CN108855095B - Methane reforming multi-core-shell hollow catalyst nickel-nickel silicate-SiO2Preparation method of (1) - Google Patents

Methane reforming multi-core-shell hollow catalyst nickel-nickel silicate-SiO2Preparation method of (1) Download PDF

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CN108855095B
CN108855095B CN201810127056.1A CN201810127056A CN108855095B CN 108855095 B CN108855095 B CN 108855095B CN 201810127056 A CN201810127056 A CN 201810127056A CN 108855095 B CN108855095 B CN 108855095B
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silicate
sio
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CN108855095A (en
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李敏
李自卫
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Guizhou Institute of Technology
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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
    • B01J23/74—Iron group metals
    • B01J23/755—Nickel
    • B01J35/393—
    • B01J35/394—
    • B01J35/50—
    • C—CHEMISTRY; METALLURGY
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    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
    • C01B3/40—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts characterised by the catalyst
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Abstract

The invention discloses a multi-core-shell hollow catalyst nickel-nickel silicate-SiO for methane reforming2The preparation method is characterized by comprising the following steps: (1) firstly, preparing silicon dioxide nano particles; (2) preparing silicon dioxide nano particles with the particle size of 500 nm-1 mu m into 1 g/L-10 g/L of concentration, adding alkali liquor to adjust the pH to 8-13, adding a nickel precursor with the concentration of 1 g/L-10 g/L, and performing heat treatment at the temperature of 50 DEG CoC～220oSynthesizing hollow nickel silicate balls under the condition of C; (3) dispersing hollow nickel silicate spheres in a mixed solution of a surfactant and water, adding alkali liquor after stirring, adjusting the pH to 10-14, adding 10mL of ethyl orthosilicate, and reacting at room temperature to obtain nickel silicate-SiO2A core-shell hollow sphere; (4) nickel silicate-SiO2The temperature of the core-shell hollow sphere is 300oC～800oReducing the mixture in a hydrogen atmosphere to obtain highly dispersed nickel-nickel silicate-SiO2A multi-core shell hollow catalyst. The catalyst prepared by the invention has the advantages of high sintering resistance, carbon deposition resistance, high-temperature stability and high specific surface area.

Description

Methane reforming multi-core-shell hollow catalyst nickel-nickel silicate-SiO2Preparation method of (1)
Technical Field
The invention relates to a multi-core-shell hollow catalyst nickel-nickel silicate-SiO for methane reforming2Belonging to the technical field of chemical production.
Background
The nickel-based catalyst has been widely studied at home and abroad due to its low price and high reforming catalytic activity, and when it is applied to CH4During the dry reforming reaction, the carbon deposition phenomenon of the nickel-based catalyst is serious, and the sintering of the nickel metal promotes the occurrence of the carbon deposition side reaction. Especially when CH4The dry reforming reaction temperature is lower than 600 DEG CoAnd C, the carbon deposition phenomenon is more serious. The present inventors have developed a core-shell structured catalyst that can effectively prevent metal sintering. However, these core-shell structures generally have problems of low specific surface area and low mass transfer efficiency.
Metal silicates are widely used as catalysts because of their low cost, high temperature stability, high specific surface area, and other advantages. However, these metal silicates are currently used only as precursors of catalysts, and after reduction at high temperatures, the metal silicates are completely decomposed, losing the advantage of their high specific surface area.
Namely: there is a need for a multiple core-shell hollow catalyst for methane reforming in the CH4The dry reforming reaction temperature was 600 deg.CoUnder the condition of C, the alloy still has high carbon deposition resistance, high specific surface area and sintering resistance.
Disclosure of Invention
The invention aims to solve the technical problem of providing a multi-core shell hollow catalyst nickel-nickel silicate-SiO for methane reforming2In CH4The dry reforming reaction temperature was 600 deg.CoUnder the condition of C, the alloy still has high sintering resistance, carbon deposition resistance, high-temperature stability and high specific surface area so as to overcome the defects of the prior art.
The technical scheme of the invention is as follows: methane reforming multi-core-shell hollow catalyst nickel-nickel silicate-SiO2The preparation method comprises the following steps: (1) the ethanol, the water and the silicon source are 0oC～70oC, uniformly mixing and stirring, adding alkali liquor to adjust the pH value to 10, stirring, separating by a centrifugal machine, washing, and finally drying to obtain silicon dioxide nano particles; (2) preparing silicon dioxide nano particles with the particle size of 500 nm-1 mu m into 1 g/L-10 g/L of concentration, adding alkali liquor to adjust the pH to 8-13, adding a nickel precursor with the concentration of 1 g/L-10 g/L, and performing heat treatment at the temperature of 50 DEG CoC～220oC, synthesizing under the condition of C, and finally cooling, centrifugally separating and washing to obtain the nickel silicate hollow spheres; (3) dispersing hollow nickel silicate spheres in a mixed solution of a surfactant and water, adding an alkali solution after stirring, adjusting the pH to 10-14, adding 10mL of ethyl orthosilicate for reaction at room temperature, and finally performing centrifugal separation, washing and drying to obtain nickel silicate-SiO2A core-shell hollow sphere; (4) nickel silicate-SiO2The temperature of the core-shell hollow sphere is 300oC～800oReducing the mixture in a hydrogen atmosphere to obtain highly dispersed nickel-nickel silicate-SiO2A multi-core shell hollow catalyst.
In the step (1), the silicon source is one or a combination of more of tetraethoxysilane, sodium silicate water glass and methyl orthosilicate.
In the step (2), the nickel precursor is one or a combination of nickel nitrate, nickel acetate, nickel acetylacetonate, nickel oxalate and nickel oleate.
In the steps (1), (2) and (3), the alkaline solution is one or a combination of several of sodium hydroxide, urea and ammonia water.
In the steps (1), (2) and (3), the washing solvent used for washing is one or a combination of several of water, ethanol, methanol, acetone and cyclohexane.
In the step (3), the surfactant is a nonionic surfactant or an ionic surfactant, wherein the nonionic surfactant is C14H22O(C2H4O)n，n=10～15，C15H24O(C2H4O)nN = 5-10; the ionic surfactant is an alkyl quaternary ammonium salt surfactant CnAnd (3) TAB, wherein n = 10-15.
In the step (4), the specific surface area of the nickel-nickel silicate-silicon dioxide core-shell hollow catalyst is 300m2•g-1～600m2•g-1The thickness of the silicon dioxide shell layer is 30 nm-80 nm.
Compared with the prior art, the methane reforming multi-core shell hollow catalyst nickel-nickel silicate-SiO2The preparation method comprises the following steps: (1) the ethanol, the water and the silicon source are 0oC～70oC, uniformly mixing and stirring, adding alkali liquor to adjust the pH value to 10, stirring, separating by a centrifugal machine, washing, and finally drying to obtain silicon dioxide nano particles; (2) preparing silicon dioxide nano particles with the particle size of 500 nm-1 mu m into 1 g/L-10 g/L of concentration, adding alkali liquor to adjust the pH to 8-13, adding a nickel precursor with the concentration of 1 g/L-10 g/L, and performing heat treatment at the temperature of 50 DEG CoC～220oC, synthesizing under the condition of C, and finally cooling, centrifugally separating and washing to obtain the nickel silicate hollow spheres; (3) dispersing hollow nickel silicate spheres in a mixed solution of a surfactant and water, stirring, adding an alkali solution, adjusting the pH to 10-14, adding 10mL of tetraethoxysilane, reacting at room temperature, and finally centrifugingSeparating, washing and drying to obtain nickel silicate-SiO2A core-shell hollow sphere; (4) nickel silicate-SiO2The temperature of the core-shell hollow sphere is 300oC～800oReducing the mixture in a hydrogen atmosphere to obtain highly dispersed nickel-nickel silicate-SiO2A multi-core shell hollow catalyst. Nickel-nickel silicate-SiO prepared by the method2Has high dispersity (grain diameter is 2 nm-7 nm) and high carbon deposition resistance (carbon deposition amount)<11%), in particular in CH4The dry reforming reaction temperature was 600 deg.CoUnder the condition of C, the carbon deposition resistance is still higher than that of the prior art of 700oCompared with the catalyst with higher carbon deposition resistance, the catalyst with higher carbon deposition resistance has obvious advantages and wider applicability; at the same time, has high specific surface area (300 m)2·g-1～600m2·g-1) Strong metal support interaction (reduction temperature 655)oC or above) has high mass transfer efficiency. The nickel nano particles are dispersed in the nickel silicate hollow spheres and SiO2In the shell layer, a multi-core shell hollow structure is formed, the grain diameter of the multi-core shell hollow structure is 500 nm-1 mu m, and the multi-core shell hollow structure is similar to the existing CH4Compared with the dry reforming nickel-based catalyst, the synthesis method is rapid, the synthesis raw materials are easy to obtain, the large-scale synthesis can be realized, and the synthesized catalyst has the advantages of high specific surface area, high dispersity, strong interaction of metal carriers, high mass transfer efficiency and good carbon deposition resistance.
Drawings
FIG. 1 is a nickel-nickel silicate-SiO2Schematic diagram of preparation method of multi-core-shell hollow type.
FIG. 2 is a transmission electron micrograph of a nickel silicate hollow sphere.
FIG. 3 is a high resolution transmission electron microscope image of NiSi hollow sphere.
FIG. 4 is a nickel silicate-SiO2Transmission electron micrographs of core-shell hollow spheres.
FIG. 5 is a nickel silicate-SiO2High resolution transmission electron microscopy images of core-shell hollow spheres.
FIG. 6 is a nickel-nickel silicate-SiO2Transmission electron microscopy of multi-core shell hollow catalysts.
FIG. 7 is a nickel-nickel silicate-SiO2Multiple core-shell hollow typeHigh resolution transmission electron microscopy images of the catalyst.
FIG. 8 is a nickel silicate hollow sphere-nickel silicate-SiO2And (4) performing temperature programmed reduction on the core-shell hollow sphere.
FIG. 9 is a nickel silicate hollow sphere-nickel silicate-SiO2Core-shell hollow catalyst CH4Dry reforming reaction activity plot.
FIG. 10 is a nickel silicate hollow sphere-nickel silicate-SiO2Core-shell hollow catalyst CH4Thermogravimetric analysis profile after dry reforming reaction.
Detailed Description
Methane reforming multi-core-shell hollow catalyst nickel-nickel silicate-SiO2The preparation method comprises the steps of adding 0 of ethanol, water and silicon sourceoC～70oC, uniformly mixing and stirring, adding alkali liquor to adjust the pH value to 10, stirring, separating by a centrifugal machine, washing, and finally drying to obtain silicon dioxide nano particles; preparing silicon dioxide nano particles with the particle size of 500 nm-1 mu m into 1 g/L-10 g/L of concentration, adding alkali liquor to adjust the pH to 8-13, adding a nickel precursor with the concentration of 1 g/L-10 g/L, and performing heat treatment at the temperature of 50 DEG CoC～220oC, synthesizing under the condition of C, and finally cooling, centrifugally separating and washing to obtain the nickel silicate hollow spheres; dispersing hollow nickel silicate spheres in a mixed solution of a surfactant and water, adding an alkali solution after stirring, adjusting the pH to 10-14, adding 10mL of ethyl orthosilicate for reaction at room temperature, and finally performing centrifugal separation, washing and drying to obtain nickel silicate-SiO2A core-shell hollow sphere; nickel silicate-SiO2The temperature of the core-shell hollow sphere is 300oC～800oReducing the mixture in a hydrogen atmosphere to obtain highly dispersed nickel-nickel silicate-SiO2A multi-core shell hollow catalyst.
Example 1:
(1) 200mL of ethanol, 100mL of water and 40mL of methyl orthosilicate in the presence of 0oAnd C, mixing and stirring uniformly. Urea was added to adjust the pH to 10. After stirring for 2h, the mixture was centrifuged. Washing with methanol and water mixture. Finally, the 600nm silicon dioxide nano-particles are obtained, and the particle size is 150oAnd C, drying for 24 h.
(2) Taking 2g of dioxideSilicon, 0.3g nickel nitrate, ammonia was added to adjust the pH to 8. And (3) putting the mixed solution into a high-pressure reaction kettle, heating to 50 ℃, reacting for 24 hours, and cooling to room temperature. Centrifugally separating, washing with methanol, ethanol and water, and drying in a 100-degree drying oven. Obtaining hollow nickel silicate balls (as shown in figures 2 and 3) with specific area of 250m2·g-1。
(3) Dispersing hollow nickel silicate spheres in ethanol (30 mL), water (10 mL) and CnTAB (n =10) (30 mg) in a mixed solution. After stirring for 30min, ammonia (30 mL) was added. The pH was adjusted to 10, and after stirring for 30min, 10mL of ethyl orthosilicate was added. After 48 hours of reaction at room temperature, it was centrifuged and washed 3 times with a mixed solution of methanol and water. Put into a drying oven at 100oAnd C, drying for 24 h. To obtain nickel silicate-SiO2Hollow core-shell spheres of SiO2The thickness of a shell layer is 40nm, and the specific surface area is 400m2·g-1(as shown in fig. 4, 5).
(4) Nickel silicate-SiO2And putting the core-shell hollow spheres into a muffle furnace to calcine for 4 hours at 700 ℃. Then pure hydrogen is introduced and reduced for 0.5h at 700 ℃. Finally obtaining the nickel-nickel silicate-SiO2The multi-core shell hollow sphere catalyst (shown in figures 6 and 7). As can be seen from fig. 6 and 7, the acicular nickel silicate phase still exists although it is calcined at a high temperature and reduced. It can be seen that the nickel silicate is not completely decomposed in the catalyst obtained by the present synthesis method. The particle size of the highly dispersed nickel is about 5 nm. In addition, compared to the nickel silicate hollow sphere catalyst, nickel silicate-SiO2The core-shell hollow sphere catalyst has higher reduction temperature, which indicates that the core-shell catalyst has higher metal carrier strong interaction (as shown in fig. 8).
(5) At normal pressure, adding CH4、CO2And He at 1:1:1 (space velocity 36L. g)-1cat·h-1) Respectively introducing nickel-nickel silicate hollow spheres and nickel-nickel silicate-SiO2Multi-core-shell hollow catalyst fixed bed reactor (600)oC) And reacting for 50 hours. For the nickel-nickel silicate hollow sphere catalyst, although the initial conversion was slightly higher due to its higher nickel loading. But instead of the other end of the tubeThe conversion of methane and carbon dioxide decreased by 36% and 31%, respectively. In comparison, for nickel-nickel silicate-SiO2The conversion rates of methane and carbon dioxide of the core-shell hollow sphere catalyst were respectively reduced by 23% and 20% (fig. 9). The thermogravimetric differential thermal analysis can show that the nickel-nickel silicate-SiO2Multi-core-shell hollow sphere catalyst nickel-nickel silicate-SiO2The weight loss of the core-shell hollow sphere catalyst is only 1/7 of that of the nickel-nickel silicate catalyst, which shows that the former has high carbon deposition resistance (figure 10).
Example 2:
(1) 200mL of ethanol, 100mL of water and 40mL of methyl orthosilicate in 35 mL ofoAnd C, mixing and stirring uniformly. Urea was added to adjust the pH to 10. After stirring for 2h, the mixture was centrifuged. Washing with methanol and water mixture. Finally, the 600nm silicon dioxide nano-particles are obtained, and the particle size is 150oAnd C, drying for 24 h.
(2) 2g of silicon dioxide and 0.3g of nickel nitrate are taken, ammonia water is added, and the pH value is adjusted to 11. And (3) putting the mixed solution into a high-pressure reaction kettle, heating to 50 ℃, reacting for 24 hours, and cooling to room temperature. Centrifugally separating, washing with methanol, ethanol and water, and drying in a 100-degree drying oven. Obtaining hollow nickel silicate balls (as shown in figures 2 and 3) with specific area of 250m2·g-1。
(3) Dispersing hollow nickel silicate spheres in ethanol (30 mL), water (10 mL) and CnTAB (n =10) (30 mg) in a mixed solution. After stirring for 30min, ammonia (30 mL) was added. The pH was adjusted to 12, and after stirring for 30min, 10mL of ethyl orthosilicate was added. After 48 hours of reaction at room temperature, it was centrifuged and washed 3 times with a mixed solution of methanol and water. Put into a drying oven at 100oAnd C, drying for 24 h. To obtain nickel silicate-SiO2Hollow core-shell spheres of SiO2The thickness of a shell layer is 40nm, and the specific surface area is 400m2·g-1(as shown in fig. 4, 5).
(4) Nickel silicate-SiO2And putting the core-shell hollow spheres into a muffle furnace to calcine for 4 hours at 700 ℃. Then pure hydrogen is introduced and reduced for 0.5h at 700 ℃. Finally obtaining the nickel-nickel silicate-SiO2The multi-core shell hollow sphere catalyst (shown in figures 6 and 7). As can be seen from FIGS. 6 and 7The acicular nickel silicate phase still exists despite the high temperature calcination and reduction. It can be seen that the nickel silicate is not completely decomposed in the catalyst obtained by the present synthesis method. The particle size of the highly dispersed nickel is about 5 nm. In addition, compared to the nickel silicate hollow sphere catalyst, nickel silicate-SiO2The core-shell hollow sphere catalyst has higher reduction temperature, which indicates that the core-shell catalyst has higher metal carrier strong interaction (as shown in fig. 8).
(5) At normal pressure, adding CH4、CO2And He at 1:1:1 (space velocity 36L. g)-1cat·h-1) Respectively introducing nickel-nickel silicate hollow spheres and nickel-nickel silicate-SiO2Fixed bed reactor with multi-core-shell hollow sphere catalyst (600)oC) And reacting for 50 hours. For the nickel-nickel silicate hollow sphere catalyst, although the initial conversion was slightly higher due to its higher nickel loading. However, the conversion of methane and carbon dioxide decreased 36% and 31%, respectively. In comparison, for nickel-nickel silicate-SiO2The conversion rates of methane and carbon dioxide of the core-shell hollow sphere catalyst are respectively reduced by 19 percent and 22 percent. The thermogravimetric differential thermal analysis can show that the nickel-nickel silicate-SiO2The weight loss of the multi-core shell hollow sphere catalyst is 1/8 of a nickel-nickel silicate catalyst, which shows that the catalyst has high carbon deposition resistance.
Example 3:
(1) 200mL of ethanol, 100mL of water and 40mL of methyl orthosilicate in 70oAnd C, mixing and stirring uniformly. Urea was added to adjust the pH to 10. After stirring for 2h, the mixture was centrifuged. Washing with methanol and water mixture. Finally, the 600nm silicon dioxide nano-particles are obtained, and the particle size is 150oAnd C, drying for 24 h.
(2) 2g of silicon dioxide and 0.3g of nickel nitrate are taken, ammonia water is added, and the pH value is adjusted to 13. And (3) putting the mixed solution into a high-pressure reaction kettle, heating to 50 ℃, reacting for 24 hours, and cooling to room temperature. Centrifugally separating, washing with methanol, ethanol and water, and drying in a 100-degree drying oven. Obtaining hollow nickel silicate balls (as shown in figures 2 and 3) with specific area of 250m2·g-1。
(3) Dispersing hollow nickel silicate spheres inEthanol (30 mL), water (10 mL), CnTAB (n =10) (30 mg) in a mixed solution. After stirring for 30min, ammonia (30 mL) was added. The pH was adjusted to 14, and after stirring for 30min, 10mL of ethyl orthosilicate was added. After 48 hours of reaction at room temperature, it was centrifuged and washed 3 times with a mixed solution of methanol and water. Put into a drying oven at 100oAnd C, drying for 24 h. To obtain nickel silicate-SiO2Hollow core-shell spheres of SiO2The thickness of a shell layer is 40nm, and the specific surface area is 400m2·g-1(as shown in fig. 4, 5).
(4) Nickel silicate-SiO2And putting the core-shell hollow spheres into a muffle furnace to calcine for 4 hours at 700 ℃. Then pure hydrogen is introduced and reduced for 0.5h at 700 ℃. Finally obtaining the nickel-nickel silicate-SiO2The multi-core shell hollow sphere catalyst (shown in figures 6 and 7). As can be seen from fig. 6 and 7, the acicular nickel silicate phase still exists although it is calcined at a high temperature and reduced. It can be seen that the nickel silicate is not completely decomposed in the catalyst obtained by the present synthesis method. The particle size of the highly dispersed nickel is about 5 nm. In addition, compared to the nickel silicate hollow sphere catalyst, nickel silicate-SiO2The core-shell hollow sphere catalyst has higher reduction temperature, which indicates that the core-shell catalyst has higher metal carrier strong interaction (as shown in fig. 8).
(5) At normal pressure, adding CH4、CO2And He at 1:1:1 (space velocity 36L. g)-1cat·h-1) Respectively introducing nickel-nickel silicate hollow spheres and nickel-nickel silicate-SiO2Fixed bed reactor with multi-core-shell hollow sphere catalyst (600)oC) And reacting for 50 hours. For the nickel-nickel silicate hollow sphere catalyst, although the initial conversion was slightly higher due to its higher nickel loading. However, the conversion of methane and carbon dioxide decreased 36% and 31%, respectively. In comparison, for nickel-nickel silicate-SiO2The conversion rates of methane and carbon dioxide of the core-shell hollow sphere catalyst are respectively reduced by 30 percent and 29 percent. The thermogravimetric differential thermal analysis can show that the nickel-nickel silicate-SiO2The weight loss of the multi-core shell hollow sphere catalyst is 90 percent of that of the nickel-nickel silicate catalyst, which shows that the catalyst has high carbon deposition resistance.
Example 4:
(1) 200mL of ethanol, 100mL of water and 40mL of methyl orthosilicate were mixed and stirred at room temperature. Urea was added to adjust the pH to 10. After stirring for 2h, the mixture was centrifuged. Washing with methanol and water mixture. Finally, the 600nm silicon dioxide nano-particles are obtained, and the particle size is 150oAnd C, drying for 24 h.
(2) 2g of silicon dioxide and 0.3g of nickel nitrate are taken, ammonia water is added, and the pH value is adjusted to 12. And (3) putting the mixed solution into a high-pressure reaction kettle, heating to 120 ℃, reacting for 24 hours, and cooling to room temperature. Centrifugally separating, washing with methanol, ethanol and water, and drying in a 100-degree drying oven. Obtaining hollow nickel silicate balls (as shown in figures 2 and 3) with specific area of 250m2·g-1。
(3) Dispersing hollow nickel silicate spheres in ethanol (30 mL), water (10 mL) and CnTAB (n =10) (30 mg) in a mixed solution. After stirring for 30min, ammonia (30 mL) was added. After stirring for 30min, 10mL of tetraethyl orthosilicate was added. After 48 hours of reaction at room temperature, it was centrifuged and washed 3 times with a mixed solution of methanol and water. Put into a drying oven at 100oAnd C, drying for 24 h. To obtain nickel silicate-SiO2Hollow core-shell spheres of SiO2The thickness of a shell layer is 40nm, and the specific surface area is 400m2·g-1(as shown in fig. 4, 5).
(4) Nickel silicate-SiO2And putting the core-shell hollow spheres into a muffle furnace to calcine for 4 hours at 700 ℃. Then pure hydrogen is introduced and reduced for 0.5h at 700 ℃. Finally obtaining the nickel-nickel silicate-SiO2The multi-core shell hollow sphere catalyst (shown in figures 6 and 7). As can be seen from fig. 6 and 7, the acicular nickel silicate phase still exists although it is calcined at a high temperature and reduced. It can be seen that the nickel silicate is not completely decomposed in the catalyst obtained by the present synthesis method. The particle size of the highly dispersed nickel is about 5 nm. In addition, compared to the nickel silicate hollow sphere catalyst, nickel silicate-SiO2The core-shell hollow sphere catalyst has higher reduction temperature, which indicates that the core-shell catalyst has higher metal carrier strong interaction (as shown in fig. 8).
(5) At normal pressure, adding CH4、CO2And He at 1:1:1 (space velocity 36L. g)-1cat·h-1) Respectively introducing nickel-nickel silicate hollow spheres and nickel-nickel silicate-SiO2Fixed bed reactor with multi-core-shell hollow sphere catalyst (600)oC) And reacting for 50 hours. For the nickel-nickel silicate hollow sphere catalyst, although the initial conversion was slightly higher due to its higher nickel loading. However, the conversion of methane and carbon dioxide decreased 36% and 31%, respectively. In comparison, for nickel-nickel silicate-SiO2The conversion rates of methane and carbon dioxide of the core-shell hollow sphere catalyst were respectively reduced by 23% and 20% (fig. 9). The thermogravimetric differential thermal analysis can show that the nickel-nickel silicate-SiO2The weight loss of the multi-core-shell hollow sphere catalyst is only 1/7 of that of the nickel-nickel silicate catalyst, which shows that the former has high carbon deposition resistance (figure 10).
Example 5:
(1) 200mL of ethanol, 100mL of water and 10mL of sodium silicate in a mixture of 0oAnd C, mixing and stirring uniformly. Ammonia was added to adjust the pH to 10. After stirring for 2h, the mixture was centrifuged. Washing with ethanol and water. Finally, the silica nanoparticles with the particle size of 200nm are obtained and dried for 24h at 150 ℃.
(2) 2g of silicon dioxide and 0.3g of nickel acetate are taken, sodium hydroxide is added, and the pH value is adjusted to 12. And (3) putting the mixed solution into a high-pressure reaction kettle, heating to 120 ℃, reacting for 24 hours, and cooling to room temperature. Centrifuging, washing with methanol, ethanol, and water, and preventing 100 deg.CoAnd C, drying in a drying oven. Obtaining the hollow nickel silicate sphere. Specific area of 230m2·g-1。
(3) Dispersing hollow nickel silicate spheres in ethanol (30 mL), water (10 mL) and CnTAB (n =10) (30 mg) in a mixed solution. After stirring for 30min, ammonia (30 mL) was added. After stirring for 30min, 30mL of tetraethyl orthosilicate was added. After 80 hours of reaction at room temperature, it was centrifuged and washed 3 times with a mixed solution of methanol and water. Put into a drying oven at 100oAnd C, drying for 24 h. To obtain nickel silicate-SiO2Hollow core-shell spheres of SiO2The thickness of a shell layer is 80nm, and the specific surface area is 600m2·g-1。
(4) Nickel is mixed withsilicate-SiO2And putting the core-shell hollow spheres into a muffle furnace to calcine for 4 hours at 700 ℃. Then 5% hydrogen is introduced, and reduction is carried out for 0.5h at 700 ℃. Finally obtaining the nickel-nickel silicate-SiO2Catalyst of hollow ball with multi-core shell. Despite the high temperature calcination and reduction, a needle-like nickel silicate phase still exists. It can be seen that the nickel silicate is not completely decomposed in the catalyst obtained by the present synthesis method. The particle size of the highly dispersed nickel is about 6 nm. In addition, compared to the nickel silicate hollow sphere catalyst, nickel silicate-SiO2The core-shell hollow sphere catalyst has higher reduction temperature, which shows that the core-shell catalyst has higher metal carrier strong interaction.
(5) At normal pressure, adding CH4、CO2And He at 1:1:1 (space velocity 36L. g)-1cat·h-1) Respectively introducing nickel-nickel silicate hollow spheres and nickel-nickel silicate-SiO2Fixed bed reactor with multi-core-shell hollow sphere catalyst (600)oC) And reacting for 50 hours. For the nickel-nickel silicate hollow sphere catalyst, although the initial conversion was slightly higher due to its higher nickel loading. However, the conversion of methane and carbon dioxide decreased 36% and 31%, respectively. In comparison, for nickel-nickel silicate-SiO2The conversion rates of methane and carbon dioxide of the multi-core-shell hollow sphere catalyst are respectively reduced by 19 percent and 22 percent. The thermogravimetric differential thermal analysis can show that the nickel-nickel silicate-SiO2The weight loss of the core-shell hollow sphere catalyst is 1/8 of a nickel-nickel silicate catalyst, which shows that the core-shell hollow sphere catalyst has high carbon deposition resistance.
Example 6:
(1) 200mL of ethanol, 100mL of water and 10mL of sodium silicate were mixed and stirred at room temperature. Ammonia was added to adjust the pH to 10. After stirring for 12h, the mixture was centrifuged. Washing with ethanol and water. Finally obtaining 1 mu m silicon dioxide nano particles, and drying at 150 ℃ for 24 h.
(2) 2g of silicon dioxide and 0.3g of nickel acetylacetonate are taken, added with urea and the pH is adjusted to 12. And (3) putting the mixed solution into a high-pressure reaction kettle, heating to 120 ℃, reacting for 24 hours, and cooling to room temperature. Centrifugally separating, washing with methanol, ethanol and water, and drying in a 100-degree drying oven. Obtaining the nickel silicate blankThe heart ball. Specific area of 328m2·g-1The nickel loading was 35 wt%.
(3) Dispersing hollow nickel silicate spheres in ethanol (30 mL), water (10 mL) and CnTAB (n =10) (30 mg) in a mixed solution. After stirring for 30min, ammonia (30 mL) was added. After stirring for 30min, 1mL of tetraethyl orthosilicate was added. After 1 hour of reaction at room temperature, it was centrifuged, and washed 3 times with a mixed solution of methanol and water. Put into a drying oven at 100oAnd C, drying for 24 h. To obtain nickel silicate-SiO2Hollow core-shell spheres of SiO2The thickness of a shell layer is 20nm, and the specific surface area is 300m2·g-1。
(4) Nickel silicate-SiO2And putting the core-shell hollow spheres into a muffle furnace to calcine for 4 hours at 700 ℃. Then 15% hydrogen is introduced, and the mixture is reduced for 0.5h at 700 ℃. Finally obtaining the nickel-nickel silicate-SiO2Catalyst of hollow ball with multi-core shell. Despite the high temperature calcination and reduction, a needle-like nickel silicate phase still exists. It can be seen that the nickel silicate is not completely decomposed in the catalyst obtained by the present synthesis method. The particle size of the highly dispersed nickel is about 7 nm. In addition, compared to the nickel silicate hollow sphere catalyst, nickel silicate-SiO2The core-shell hollow sphere catalyst has higher reduction temperature, which shows that the core-shell catalyst has higher metal carrier strong interaction.
(5) At normal pressure, adding CH4、CO2And He at 1:1:1 (space velocity 36L. g)-1cat·h-1) Respectively introducing nickel-nickel silicate hollow spheres and nickel-nickel silicate-SiO2Fixed bed reactor with multi-core-shell hollow sphere catalyst (600)oC) And reacting for 50 hours. For the nickel-nickel silicate hollow sphere catalyst, although the initial conversion was slightly higher due to its higher nickel loading. However, the conversion of methane and carbon dioxide decreased 36% and 31%, respectively. In comparison, for nickel-nickel silicate-SiO2The conversion rates of methane and carbon dioxide of the multi-core-shell hollow sphere catalyst are respectively reduced by 30 percent and 29 percent. The thermogravimetric differential thermal analysis can show that the nickel-nickel silicate-SiO2The weight loss of the core-shell hollow sphere catalyst is 90 percent of that of the nickel-nickel silicate catalyst, which shows that the core-shell hollow sphere catalyst has high weight lossAnti-carbon deposition capability.

Claims (6)

1. Methane reforming multi-core-shell hollow catalyst nickel-nickel silicate-SiO2Is characterized in that the nickel-nickel silicate-SiO prepared by the method2The multi-core-shell hollow catalyst is suitable for the temperature of 600 DEG CoCH at C4Dry reforming reaction, the method comprising the steps of:
(1) the ethanol, the water and the silicon source are 0oC～70oC, uniformly mixing and stirring, adding alkali liquor to adjust the pH value to 10, stirring, separating by a centrifugal machine, washing, and finally drying to obtain silicon dioxide nano particles;
(2) preparing silicon dioxide nano particles with the particle size of 500 nm-1 mu m into 1 g/L-10 g/L of concentration, adding alkali liquor to adjust the pH to 8-13, adding a nickel precursor with the concentration of 1 g/L-10 g/L, and performing heat treatment at the temperature of 50 DEG CoC～220oC, synthesizing under the condition of C, and finally cooling, centrifugally separating and washing to obtain the nickel silicate hollow spheres;
(3) dispersing hollow nickel silicate spheres in a mixed solution of a surfactant and water, adding an alkali solution after stirring, adjusting the pH to 10-14, adding 10mL of ethyl orthosilicate for reaction at room temperature, and finally performing centrifugal separation, washing and drying to obtain nickel silicate-SiO2A core-shell hollow sphere;
(4) nickel silicate-SiO2The temperature of the core-shell hollow sphere is 300oC～800oReducing the mixture in a hydrogen atmosphere to obtain highly dispersed nickel-nickel silicate-SiO2A multi-core-shell hollow catalyst;
in the step (2), the nickel precursor is one or a combination of nickel nitrate, nickel acetate, nickel acetylacetonate, nickel oxalate and nickel oleate.
2. The methane reforming multi-core-shell hollow catalyst nickel-nickel silicate-SiO of claim 12The preparation method is characterized by comprising the following steps: in the step (1), the silicon source is one or a combination of more of tetraethoxysilane, sodium silicate sodium glass and methyl orthosilicate.
3. The methane reforming multi-core-shell hollow catalyst nickel-nickel silicate-SiO of claim 12The preparation method is characterized by comprising the following steps: in the steps (1), (2) and (3), the alkali liquor is one or a combination of several of sodium hydroxide, urea and ammonia water.
4. The methane reforming multi-core-shell hollow catalyst nickel-nickel silicate-SiO of claim 12The preparation method is characterized by comprising the following steps: in the steps (1), (2) and (3), the washing solvent used for washing is one or a combination of several of water, ethanol, methanol, acetone and cyclohexane.
5. The methane reforming multi-core-shell hollow catalyst nickel-nickel silicate-SiO of claim 12The preparation method is characterized by comprising the following steps: in the step (3), the surfactant is a nonionic surfactant or an ionic surfactant, wherein the nonionic surfactant is C14H22O(C2H4O)n，n=10～15，C15H24O(C2H4O)nN = 5-10; the ionic surfactant is an alkyl quaternary ammonium salt surfactant CnAnd (3) TAB, wherein n = 10-15.
6. The methane reforming multi-core-shell hollow catalyst nickel-nickel silicate-SiO of claim 12The preparation method is characterized by comprising the following steps: in the step (4), the specific surface area of the nickel-nickel silicate-silicon dioxide core-shell hollow catalyst is 300m2•g-1～600m2•g-1The thickness of the silicon dioxide shell layer is 30 nm-80 nm.
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