CN115155595A - Core-shell structure nickel catalyst and preparation method thereof - Google Patents

Core-shell structure nickel catalyst and preparation method thereof Download PDF

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CN115155595A
CN115155595A CN202210742582.5A CN202210742582A CN115155595A CN 115155595 A CN115155595 A CN 115155595A CN 202210742582 A CN202210742582 A CN 202210742582A CN 115155595 A CN115155595 A CN 115155595A
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core
shell structure
preparation
catalyst
nickel catalyst
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边洲峰
邓少碧
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Southeast University
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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
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/16—Reducing
    • B01J37/18—Reducing with gases containing free hydrogen
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
    • C01B2203/0238—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a carbon dioxide reforming step
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1047—Group VIII metal catalysts
    • C01B2203/1052—Nickel or cobalt catalysts
    • C01B2203/1058—Nickel catalysts
    • 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

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  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
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  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
  • Catalysts (AREA)

Abstract

A core-shell structure nickel catalyst and a preparation method thereof are provided, wherein the core of the catalyst is a NixMgyAlz ternary hydrotalcite nanosheet, xyz respectively represents the mass percent of each substance in the ternary hydrotalcite, the shell is mesoporous silica, and nickel nanoparticles are coated between the interfaces of a Mg-Al mixed oxide and a silica shell layer. According to the invention, the NixMgyAlz ternary hydrotalcite nanosheet is taken as the core, the mesoporous silica is taken as the shell, the sintering of metal active sites is effectively inhibited under the limiting action of the shell layer, and the interaction between metal and a carrier is enhanced by the core-shell structure, so that the catalyst has more excellent catalytic performance in the dry weight regulation of methane.

Description

Core-shell structure nickel catalyst and preparation method thereof
Technical Field
The invention relates to a nickel catalyst, in particular to a core-shell structure nickel catalyst and a preparation method thereof, belonging to the technical field of catalysts.
Background
The development of modern industry discharges greenhouse gases which are responsible for global climate change, and how to solve the greenhouse effect is the subject of current research. Methane is also a gas with a strong greenhouse effect, and the dry reforming of methane and carbon dioxide reduces greenhouse gas emissions, while the syngas produced can be used to produce various chemicals and fuels.
The dry reforming reaction of methane is as follows: CH (CH) 4 +CO 2 →2H 2 +2CO, Δ H298=247KJ/mol, which is a strongly endothermic reaction. In addition, in the methane dry reforming reactionThe reaction process is also accompanied by the occurrence of other side reactions: reverse water gas reaction: CO 2 2 +H 2 →CO+2H 2 Δ H298=41KJ/mol, CO disproportionation: 2CO → CO 2 + C, ah 298= -172 KJ/mol, methane cracking: CH (CH) 4 →2H 2 + C, Δ H298=75KJ/mol. Due to CH 4 And CO 2 The reaction needs to be carried out at a higher temperature to achieve the desired conversion.
The methane dry reforming catalyst mainly comprises two main types of precious metals (Ru, rh, pd and Pt) and non-precious metals (Ni, co, cu and Fe). The noble metal has better activity and carbon deposition resistance, but the resource is limited. Among non-noble metals, the nickel-based catalyst has good selectivity and activity. The nickel-based catalyst has two problems, namely, the nickel nano particles are easy to sinter at high temperature; secondly, carbon deposition can occur during the reaction, leading to catalyst deactivation.
Disclosure of Invention
The invention provides a core-shell structure nickel catalyst and a preparation method thereof, aiming at the defects of the prior art.
The technical problem of the invention is solved by the following technical scheme:
a nickel catalyst with core-shell structure has Ni as kernel 1 Mg 6 Al 2.33 The catalyst shell of the ternary hydrotalcite nanosheet is mesoporous silica, the average pore diameter is 3.8nm, and the nickel nanoparticles are coated between the interface of the Mg-Al mixed oxide and the silica shell layer. The Ni nano-particle size is 11-13nm.
The preparation method of the core-shell structure nickel catalyst comprises the following steps:
a. adding a nickel source, a magnesium source, an aluminum source and urea into deionized water, stirring uniformly, transferring the solution into a hydrothermal kettle for reaction, naturally cooling after the reaction is finished, centrifuging, and washing twice with the deionized water to obtain Ni 1 Mg 6 Al 2.33 Placing the ternary hydrotalcite nanosheet into an oven for drying;
b. subjecting the Ni obtained in step a to 1 Mg 6 Al 2.33 Adding the ternary hydrotalcite nanosheet and a surfactant into a mixed solution of ethanol and deionized water, adding ammonia water into the solution, performing ultrasonic treatment, adding a silicon source after ultrasonic treatment, and stirring to obtain a solution A;
c. centrifuging the solution A, washing a solid B obtained by centrifuging, and drying by using an oven;
d. calcining the solid B powder in a muffle furnace to obtain a solid C;
e. placing the solid C in a tube furnace 10% 2 /N 2 And (4) reducing in the atmosphere.
In the preparation method of the core-shell structure nickel catalyst, in the step a, the nickel source is nickel nitrate; the magnesium source is magnesium acetate, and the aluminum source is aluminum nitrate.
In the preparation method of the core-shell structure nickel catalyst, the hydrothermal kettle in the step a is placed at 180 ℃ for reaction for 48 hours.
According to the preparation method of the core-shell structure nickel catalyst, the drying oven in the step a is set to be 80 ℃, and the drying is carried out for 12 hours.
In the preparation method of the core-shell structure nickel catalyst, in the step b, the surfactant is Cetyl Trimethyl Ammonium Bromide (CTAB), the using amount is 0.45g, the ultrasonic time is 30 to 60min, the silicon source is Tetraethoxysilane (TEOS), and the using amount is 0.3 to 0.9ml.
In the preparation method of the core-shell structure nickel catalyst, the drying oven is set to 80 ℃ in the step c, and the drying is carried out for 12 hours.
In the preparation method of the core-shell structure nickel catalyst, in the step d, the temperature rise rate of the muffle furnace is 3 ℃/min, the roasting temperature is 750 ℃, and the roasting time is 4h.
The preparation method of the core-shell structure nickel catalyst is characterized in that the content of H is 10 percent 2 /N 2 Reducing for 2h under the environment of 750 ℃.
The invention has the following advantages:
the kernel of the invention is Ni 1 Mg 6 Al 2.33 The shell of the ternary hydrotalcite nanosheet is mesoporous silica, and the space confinement effect of the shell layer restricts the mutual sintering of nickel metal particles, so that the sintering of metal active sites and the generation of carbon deposition are effectively inhibited, and the nickel and magnesium-aluminum mixed oxide carrier has stronger nickel and magnesium-aluminum mixed oxide carrierThe metal-carrier interaction further improves the anti-sintering and anti-carbon deposition capabilities of the catalyst, so that the catalyst shows more excellent catalytic performance in the dry reforming of methane. The nickel nano particles have the diameter of about 13nm and are uniformly distributed, so that the nickel nano particles have better catalytic performance. With the preceding Ni @ SiO 2 Compared with a core-shell structure, the preparation method has the advantages that the preparation of independent Ni nano particles is not needed, the preparation efficiency is higher, an organic solvent is not needed, and the preparation method is more environment-friendly.
Drawings
FIG. 1 is a transmission electron microscope image of a core-shell structured nickel catalyst prepared in example 1 of the present invention;
FIG. 2 is a graph of the pore size distribution for various catalysts of the present invention;
FIG. 3 shows CH in dry reforming of methane for different catalysts of the present invention 4 Schematic plot of conversion over time;
FIG. 4 is a graph of CO in dry reforming of methane for various catalysts of the present invention 2 Schematic of conversion over time;
FIG. 5 is a thermogravimetric TGA plot of different catalysts after the methane dry reforming reaction of the present invention, with weight loss being the amount of carbon deposition.
Detailed Description
Referring to FIG. 1, the catalyst core of the present invention is Ni 1 Mg 6 Al 2.33 The ternary hydrotalcite nanosheets 1,6 and 2.33 respectively represent the relative molar ratio of each substance in the ternary hydrotalcite, the shells are mesoporous silica, the average pore diameter is about 3.8nm, and the nickel nanoparticles are coated between the interfaces of the Mg-Al mixed oxide and the silica shell layers. The Ni nano-particle size is 11-13nm. The catalyst of the invention has a three-layer structure, and comprises the following components from outside to inside: a silicon oxide layer, a nickel nanoparticle layer, a Mg-Al mixed oxide layer. The nickel nano particle layer is positioned at the interlayer position, so that the sintering of the active component nickel of the catalyst and the formation of carbon deposition can be effectively prevented, and the stability is good.
Example 1
0.29g of Ni (NO) 3 ) 3 ·6H 2 O、1.28g Mg(CH 3 COO) 2 ·4H 2 O、0.974g Al(NO 3 ) 3 ·9H 2 O and 0.81g urea dissolved in 70ml deionized water. After stirring uniformly, transferring the solution into a hydrothermal kettle, and reacting for 48 hours at a hydrothermal temperature of 180 ℃. When cooled to room temperature, centrifuged, then washed with deionized water and dried in an oven at 80 ℃ for 12h.
0.2g of the solid obtained above was taken in a mixture of 100ml of deionized water and 100ml of ethanol. 0.45g of cetyltrimethylammonium bromide and 2ml of ammonia (35% by weight) were added and sonicated for 30min. Then, 0.3ml of ethyl orthosilicate was added and stirred for 12 hours.
The solid was collected with a centrifuge and washed twice with deionized water. The catalyst is calcined in a muffle furnace at 750 ℃ for 4h, and reduced in a hydrogen atmosphere at 750 ℃ for 2h, and the obtained catalyst is recorded as LDH @ SiO2-thin.
Example 2
0.29g of Ni (NO) 3 ) 3 ·6H 2 O、1.28g Mg(CH 3 COO) 2 ·4H 2 O、0.974g Al(NO 3 ) 3 ·9H 2 O and 0.81g urea were dissolved in 70ml deionized water. After being stirred uniformly, the solution is transferred into a hydrothermal kettle and reacts for 48 hours at a hydrothermal temperature of 180 ℃. When cooled to room temperature, centrifuged, then washed with deionized water and dried in an oven at 80 ℃ for 12h.
0.2g of the solid obtained above was put into a mixture of 100ml of deionized water and 100ml of ethanol. 0.45g of cetyltrimethylammonium bromide and 2ml of ammonia (35% by weight) were added and sonicated for 30min. Then 0.9ml of ethyl orthosilicate is added and stirred for 12h.
The solid was collected with a centrifuge and washed twice with deionized water. Calcining in muffle furnace at 750 deg.C for 4h, and reducing at 750 deg.C in hydrogen atmosphere for 2h to obtain catalyst (LDH @ SiO) 2 -thick。
In the above examples, the nickel source was nickel nitrate hexahydrate, and the manufacturer was shanghai Lingfeng; the magnesium source is magnesium acetate tetrahydrate, and the manufacturer is a Maya reagent; the aluminum source is aluminum nitrate nonahydrate, and the manufacturer is aladine. A manufacturer of Cetyl Trimethyl Ammonium Bromide (CTAB) is Michelin, a manufacturer of Tetraethoxysilane (TEOS) is Aladdin, and the usage amount of the CTAB is 0.3 to 0.9ml.
Comparative example 1
0.29g of Ni (NO) 3 ) 3 ·6H 2 O、1.28g Mg(CH 3 COO) 2 ·4H 2 O、0.974g Al(NO 3 ) 3 ·9H 2 O and 0.81g urea were dissolved in 70ml deionized water. After being stirred uniformly, the solution is transferred into a hydrothermal kettle and reacts for 48 hours at a hydrothermal temperature of 180 ℃. When cooled to room temperature, centrifuged, then washed with deionized water and dried in an oven at 80 ℃ for 12h.
The solid obtained above was calcined in a muffle furnace at a temperature of 750 ℃ for 4h, and the catalyst obtained was recorded as LDH.
Performance test
To ensure that the same amount of nickel was used, 8mg LDH and 15mg LDH @ SiO were taken 2 -thin、44mg LDH@SiO 2 -thick tests with different catalysts for their CH at different temperatures in the dry reforming reaction of methane 4 Conversion, CO 2 Conversion and catalytic stability.
Wherein the test conditions are as follows:
the dry reforming reaction of methane is carried out on a fixed bed at normal pressure, and the catalyst is placed in the middle of a quartz tube with the diameter of 6 mm. The reaction is started at the temperature of 600 ℃, and the reaction gas is CH with the volume fraction of 25 percent 4 25% CO 2 50% of N 2 The gas flow rate was 60ml/min.
Catalysts prepared in embodiment examples 1 and 2 of the present invention and comparative example 1 in dry reforming of methane 4 The conversion is shown in FIG. 2; CO 2 2 The conversion is shown in FIG. 3. As can be seen from the figure, examples 1 and 2 show that in 16 hours of reaction, CH 4 And CO 2 The conversion rate is stable. Comparative example 1 CH after 16 hours reaction 4 And CO 2 The conversion rate is reduced by 10 percent. It can be seen that the catalyst of the present invention has excellent stability. Meanwhile, the TGA result shows that the carbon deposition amount of the catalyst coated with the silicon oxide shell layer is only 2%, and the carbon deposition amount of the catalyst not coated with the silicon oxide is up to 68%, so that the existence of the silicon oxide shell layer can effectively inhibit the formation of the carbon deposition.

Claims (9)

1. A nickel catalyst with a core-shell structure, which is characterized in thatCharacterized in that the core of the catalyst is Ni 1 Mg 6 Al 2.33 The catalyst shell is mesoporous silica with an average pore diameter of 3.8nm,
wherein the nickel nanoparticles are coated between the interface of the Mg-Al mixed oxide and the silica shell layer.
2. The preparation method of the core-shell structure nickel catalyst according to claim 1, characterized by comprising the following steps:
a. adding a nickel source, a magnesium source, an aluminum source and urea into deionized water, stirring uniformly, transferring the solution into a hydrothermal kettle for reaction, naturally cooling after the reaction is finished, centrifuging, and washing twice with the deionized water to obtain Ni 1 Mg 6 Al 2.33 Placing the ternary hydrotalcite nanosheet into an oven for drying;
b. subjecting the Ni obtained in step a to 1 Mg 6 Al 2.33 Adding the ternary hydrotalcite nanosheet and a surfactant into a mixed solution of ethanol and deionized water, adding ammonia water into the solution, performing ultrasonic treatment, adding a silicon source after ultrasonic treatment, and stirring to obtain a solution A;
c. centrifuging the solution A, washing a solid B obtained by centrifuging, and drying by using an oven;
d. calcining the solid B powder in a muffle furnace to obtain a solid C;
e. placing the solid C in a tube furnace 10% 2 /N 2 And (4) reducing in the atmosphere.
3. The preparation method of the core-shell structure nickel catalyst as claimed in claim 2, wherein in the step a, the nickel source is nickel nitrate, the magnesium source is magnesium acetate, and the aluminum source is aluminum nitrate.
4. The preparation method of the core-shell structure nickel catalyst according to claim 2, wherein the hydrothermal kettle in the step a is placed at a temperature of 180 ℃ for reaction for 48 hours.
5. The preparation method of the core-shell structure nickel catalyst, according to claim 2, is characterized in that the drying oven of step a is set at 80 ℃ and dried for 12h.
6. The preparation method of the core-shell structure nickel catalyst, according to claim 2, characterized in that in the step b, the surfactant is Cetyl Trimethyl Ammonium Bromide (CTAB) with an amount of 0.45g, the ultrasonic time is 30 to 60min, the silicon source is Tetraethoxysilane (TEOS) with an amount of 0.3 to 0.9ml.
7. The preparation method of the core-shell structure nickel catalyst, according to claim 2, is characterized in that the drying oven in the step c is set at 80 ℃ and dried for 12h.
8. The preparation method of the core-shell structure nickel catalyst according to claim 2, wherein the muffle furnace temperature rise rate in the step d is 3 ℃/min, the roasting temperature is 750 ℃, and the roasting time is 4h.
9. The process for preparing a nickel catalyst having a core-shell structure according to claim 2, wherein in step e, the result is put in a tube furnace 10% 2 /N 2 And reducing for 2h in the atmosphere.
CN202210742582.5A 2022-06-27 2022-06-27 Core-shell structure nickel catalyst and preparation method thereof Pending CN115155595A (en)

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Cited By (1)

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CN117244563A (en) * 2023-11-15 2023-12-19 内蒙古鄂尔多斯电力冶金集团股份有限公司 Coated Ni-based photo-thermal catalyst and preparation method and application thereof

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