transmission electron microscope;
Fig. 7 is the X-ray diffractogram of differing temps to the formation influence of nickel-molybdenum carbide;
Fig. 8 is the X-ray diffractogram of the nickel-molybdenum carbide of different nickel molybdenum ratio;
Fig. 9 is the X-ray diffractogram of differing temps to the formation influence of cobalt carbide molybdenum;
Figure 10 is the X-ray diffractogram of the cobalt carbide molybdenum of different cobalt molybdenum ratio.
Embodiment
Embodiment below by molybdenum carbide, nickel-molybdenum carbide and cobalt carbide molybdenum describes the present invention in detail.
The preparation of embodiment 1 molybdenum carbide precursor
With molybdate (preferably adopting ammonium molybdate) ammonium phosphomolybdate is water-soluble or ammoniacal liquor in be configured to steeping fluid, added the absorbent charcoal carrier dipping 2 hours.Activated carbon surface is long-pending to be 1000m
2/ g.Boil off solution under stirring, 100 ℃ of bakings 10 hours, promptly get the molybdenum carbide precursor again at 200 ℃ of inert atmospheres or vacuum-treat.Change the steeping fluid add-on, can make the molybdenum carbide precursor of different loadings.
The preparation of embodiment 2 nickel-molybdenum carbide precursors
With molybdate (preferably adopting ammonium molybdate) and nickel salt (as nickelous nitrate, nickelous oxalate etc.) is water-soluble or ammoniacal liquor in form homogeneous solution, added the absorbent charcoal carrier dipping described in the embodiment 1 then 5 hours, boil off solution under stirring, 110 ℃ of bakings 15 hours, promptly get the nickel-molybdenum carbide precursor again at 300 ℃ of inert atmospheres or vacuum-treat.
The nickel-molybdenum carbide precursor also can adopt step impregnation method, and promptly the dipping molybdate floods nickel salt more earlier, and perhaps the dipping nickel salt floods molybdate more earlier.All need stir down behind per step dipping and boil off solution, 100-120 ℃ of baking 10-24 hour,, obtain the nickel-molybdenum carbide precursor at last again in 200-400 ℃ of inert atmosphere or vacuum-treat.
Change the add-on of molybdate and nickel salt, can prepare and have different Ni/(Ni+Mo) the nickel-molybdenum carbide precursor of atomic ratio
The preparation of embodiment 3 cobalt carbide molybdenum precursors
With molybdate (preferably adopting ammonium molybdate) and cobalt salt (as Xiao Suangu, cobalt oxalate etc.) is water-soluble or ammoniacal liquor in form homogeneous solution, added the absorbent charcoal carrier dipping described in the embodiment 1 then 10 hours, boil off solution under stirring, 120 ℃ of bakings 24 hours, promptly get cobalt carbide molybdenum precursor again at 400 ℃ of inert atmospheres or vacuum-treat.
The nickel-molybdenum carbide precursor also can adopt step impregnation method, and promptly the dipping molybdate floods cobalt salt more earlier, and perhaps the dipping cobalt salt floods molybdate more earlier.All need stir down behind per step dipping and boil off solution, 100-120 ℃ of baking 10-24 hour,, obtain cobalt carbide molybdenum precursor at last again in 200-400 ℃ of inert atmosphere or vacuum-treat.
Change the add-on of molybdate and cobalt salt, can prepare cobalt carbide molybdenum precursor with different Co/ (Co+Mo) atomic ratio.
Molybdenum carbide, nickel-molybdenum carbide and cobalt carbide molybdenum precursor by embodiment 1,2,3 preparations are carried out the hot hydrogen reduction of carbon handle, prepare corresponding transition metal carbide.
The hot hydrogen reduction preparation of the carbon of embodiment 4 molybdenum carbides
The hot hydrogen reduction of carbon is carried out in crystal reaction tube, add thermal recovery tube furnace temperature programming heating, drop to room temperature in nitrogen atmosphere and drop to room temperature, promptly obtain corresponding transition metal carbide with (in the mixed volume of oxygen and the nitrogen) passivation of 1% oxygen or at inert atmosphere.10 milliliters of sample loading amounts.
1. get the molybdenum carbide precursor of implementing 1 preparation, hydrogen flowing quantity is 10 ml/min, and temperature rise rate is 0.1 ℃/minute, 500 ℃ of the hot hydrogen reduction outlet temperatures of carbon, and carbonization time is 0.1 hour.
2. get the molybdenum carbide precursor of implementing 1 preparation, hydrogen flowing quantity is 100 ml/min, and temperature rise rate is 1 ℃/minute, 600 ℃ of the hot hydrogen reduction outlet temperatures of carbon, and carbonization time is 5 hours.
3. get the molybdenum carbide precursor of implementing 1 preparation, hydrogen flowing quantity is 150 ml/min, and temperature rise rate is 5 ℃/minute, and the hot hydrogen reduction outlet temperature of carbon is 800 ℃, and carbonization time is 2 hours.
4. get the molybdenum carbide precursor of implementing 1 preparation, hydrogen flowing quantity is 300 ml/min, and temperature rise rate is 10 ℃/minute, and the hot hydrogen reduction outlet temperature of carbon is at 700 ℃, and carbonization time was at 4 hours.
5. get the molybdenum carbide precursor of implementing 1 preparation, hydrogen flowing quantity is 500 ml/min, and temperature rise rate is 20 ℃/minute, and the hot hydrogen reduction outlet temperature of carbon is in 1000 ℃, and carbonization time is between 10 hours.
Get and preparedly in 3 contain molybdenum carbide XRD that molybdenum 5%, 10%, 15% and 20% sample obtained 800 ℃ of carbothermic reductions in 2 hours as shown in Figure 1.Along with the increase of molybdenum loading, the diffraction peak of carbide strengthens gradually as can be seen from Figure, shows that the granularity of carbide increases with loading.
The carbide sample is carried out the BET specific surface that nitrogen adsorption test obtains to be changed as shown in Figure 2 with the molybdenum loading.The carbide sample increases with the molybdenum loading, and specific surface reduces gradually, shows that carbide is present in the hole of gac.High-resolution electron microscope studies show that the about 10nm of the granularity of molybdenum carbide, and ultimate analysis shows that its composition contains oxygen element, shows the oxidized oxygen molybdenum carbide that formed in molybdenum carbide surface.
According to embodiment 1, use active carbon with high specific surface area (HSAC) and commercial Xc-72 to be carbon source/carrier, prepare the molybdenum carbide precursor.The specific surface of active carbon with high specific surface area is 3200m
2/ g, the specific surface of Xc-72 charcoal are 142m
2/ g.The XRD of the carbide for preparing according to embodiment 4 as shown in Figure 3.On different carbon materials, all obtained molybdenum carbide as can be seen from Figure, and the granularity of gained carbide is in nanometer range.
The hot hydrogen reduction temperature of embodiment 6 carbon relatively
According to embodiment 4, under other identical condition, the hot hydrogen reduction temperature of carbon is respectively at 600,700,800 ℃, and the XRD of gained molybdenum carbide sample as shown in Figure 4.On 600 ℃, obtained molybdenum carbide as can be seen from Figure, and the granularity of gained carbide is in nanometer range.The transmission electron microscope photo of gained sample is seen Fig. 5, Fig. 6.Raise with temperature of reaction as seen from the figure, it is big that the molybdenum carbide granularity becomes, the granularity of 700 and 800 ℃ of gained molybdenum carbides be respectively 10 and 25nm about.
The hot hydrogen reduction atmosphere of embodiment 7 carbon relatively
According to embodiment 4, under other identical condition, the hot hydrogen reduction temperature of carbon is 700 ℃, and atmosphere adopts nitrogen/argon gas, hydrogen and hydrogen+argon gas respectively.The result is presented at no molybdenum carbide generation under the nitrogen/argon gas, and then both have all generated molybdenum carbide.
The hot hydrogen reduction preparation of the carbon of embodiment 8 double elements nickel-molybdenum carbides
Selecting gac AC for use is carrier and carbon source, has investigated the hot hydrogen reduction Temperature Influence of carbon.For nickel-molybdenum carbide, as seen from Figure 7, nickel be added in 600 ℃ of thing phases (NixMoyC) that just formed carbide, but along with temperature of reaction increases, strengthen gradually corresponding to the diffraction peak of nickel-molybdenum carbide, the diffraction peak of MoCx thing phase strengthens gradually.Obviously, the adding of nickel greatly reduces the temperature that the hot hydrogen reduction of carbon prepares carbide.Along with nickel molybdenum ratio increases the diffraction peak intensity (see figure 8) of nickel-molybdenum carbide.The increase of nickel molybdenum ratio helps the generation of nickel-molybdenum carbide.
The hot hydrogen reduction preparation of the carbon of embodiment 9 double elements cobalt carbide molybdenums
Selecting gac AC for use is carrier and carbon source, has investigated the hot hydrogen reduction Temperature Influence of carbon.For the cobalt carbide molybdenum, as seen from Figure 9, cobalt be added in 600 ℃ of thing phases (CoxMoyC) that just formed carbide, but along with temperature of reaction increases, strengthen gradually corresponding to the diffraction peak of cobalt carbide molybdenum, the diffraction peak of MoCx thing phase strengthens gradually.Obviously, the adding of cobalt greatly reduces the temperature that the hot hydrogen reduction of carbon prepares carbide.Along with cobalt molybdenum ratio increases the diffraction peak intensity (see figure 10) of cobalt carbide molybdenum.The increase of cobalt molybdenum ratio helps the generation of cobalt carbide molybdenum.
The hydrogenating desulfurization catalytic activity of embodiment 10 transition metal carbides
Test for transition metal carbide MoCx/C, the NiMoC/C of preparation, the dibenzothiophene hydrodesulfurization performance of CoMoC/C catalyzer.Reaction conditions: 573K, 3.0MPa, 3.0h
-1, inlet sulphur concentration 685ng/ μ l; React that three catalyzer upper outlet sulphur concentrations are lower than 15ng/ μ l after 2 hours, desulfurization degree reaches 98%.
The selection high active of hydrogenation catalysis of embodiment 11 transition metal carbides
Test for transition metal carbide MoCx/C, the NiMoC/C of preparation, the acetylene and the selective hydrogenation of butadiene performance of CoMoC/C catalyzer.The result shows that MoCx/C, NiMoC/C, CoMoC/C catalyzer have just shown very high selectivity (98%, 95%, 95%) and transformation efficiency (50%, 85%, 85%) in room temperature.
Claims (9)
1. the preparation method of a transition metal carbide catalyst is characterized in that: precursor is made up of carbon material and transistion metal compound or mixture; The preparation process of precursor is to adopt the aqueous solution or ammonia soln dipping method that transistion metal compound or mixture are loaded on the carbon material, and the weight percent of transistion metal compound loading is in the 1-200% scope; Flooded 2-10 hour, and boiled off solution under stirring, 100-120 ℃ of baking 10-24 hour, promptly get the carbide precursor again at 200-400 ℃ of inert atmosphere or vacuum-treat; Be to rise to 500-1000 ℃ with 1-20 ℃ of/minute intensification speed under the nitrogen atmosphere of 10～500 ml/min at hydrogen flowing quantity, constant temperature reduction 0.1-10 hour, drop to room temperature in nitrogen atmosphere and drop to room temperature, promptly obtain corresponding transition metal carbide or be carried on transition metal carbide on the carbon material with 1% oxygen passivation or at inert atmosphere.
2. according to the preparation method of the described transition metal carbide of claim 1, it is characterized in that: hydrogen flowing quantity is the 10-500 ml/min; Temperature rise rate is 1-5 ℃/minute; The hot hydrogen reduction temperature of carbon is 600-800 ℃; Recovery time is 1-5 hour.
3. according to the preparation method of the described transition metal carbide of claim 2, it is characterized in that hydrogen flowing quantity is 150 ml/min.
4. according to the preparation method of the described transition metal carbide catalyst of claim 1, it is characterized in that the carbon material in the described precursor is gac, carbon black, carbon nanotube or carbon fiber; Transistion metal compound is oxide compound, sulfide, halogenide or transition metal mixtures and their mixture or mixture.
5. according to the preparation method of the described transition metal carbide of claim 1, it is characterized in that the multicomponent transition metal carbide can be expressed as: MxM ' yC, wherein M is the group VIII element, M ' is IVB, VB, VIB, VIIB subgroup element; Wherein 0＜X＜2,0＜Y＜2.
6. according to the preparation method of the described transition metal carbide of claim 5, it is characterized in that: wherein M is Co, and Fe or Ni, M ' are Mo, V, W, Nb, Cr or Ta.
7. according to the preparation method of the described transition metal carbide of claim 5, it is characterized in that multicomponent transition metal carbide MxM ' yC, wherein X=1, Y=1.
8. according to the preparation method of the described transition metal carbide of claim 1, it is characterized in that, adopt step impregnation, be total to steep water solution or ammonia soln method making precursor for the multicomponent carbide.
9. the transition metal carbide catalyst that makes according to the described preparation method of claim 1, the application in hydrogenating desulfurization, two key or triple bond selective hydrogenation reaction.
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