CN111437830B - Yolk-eggshell type SiO2-Al2O3Noble metal propane dehydrogenation catalyst and preparation method thereof - Google Patents

Yolk-eggshell type SiO2-Al2O3Noble metal propane dehydrogenation catalyst and preparation method thereof Download PDF

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CN111437830B
CN111437830B CN202010348244.4A CN202010348244A CN111437830B CN 111437830 B CN111437830 B CN 111437830B CN 202010348244 A CN202010348244 A CN 202010348244A CN 111437830 B CN111437830 B CN 111437830B
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sio
yolk
catalyst
eggshell
noble metal
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CN111437830A (en
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田俊凯
高军
杨卫东
范昌海
周轶
单寅昊
陆朝阳
亓虎
寇亮
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Zhejiang Satellite Energy Co ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8966—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with germanium, tin or lead
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/396—Distribution of the active metal ingredient
    • B01J35/397—Egg shell like
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/396—Distribution of the active metal ingredient
    • B01J35/398—Egg yolk like
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • C—CHEMISTRY; METALLURGY
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
    • C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
    • C07C5/333—Catalytic processes
    • C07C5/3335—Catalytic processes with metals
    • C07C5/3337—Catalytic processes with metals of the platinum group
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    • Y02P20/00—Technologies relating to chemical industry
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    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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Abstract

The invention discloses a yolk-eggshell type SiO2‑Al2O3Noble metal propane dehydrogenation catalyst and preparation method thereof, wherein the catalyst is solid SiO2‑Al2O3The microspheres are yolk and porous SiO2‑Al2O3The hollow sphere is an eggshell, effective catalytic active ingredients with different functions are respectively loaded on the yolk and the eggshell layer, and the obtained catalyst has a large specific surface area, so that the activity and the selectivity of the catalyst are increased, the carbon deposition rate is reduced, and the single-pass yield is improved; meanwhile, the catalyst has higher strength, avoids the catalyst from cracking due to the generation of core coke, and effectively solves the problems of blockage of inner and outer networks of the reactor, short operation period of the device and the like caused by the cracking of the catalyst.

Description

Yolk-eggshell type SiO2-Al2O3Noble metal propane dehydrogenation catalyst and preparation method thereof
Technical Field
The invention belongs to the field of catalyst preparation, and particularly relates to yolk-eggshell type SiO2-Al2O3A noble metal propane dehydrogenation catalyst and a preparation method thereof.
Background
Propylene is an important national strategic substance, and along with the increasing domestication of nontoxic polypropylene PP, the propylene market has been increased at a high speed in the last 5 years, the growth rate is kept at 8.7%, and the domestic gap reaches about 1200 tons. The process for preparing propylene by high-consumption steam cracking is gradually eliminated by the market and governments, and the green and environment-friendly propane dehydrogenation technology is accepted and pursued by the market. The domestic propane investment heat will continue in the future, and at present, the domestic noble metal platinum gold catalyst of UOP and chromium catalyst of Rumes are mainly available. The noble metal platinum-gold catalyst can be repeatedly recycled, so that the noble metal platinum-gold catalyst currently occupies the mainstream in the domestic market. The existing domestic propane dehydrogenation device of the UOP process has the problems of low catalyst strength, low single-pass yield, easy blockage of an internal net and an external net of a reactor, short operation period and the like.
In addition, the chromium-based catalyst and the preparation method disclosed in chinese patent CN110560038A are toxic from the viewpoint of environmental protection, and the subsequent treatment involves many environmental problems, and the like, and is not mainstream for the development of propane dehydrogenation, and the use is limited to a certain extent due to the environmental problems. The propane dehydrogenation catalyst disclosed in Chinese patent CN101411978A uses gamma-Al2O3The carrier is low in strength, the preparation process is long, and the raw materials contain nitrogen, so that the subsequent separation is inconvenient, and the industrial production is difficult. The propane dehydrogenation catalyst of the chinese patent CN109746027A mainly relates to the preparation of catalyst carrier, and has better specific surface area and porosity than UOP carrier, and better catalyst activity than UOP, but does not improve the strength of catalyst carrier.
The catalyst carrier of the propane dehydrogenation catalyst disclosed at present has low strength, and is easy to produce fine powder and crushed particles to block inner and outer nets. In addition, the dehydrogenation of propane to propylene is an endothermic reaction, the reaction is limited by thermodynamic equilibrium, negative pressure and high temperature are needed to obtain high conversion rate, and the high temperature easily causes the catalyst to be deactivated by carbon deposition, thus reducing the selectivity of the catalyst. Therefore, the development of propane dehydrogenation catalysts with high carrier strength and high catalyst selectivity is the research focus and difficulty of the propane dehydrogenation industry at present.
Disclosure of Invention
Hair brushAims to improve eyesight by providing yolk-eggshell type SiO2-Al2O3The catalyst obtained by the method has larger specific surface area, higher catalytic activity and selectivity, reduces carbon deposition rate and improves single-pass yield; the catalyst has high strength, avoids the catalyst from cracking caused by the generation of core coke, and effectively solves the problems of blockage of inner and outer nets of a reactor, short operation period of the device and the like caused by the cracking of the catalyst.
The technical scheme of the invention is as follows:
yolk-eggshell type SiO2-Al2O3A catalyst for dehydrogenating noble metal propane features that solid SiO is used2-Al2O3Slightly yolk and porous SiO2-Al2O3The hollow sphere is an eggshell, the egg yolk is loaded with a hydrogenation catalytic active component, the eggshell is loaded with a metal dehydrogenation catalytic active component, and the solid SiO is2-Al2O3SiO in microsphere2The content is 5.5-18.8 wt%; the porous SiO2-Al2O3SiO in hollow ball2The content is 1.5-7.5 wt%; the solid SiO2-Al2O3Microspheres and porous SiO2-Al2O3The diameter ratio of the hollow sphere is 1: 3-6.
Preferably, the load capacity of the dehydrogenation catalytic active component is 0.01-0.3 wt%.
Preferably, the load capacity of the dehydrogenation catalytic active component is 0.05-0.1 wt%.
Preferably, the loading amount of the hydrogenation catalytic active component is 0.26-1 wt%.
Preferably, the dehydrogenation catalytic active component is one or more of Fe, Co, Ni, Ru, Rh, Pd, Os, Ir.
Preferably, the dehydrogenation catalytically active component is a mixture of Ni-Pd.
Preferably, the hydrogenation catalytic active component is one or more of Cr, Ni, Zn, Fe, Pt, Sn, Ca, Cu and Al.
Preferably, the hydrogenation catalytic active component is a mixture of Pt-Sn-Zn.
Preferably, the solid SiO2-Al2O3SiO in microsphere2The content is 12.5-15.5 wt%.
Preferably, the porous SiO2-Al2O3SiO in hollow ball2The content is 2.5-3.5 wt%.
The yolk-eggshell type SiO2-Al2O3The preparation method of the noble metal catalyst comprises the following steps:
1) preparation of solid SiO2-Al2O3Microspheres
Dissolving water-soluble aluminum salt in desalted water to prepare a solution, heating to 40-75 ℃, adding tetraethoxysilane or an organic silicon compound for several times under stirring, then adding alkali liquor to neutralize until the pH value is 7-11, carrying out suction filtration after the reaction is finished, and washing the obtained filter cake with desalted water until the washed solution is neutral; adding an adhesive into the obtained filter cake, stirring and adding an ammonia water ethanol solution to make the final slurry neutral, and filtering to obtain SiO2-Al2O3The filter cake is then dried to obtain SiO2-Al2O3Nanomaterial, then to SiO2-Al2O3Adding desalted water into the nano material for pasting to prepare solid SiO2-Al2O3Carrying out rotary atomization drying on the microspheres, and obtaining dried solid SiO2-Al2O3The microspheres are used as core spheres for standby;
2) loaded hydrogenation catalytic active component
Solid SiO prepared in the step 1)2-Al2O3Dipping the microspheres in a salt solution containing a hydrogenation catalytic active component for 1-4 h, and drying by using a vacuum rotary drying method to obtain solid SiO loaded with the hydrogenation catalytic active component2-Al2O3Microspheres;
3) preparation of porous SiO2-Al2O3Hollow ball
Dissolving water-soluble aluminum salt in desalted water to prepare a solution, and heating the solution to 40-75 DEG CAdding tetraethoxysilane or an organic silicon compound for several times under stirring, then adding alkali liquor for neutralization until the pH value is 7-11, after the reaction is finished, carrying out suction filtration, washing the obtained filter cake with desalted water until the washed solution is neutral, drying, grinding and sieving to obtain porous SiO2-Al2O3A nanomaterial; into porous SiO2-Al2O3Adding template agent and adhesive into the nano material to prepare porous SiO2-Al2O3Suspending the slurry;
then rolling the ball to make the porous SiO2-Al2O3The suspension slurry is attached to the solid SiO containing the hydrogenation catalytic active component prepared in the step 2)2-Al2O3The surface of the microsphere is put into a ball shaping machine for shaping and screening, and then is subjected to rotary atomization drying and roasting to obtain solid SiO2-Al2O3The microspheres are yolk and porous SiO2-Al2O3The hollow sphere is a catalyst carrier of an eggshell; wherein the roasting conditions are as follows: keeping the temperature of 300-500 ℃ for 1-10 h, keeping the temperature of 500-800 ℃ for 1-10 h, and keeping the temperature of 1000 ℃ for 1-2 h, wherein the heating rate is 5-50 ℃/h;
4) loaded dehydrogenation catalyst active component
The solid SiO obtained in the step 3) is used2-Al2O3The microspheres are yolk and porous SiO2-Al2O3Soaking a catalyst carrier with a hollow sphere as an eggshell in a solution containing dehydrogenation catalytic active components at the temperature of 10-50 ℃ for 3-8 h, and evaporating excessive water in a rotary evaporator to obtain the yolk-eggshell type SiO2-Al2O3Drying the noble metal propane dehydrogenation catalyst wet body for 2-6 h at 120 ℃, and calcining and forming to obtain the yolk-eggshell type SiO2-Al2O3A noble metal propane dehydrogenation catalyst; wherein the calcining conditions are as follows: roasting at 260-280 ℃ for 10-12 h, roasting at 400-430 ℃ for 8-10 h, roasting at 530-550 ℃ for 8-10 h, roasting at 650-700 ℃ for 2-4 h, and heating at a rate of 15-20 ℃/h;
5) catalyst activation
Step 4) Yolk-eggshell type SiO in the egg2-Al2O3Transferring the noble metal propane dehydrogenation catalyst into a reduction container, and reducing for 0.5-4 h at the temperature of 500-600 ℃ in a hydrogen atmosphere to obtain activated yolk-eggshell structure SiO2-Al2O3A noble metal propane dehydrogenation catalyst.
Preferably, the water-soluble aluminum salt is one or more selected from aluminum chloride, aluminum sulfate, aluminum nitrate, sodium aluminate and potassium aluminate.
Preferably, the alkali liquor is potassium hydroxide solution or sodium hydroxide solution.
Preferably, the alkali liquor is sodium hydroxide solution.
Preferably, the adhesive is one or more of acetic acid, nitric acid, hydrochloric acid, sulfuric acid, acrylic acid and citric acid.
Preferably, the template agent is one or two of trimethylpentane and polyoxypropylene-polyoxyethylene.
In the invention, effective catalytic active ingredients for dehydrogenation and hydrogenation are respectively loaded on the yolk layer and the eggshell layer of the catalyst, so that the excessive dehydrogenation of the core of the catalyst in the propane dehydrogenation process can be effectively avoided.
In the invention, the catalyst adopts a yolk-eggshell structure and is solid SiO2-Al2O3The microspheres are yolk and porous SiO2-Al2O3The hollow sphere is an eggshell, and the egg yolk part loaded with the hydrogenation catalytic active component is wrapped in the eggshell loaded with the metal dehydrogenation catalytic active component, so that catalyst components can be prevented from penetrating into a carrier core, and the catalyst is prevented from cracking due to the generation of core coke in the catalyst regeneration process; in addition, the yolk-eggshell type structure can enhance the physical strength of the catalyst, avoid the catalyst from being broken to cause the blockage of an inner net and an outer net of the device, and effectively prolong the operation period of the device and the service life of the catalyst.
The catalyst is SiO for both yolk and eggshell carriers2-Al2O3Nano-materials, but wherein SiO2The content is different mainly because of SiO in the nanometer material2The specific surface area of the material is different due to different contents, and SiO in the nano material2The content is high, the pore diameter of the micropores can be enlarged, the strength of the sphere made of the corresponding material can be reduced, and SiO in the nano material can be controlled2Content of SiO maximizes the specific surface area of the catalyst on the basis of higher physical strength of the catalyst support, thereby2The content needs to be specially controlled, so that the catalyst carrier with higher strength and larger specific surface area can be prepared, the specific surface area of the catalyst is increased, the average pore diameter is reduced, the strong acid center is weakened, and the dust content is reduced.
In the catalyst carrier, if the diameter ratio of the egg yolk to the eggshell layer is too small, the eggshell layer is not enough to load enough dehydrogenation catalytic active components, the catalytic activity of the catalyst is not high, and if the ratio is too large, the strength of the prepared integral catalyst is not enough, and the diameter ratio of the egg yolk to the eggshell layer is set to be 1: 3-6, so that the requirement can be met.
In the invention, the dehydrogenation catalytic active component is loaded on the surface of the eggshell layer and in the micropores, the micropore structure is beneficial to uniform dispersion of the dehydrogenation catalytic active component, the loading capacity on the unit effective specific surface is increased, the distribution of the dehydrogenation catalytic active component is optimized, the effective contact area of the material and the dehydrogenation catalytic active component is increased, the activity and the selectivity of the catalyst are enhanced, and the problem of low single-pass yield of the traditional catalyst is solved.
The rotary atomization drying is adopted in the preparation process of the catalyst, because the drying is prevented from being too fast, and the moisture can not be completely evaporated to cause the crushing of the catalyst.
The preparation method disclosed by the invention is short in preparation period, reduces the energy consumption in the material preparation process, can realize large-scale production by modularizing each step, improves the preparation efficiency, and can realize industrial continuous production.
The invention has the beneficial effects that:
the catalyst of the invention is solid SiO2-Al2O3The microspheres are yolk and porousSiO2-Al2O3The hollow sphere is an eggshell, and the yolk and the eggshell layer are respectively loaded with catalytic active ingredients with different functions, so that the generation of core coke can be effectively avoided, the physical strength of the catalyst is enhanced, the blockage of an inner net and an outer net of the reactor due to the breakage of the catalyst is avoided, the operation period of the device is effectively prolonged, and the service life of the catalyst is effectively prolonged.
The eggshell layer of the propane dehydrogenation catalyst is porous SiO2-Al2O3Hollow ball, increased catalyst comparison area, dehydrogenation catalytic active component distributed in porous SiO2-Al2O3The pore and surface of the hollow sphere and the loading capacity of the dehydrogenation catalytic active component on the unit effective specific surface are increased, and the effective contact area of the material and the catalyst is increased, so that the activity and selectivity of the catalyst are improved, and the one-way yield is increased.
The preparation method has simple preparation process, reduces the energy consumption in the material preparation process, can realize large-scale production in each step of operation, and can realize industrialized continuous operation.
Drawings
FIG. 1 is a schematic diagram of the structure of the catalyst of example 1 of the present invention.
FIG. 2 is a sectional view of a catalyst carrier in example 1 of the present invention.
FIG. 3 is a comparison of the coking on the surface of the DEH-16 catalyst in example 1 of the present invention.
Detailed Description
The present invention is further illustrated by the following specific examples, which are not intended to limit the scope of the invention.
Example 1:
1) preparation of SiO2-Al2O3Nanosphere
Mixing acidic aluminum sulfate and alkaline potassium aluminate according to the molar ratio of 7:3, then adding desalted water to prepare a solution, heating to 55 ℃, and adding tetraethoxysilane for three times under the condition of stirring, wherein the molar ratio of the tetraethoxysilane to the acidic aluminum sulfate is 1: 3; then adding sodium hydroxide, adjusting the pH value of the solution to 11, after the reaction is completed, carrying out suction filtration, and washing the obtained filter cake with desalted waterExcess sodium, potassium and sulfate ions were washed until the washed solution showed a pH of 7. Adding acetic acid into the filter cake, stirring and adding ammonia water ethanol solution to make the final slurry neutral, and filtering to obtain SiO2-Al2O3The filter cake is then dried to obtain SiO2-Al2O3Nanomaterial, then to SiO2-Al2O3Adding a small amount of desalted water into the nano material for gelatinization to prepare SiO2-Al2O3Drying the microspheres, and drying the dried SiO2-Al2O3The microspheres are used as core spheres for standby;
2) loaded hydrogenation catalytic active component
SiO prepared in the step 12-Al2O3Soaking the microspheres in a nickel salt solution for 1h, and then carrying out vacuum rotary drying to obtain Ni @ SiO2-Al2O3Microspheres;
3) preparation of porous SiO2-Al2O3Hollow ball
Mixing acidic aluminum sulfate and alkaline potassium aluminate according to a molar ratio of 7:3, adding desalted water to prepare a solution, heating to 55 ℃, adding tetraethoxysilane while stirring, adding alkali liquor to neutralize until the pH value is 9, after the reaction is finished, carrying out suction filtration, and washing the obtained filter cake with desalted water until the washed solution is neutral; drying, grinding and sieving for later use; into porous SiO2-Al2O3Adding template agent and adhesive into the nano material to prepare porous SiO2-Al2O3Suspending the slurry;
then the Ni @ SiO prepared in the step 2) is added2-Al2O3Rolling method for making porous SiO by microspheres2-Al2O3The suspension slurry is attached to the surface of the solid SiO solid, then the solid SiO solid is placed into a ball shaping machine for shaping and screening, then the solid SiO solid is subjected to rotary atomization drying, then the solid SiO solid is transferred into a muffle furnace for keeping the temperature of 400 ℃ for 4h, the temperature of 600 ℃ for 4h and the temperature of 1200 ℃ for 1h, and the heating rate is 10 ℃/h2-Al2O3The microspheres are yolk and porous SiO2-Al2O3The hollow sphere is a catalyst carrier of an eggshell;
4) loaded dehydrogenation catalyst active component
The solid SiO obtained in the step 3) is used2-Al2O3The microspheres are yolk and porous SiO2-Al2O3Soaking a catalyst carrier with a hollow ball as an eggshell in a mixed solution of chloroplatinic acid, stannic chloride and zinc chloride at the temperature of 30 ℃ for 4h, and evaporating excessive water in a rotary evaporator to obtain SiO with a yolk-eggshell structure2-Al2O3Drying the noble metal propane dehydrogenation catalyst wet body at 120 ℃ for 2h, then transferring the noble metal propane dehydrogenation catalyst wet body into a muffle furnace to be roasted at 260 ℃ for 12h, at 400 ℃ for 8h, at 550 ℃ for 8h and at 650 ℃ for 3h, wherein the heating rate is 15 ℃/h, and obtaining the yolk-eggshell type SiO2-Al2O3A noble metal propane dehydrogenation catalyst;
5) catalyst activation
The yolk-eggshell type SiO in the step 4)2-Al2O3Transferring the noble metal propane dehydrogenation catalyst into a reduction container, reducing for 3h at 550 ℃ in 99.99% hydrogen atmosphere to obtain activated SiO with a yolk-eggshell structure2-Al2O3A noble metal propane dehydrogenation catalyst.
SiO in the obtained catalyst2-Al2O3SiO in microsphere212.5% of porous SiO2-Al2O3SiO in hollow ball2The content is 2.5%, the dehydrogenation catalytic active component is Ni, the load is 0.1%, the hydrogenation catalytic active component is Pt-Sn-Zn, wherein the load of Pt is 0.30%, the load of Sn is 0.2%, and the load of Zn is 0.1%.
The structure schematic diagram of the catalyst prepared by the invention is shown in figure 1, and the cross-sectional view of the catalyst carrier prepared by the invention is shown in figure 2.
Example 2:
1) preparation of SiO2-Al2O3Microspheres
Acid aluminum sulfate and alkaline potassium aluminate are mixed according to the mole ratioMixing according to a molar ratio of 7:3, adding desalted water to prepare a solution, heating to 60 ℃, and adding tetraethoxysilane for three times under the condition of stirring, wherein the molar ratio of tetraethoxysilane to acidic aluminum sulfate is 1: 2; then sodium hydroxide was added to adjust the pH of the solution to 10, after completion of the reaction, suction filtration was carried out, and the resulting filter cake was washed with desalted water to wash excess sodium, potassium and sulfate ions until the washed solution showed a pH of 7. Adding acetic acid into the filter cake, stirring and adding ammonia water ethanol solution to make the final slurry neutral, and filtering to obtain SiO2-Al2O3The filter cake is then dried to obtain SiO2-Al2O3Nanomaterial, then to SiO2-Al2O3Adding a small amount of desalted water into the nanometer material for gelatinization to prepare microspheres with the diameter of 0.5mm, drying, and drying to obtain the dried SiO2-Al2O3The microspheres are used as core spheres for standby;
2) loaded hydrogenation catalytic active component
SiO prepared in the step 12-Al2O3Soaking the microspheres in a palladium salt solution for 2 hours, and then carrying out vacuum rotary drying to obtain Ni @ SiO2-Al2O3Microspheres;
3) preparation of porous SiO2-Al2O3Hollow ball
Mixing acidic aluminum sulfate and alkaline potassium aluminate according to a molar ratio of 7:3, adding desalted water to prepare a solution, heating to 60 ℃, adding tetraethoxysilane while stirring, adding alkali liquor to neutralize until the pH value is 10, after the reaction is finished, carrying out suction filtration, washing the obtained filter cake with desalted water until the washed solution is neutral, drying, grinding and sieving for later use; into porous SiO2-Al2O3Adding template agent and adhesive into the nano material to prepare porous SiO2-Al2O3Suspending the slurry;
then the SiO prepared in the step 2 is added2-Al2O3Rolling method for making porous SiO by microspheres2-Al2O3The suspension slurry is attached to the surface of the solid SiO solid, then the solid SiO solid is put into a ball shaping machine for shaping and screening, then the solid SiO solid is subjected to rotary atomization drying, then the solid SiO solid is transferred into a muffle furnace for keeping the temperature of 400 ℃ for 4h, 650 ℃ for 4h and 1200 ℃ for 1h at a heating rate of 10 ℃/h2-Al2O3The microspheres are yolk and porous SiO2-Al2O3The hollow sphere is a catalyst carrier of an eggshell;
4) loaded dehydrogenation catalyst active component
The solid SiO obtained in the step 3) is used2-Al2O3The microspheres are yolk and porous SiO2-Al2O3Soaking the catalyst carrier with the hollow ball as the eggshell in a mixed solution of chloroplatinic acid and stannic chloride at the temperature of 20 ℃ for 6h, and evaporating excessive water in a rotary evaporator to obtain the yolk-eggshell type SiO2-Al2O3Drying the noble metal propane dehydrogenation catalyst wet body at 120 ℃ for 2h, then transferring the noble metal propane dehydrogenation catalyst wet body into a muffle furnace to be roasted at 260 ℃ for 12h, at 400 ℃ for 8h, at 550 ℃ for 8h and at 650 ℃ for 3h, wherein the heating rate is 15 ℃/h, and obtaining the yolk-eggshell type SiO2-Al2O3A noble metal propane dehydrogenation catalyst;
5) catalyst activation
SiO the yolk-eggshell structure in the step 4)2-Al2O3Transferring the noble metal propane dehydrogenation catalyst into a reduction container, reducing for 0.5h at 550 ℃ in 99.99% hydrogen atmosphere to obtain activated SiO with yolk-eggshell structure2-Al2O3A noble metal propane dehydrogenation catalyst.
SiO in the obtained catalyst2-Al2O3SiO in microsphere2Content of 15.5%, porous SiO2-Al2O3SiO in hollow ball2The content is 3.5%, the dehydrogenation catalytic active component is Pb, the loading capacity is 0.2%, the hydrogenation catalytic active component is Pt-Sn-Zn, wherein the loading capacity of Pt is 0.42%, the loading capacity of Sn is 0.3%, and the loading capacity of Zn is 0.2%.
Example 3:
1) preparation of SiO2-Al2O3Microspheres
Mixing acidic aluminum sulfate and alkaline potassium aluminate according to the molar ratio of 7:3, then adding desalted water to prepare a solution, heating to 58 ℃, and adding the solution for three times under the condition of stirring, wherein the molar ratio of the tetraethoxysilane to the acidic aluminum sulfate is 1: 2.6; then sodium hydroxide was added to adjust the pH of the solution to 10, after completion of the reaction, suction filtration was carried out, and the resulting filter cake was washed with desalted water to wash excess sodium, potassium and sulfate ions until the washed solution showed a pH of 7. Adding acetic acid into the filter cake, adding ammonia water and ethanol mixed solution under stirring to make the final slurry neutral, and filtering to obtain SiO2-Al2O3The filter cake is then dried to obtain SiO2-Al2O3Nanomaterial, then to SiO2-Al2O3Adding a small amount of desalted water into the nanometer material for gelatinization to prepare microspheres with the diameter of 0.5mm, drying, and drying to obtain the dried SiO2-Al2O3The microspheres are used as core spheres for standby;
2) loaded hydrogenation catalytic active component
SiO prepared in the step 12-Al2O3Soaking the microspheres in a mixed solution of nickel salt and palladium salt for 3 hours, and then carrying out vacuum rotary drying to obtain Ni-Pb @ SiO2-Al2O3Microspheres;
3) preparation of porous SiO2-Al2O3Hollow ball
Mixing acidic aluminum sulfate and alkaline potassium aluminate according to a molar ratio of 7:3, adding desalted water to prepare a solution, heating to 60 ℃, adding tetraethoxysilane while stirring, wherein the molar ratio of the tetraethoxysilane to the acidic aluminum sulfate is 1:12, adding an alkaline solution to neutralize until the pH value is 7, after the reaction is finished, carrying out suction filtration, washing the obtained filter cake with desalted water until the washed solution is neutral, drying, grinding and sieving for later use; into porous SiO2-Al2O3Adding template agent and adhesive into the nano material to prepare porous SiO2-Al2O3Suspending the slurry;
then preparing in step 2The obtained Ni-Pb @ SiO2-Al2O3Rolling method for making porous SiO by microspheres2-Al2O3The suspension slurry is attached to the surface of the solid SiO solid, then the solid SiO solid is put into a ball shaping machine for shaping and screening, then the solid SiO solid is subjected to rotary atomization drying, then the solid SiO solid is transferred into a muffle furnace for keeping the temperature of 400 ℃ for 4h, 650 ℃ for 4h and 1200 ℃ for 1h at a heating rate of 10 ℃/h2-Al2O3The microspheres are yolk and porous SiO2-Al2O3The hollow sphere is a catalyst carrier of an eggshell;
4) loaded dehydrogenation catalyst active component
The solid SiO obtained in the step 3) is used2-Al2O3The microspheres are yolk and porous SiO2-Al2O3Soaking the catalyst carrier with the hollow ball as the eggshell in a mixed solution of chloroplatinic acid and stannic chloride at the temperature of 25 ℃ for 5 hours, and evaporating excessive water in a rotary evaporator to obtain the yolk-eggshell type SiO2-Al2O3Drying the noble metal propane dehydrogenation catalyst wet body at 120 ℃ for 2h, then transferring the noble metal propane dehydrogenation catalyst wet body into a muffle furnace to be roasted at 260 ℃ for 12h, roasted at 400 ℃ for 8h, roasted at 550 ℃ for 8h, and roasted at 650 ℃ for 3h, wherein the heating rate is 15 ℃/h, and then obtaining the SiO with the yolk-eggshell structure2-Al2O3A noble metal propane dehydrogenation catalyst;
5) catalyst activation
SiO the yolk-eggshell structure in the step 4)2-Al2O3Transferring the noble metal propane dehydrogenation catalyst into a reduction container, reducing for 0.5h at the temperature of 555 ℃ in the atmosphere of 99.99% hydrogen to obtain activated yolk-eggshell type SiO2-Al2O3A noble metal propane dehydrogenation catalyst.
In the catalyst obtained in the process of obtaining SiO2-Al2O3SiO in microsphere2Content of 14%, porous SiO2-Al2O3SiO in hollow ball2The content is 3.0 percent, the dehydrogenation catalytic active component is Ni-Pb, the load is 0.25 percent, the hydrogenation catalytic active component is Pt-Sn-Zn, wherein the load of Pt is 0.38 percent, and the load of Sn isThe amount was 0.28%, and the Zn supporting amount was 0.15%.
The performance test data of the existing dehydrogenation catalyst and the catalyst prepared by the method are compared as follows:
the experimental conditions are as follows: temperature 620 deg.C, H/HC 0.5, H2S is 55ppm, liquid hourly space velocity is 3.0, and time is 20-30 min; the catalyst was analyzed by gas chromatography, and the specific results are shown in table 1:
TABLE 1
Figure GDA0003080295710000101
From table 1, it can be seen that the strength of the catalyst prepared by the present invention is significantly higher than that of the existing propane dehydrogenation catalyst, the strength is improved by more than 20%, and after 50 cycles of regeneration, the strength of the catalyst prepared by the present invention is still higher than that of the catalyst before regeneration of the existing propane dehydrogenation catalyst.
The specific surface and the single-pass conversion rate of the catalyst prepared by the method are obviously improved, and the carbon deposition rate of the catalyst is also obviously reduced.
The coking condition of the surface of the catalyst in the embodiment 1 of the invention is compared with that of the DEH-16 in the comparative example under the same treatment condition, and the coking condition of the DEH-16 catalyst before use and after use is shown in figure 3 on the left side, and the coking condition of the catalyst in the embodiment 1 of the invention before use and after use is shown on the right side, so that the coking condition of the catalyst prepared in the embodiment 1 of the invention is not obvious, namely the coking rate of the catalyst prepared in the embodiment 1 of the invention is far less than that of the DEH-16 catalyst, which is shown in figure 3.

Claims (16)

1. Yolk-eggshell type SiO2-Al2O3A catalyst for dehydrogenating noble metal propane features that solid SiO is used2-Al2O3The microspheres are yolk and porous SiO2-Al2O3The hollow sphere is an egg shell, the egg yolk is loaded with a hydrogenation catalytic active component, and the egg shell is loaded with a dehydrogenation catalytic active component; the solid SiO2-Al2O3SiO in microsphere2The content is 5.5-18.8 wt%; the porous SiO2-Al2O3SiO in hollow ball2The content is 1.5-7.5 wt%; the solid SiO2-Al2O3Microspheres and porous SiO2-Al2O3The diameter ratio of the hollow sphere is 1: 3-6.
2. The yolk-eggshell SiO of claim 12-Al2O3The noble metal propane dehydrogenation catalyst is characterized in that the loading amount of the dehydrogenation catalytic active component is 0.01-0.3 wt%.
3. The yolk-eggshell SiO of claim 12-Al2O3The noble metal propane dehydrogenation catalyst is characterized in that the loading amount of the dehydrogenation catalytic active component is 0.05-0.1 wt%.
4. The yolk-eggshell SiO of claim 12-Al2O3The noble metal propane dehydrogenation catalyst is characterized in that the loading amount of the hydrogenation catalytic active component is 0.26-1 wt%.
5. Yolk-shell type SiO of claim 1, 2 or 32-Al2O3The catalyst is characterized in that the dehydrogenation catalytic active component is one or more of Fe, Co, Ni, Ru, Rh, Pd, Os and Ir.
6. Yolk-shell type SiO of claim 1, 2 or 32-Al2O3The catalyst for dehydrogenating noble metal propane features that the dehydrogenation catalyst has Ni-Pd mixture as the active component.
7. Yolk-shell type SiO of claim 1 or 42-Al2O3The noble metal propane dehydrogenation catalyst is characterized in that the hydrogenation catalytic active components are Cr, Ni, Zn, Fe, Pt,One or more of Sn, Ca, Cu and Al.
8. Yolk-shell type SiO of claim 1 or 42-Al2O3The noble metal propane dehydrogenation catalyst is characterized in that the hydrogenation catalytic active component is a Pt-Sn-Zn mixture.
9. The yolk-eggshell SiO of claim 12-Al2O3Noble metal propane dehydrogenation catalyst characterized in that said solid SiO2-Al2O3SiO in microsphere2The content is 12.5-15.5 wt%.
10. The yolk-eggshell SiO of claim 12-Al2O3Noble metal propane dehydrogenation catalyst characterized in that said porous SiO2-Al2O3SiO in hollow ball2The content is 2.5-3.5 wt%.
11. The yolk-eggshell SiO of claim 12-Al2O3A method for preparing a noble metal propane dehydrogenation catalyst, comprising the steps of:
1) preparation of solid SiO2-Al2O3Microspheres
Dissolving water-soluble aluminum salt in desalted water to prepare a solution, heating to 40-75 ℃, adding tetraethoxysilane or an organic silicon compound for several times under stirring, then adding alkali liquor to neutralize until the pH value is 7-11, carrying out suction filtration after the reaction is finished, and washing the obtained filter cake with desalted water until the washed solution is neutral; adding an adhesive into the obtained filter cake, stirring and adding an ammonia water ethanol solution to make the final slurry neutral, and filtering to obtain SiO2-Al2O3The filter cake is then dried to obtain SiO2-Al2O3Nanomaterial, then to SiO2-Al2O3Adding desalted water into the nano material for pasting to prepare solid SiO2-Al2O3MicrospheresRotary atomizing for drying, and drying to obtain solid SiO2-Al2O3The microspheres are used as core spheres for standby;
2) loaded hydrogenation catalytic active component
Solid SiO prepared in the step 1)2-Al2O3Dipping the microspheres in a salt solution containing a hydrogenation catalytic active component for 1-4 h, and then carrying out vacuum rotary drying to obtain solid SiO loaded with the hydrogenation catalytic active component2-Al2O3Microspheres;
3) preparation of porous SiO2-Al2O3Hollow ball
Dissolving water-soluble aluminum salt in desalted water to prepare a solution, heating to 40-75 ℃, adding tetraethoxysilane or an organic silicon compound for several times under stirring, then adding alkali liquor to neutralize until the pH value is 7-11, performing suction filtration after the reaction is finished, washing the obtained filter cake with desalted water until the washed solution is neutral, drying, grinding and sieving to obtain the porous SiO2-Al2O3A nanomaterial; into porous SiO2-Al2O3Adding template agent and adhesive into the nano material to prepare porous SiO2-Al2O3Suspending the slurry;
then rolling the ball to make the porous SiO2-Al2O3The suspension slurry is attached to the solid SiO containing the hydrogenation catalytic active component prepared in the step 2)2-Al2O3The surface of the microsphere is put into a ball shaping machine for shaping and screening, and then is subjected to rotary atomization drying and roasting to obtain solid SiO2-Al2O3The microspheres are yolk and porous SiO2-Al2O3The hollow sphere is a catalyst carrier of an eggshell; wherein the roasting conditions are as follows: keeping the temperature of 300-500 ℃ for 1-10 h, keeping the temperature of 500-800 ℃ for 1-10 h, and keeping the temperature of 1000 ℃ for 1-2 h, wherein the heating rate is 5-50 ℃/h;
4) loaded dehydrogenation catalyst active component
The solid SiO obtained in the step 3) is used2-Al2O3The microspheres are yolk and porous SiO2-Al2O3Soaking a catalyst carrier with a hollow sphere as an eggshell in a solution containing dehydrogenation catalytic active components at the temperature of 10-50 ℃ for 3-8 h, and evaporating excessive water in a rotary evaporator to obtain the yolk-eggshell type SiO2-Al2O3Drying the noble metal propane dehydrogenation catalyst wet body for 2-6 h at 120 ℃, and calcining and forming to obtain the yolk-eggshell type SiO2-Al2O3A noble metal propane dehydrogenation catalyst; wherein the calcining conditions are as follows: roasting at 260-280 ℃ for 10-12 h, roasting at 400-430 ℃ for 8-10 h, roasting at 530-550 ℃ for 8-10 h, roasting at 650-700 ℃ for 2-4 h, and heating at a rate of 15-20 ℃/h;
5) catalyst activation
The yolk-eggshell type SiO in the step 4)2-Al2O3Transferring the noble metal propane dehydrogenation catalyst into a reduction container, and reducing for 0.5-4 h at the temperature of 500-600 ℃ in a hydrogen atmosphere to obtain activated yolk-eggshell structure SiO2-Al2O3A noble metal propane dehydrogenation catalyst.
12. The yolk-eggshell SiO of claim 112-Al2O3The preparation method of the noble metal propane dehydrogenation catalyst is characterized in that the water-soluble aluminum salt is selected from one or more of aluminum chloride, aluminum sulfate, aluminum nitrate, sodium aluminate and potassium aluminate.
13. The yolk-eggshell SiO of claim 112-Al2O3The preparation method of the noble metal propane dehydrogenation catalyst is characterized in that the alkali liquor is a potassium hydroxide solution or a sodium hydroxide solution.
14. The yolk-eggshell SiO of claim 112-Al2O3The preparation method of the noble metal propane dehydrogenation catalyst is characterized in that the alkali liquor is sodium hydroxide solution.
15. The yolk-eggshell SiO of claim 112-Al2O3The preparation method of the noble metal propane dehydrogenation catalyst is characterized in that the adhesive is one or more of acetic acid, nitric acid, hydrochloric acid, sulfuric acid, acrylic acid and citric acid.
16. The yolk-eggshell SiO of claim 112-Al2O3The preparation method of the noble metal propane dehydrogenation catalyst is characterized in that the template agent is one or two of trimethylpentane and polyoxypropylene-polyoxyethylene.
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