CN107376918A - High heat stability alundum (Al2O3)/nickel/alundum (Al2O3) sandwich catalyst and preparation method and application - Google Patents

High heat stability alundum (Al2O3)/nickel/alundum (Al2O3) sandwich catalyst and preparation method and application Download PDF

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CN107376918A
CN107376918A CN201710480165.7A CN201710480165A CN107376918A CN 107376918 A CN107376918 A CN 107376918A CN 201710480165 A CN201710480165 A CN 201710480165A CN 107376918 A CN107376918 A CN 107376918A
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catalyst
sandwich
high heat
heat stability
film
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赵羽
康运卿
李辉
李和兴
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Shanghai Normal University
University of Shanghai for Science and Technology
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Shanghai Normal University
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    • 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
    • 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
    • B01J35/391—Physical properties of the active metal ingredient
    • B01J35/393—Metal or metal oxide crystallite size
    • 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
    • B01J35/391—Physical properties of the active metal ingredient
    • B01J35/394—Metal dispersion value, e.g. percentage or fraction
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • 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
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    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1205—Composition of the feed
    • C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
    • C01B2203/1235—Hydrocarbons
    • C01B2203/1241—Natural gas or methane
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    • 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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Abstract

The present invention relates to a kind of high heat stability alundum (Al2O3)/nickel/alundum (Al2O3) sandwich catalyst and preparation method and application, high heat stability Al2O3/Ni/Al2O3Sandwich catalyst is the sandwich of sandwich-like, including γ Al2O3Basalis, positioned at γ Al2O3Ni nanoparticle layers on basalis, and the inertia Al on Ni nanoparticle layers2O3Film.Described Al2O3/Ni/Al2O3Sandwich catalyst is used for CH4‑CO2In reforming reaction.Compared with prior art, the present invention utilizes internal layer Al2O3Carrier and outer layer Al2O3Film is protected and stabilizes Ni nanometer examples well, prevents its sintering of reuniting, so as to suppress the carbon distribution in course of reaction and poisoning etc., catalyst is shown high thermal stability, while has high activity, in CH4‑CO2Reforming reaction and other high temperature heat catalysises have a good application prospect.

Description

High heat stability alundum (Al2O3)/nickel/alundum (Al2O3) sandwich catalyst and its system Preparation Method and application
Technical field
The present invention relates to a kind of catalyst material and preparation method thereof, more particularly, to a kind of high heat stability Al2O3/Ni/ Al2O3Sandwich catalyst and preparation method and application.
Background technology
In recent years, demand for energy is big and elevated height, and most of energy come from fossil fuel, thus produce a large amount of CO2Discharge, does not only result in greenhouse effects, and cause the significant wastage of resource.CH4-CO2Reforming reaction can be by CO2With CH4 It is converted into H2/ CO ratios it is relatively low (<1) synthesis gas, can not only solve environmental problem, moreover it is possible to realize pollutant resources.
W metal is in CH4-CO2Catalytic activity in reforming reaction is and cheap close to noble metal, is more suitable for industry Using.But Ni catalyst easy in inactivation, main cause one is that active sites are reunited, because CH4-CO2Reforming reaction is the endothermic reaction, is needed High temperature is wanted to improve efficiency, so reaction temperature, all more than 700 DEG C, the heat endurance of catalyst is the prerequisite bar of industrial applications Part；Second, carbon distribution problem, because reaction temperature is high, easily occurs CO2Disproportionated reaction and CH4Cracking reaction, cause surface area Carbon.Therefore, prepare high activity and the catalyst of high thermal stability is particularly critical.
Chinese patent CN106807387A discloses a kind of double work(for absorption enhancement hydrogen production by bio-oil steam reforming Energy catalyst and preparation method thereof, the active component of the catalyst is Ni, auxiliary agent Co, CeO2、MgO、K2At least one of O, carry Body is ZrO2Or Al2O3With CaO compound；In the catalyst active component account for 5wt%~20wt%, auxiliary agent account for 1wt~ 15wt%, CaO account for 10wt%~60wt%.Above-mentioned catalyst is not suitable for CH4-CO2In reforming reaction, and its activity is steady with heat It is qualitative poor.
The content of the invention
It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide a kind of high heat stability Al2O3/ Ni/Al2O3Sandwich catalyst and preparation method and application.
The purpose of the present invention can be achieved through the following technical solutions：
A kind of high heat stability Al2O3/Ni/Al2O3Sandwich catalyst, is the sandwich of sandwich-like, including γ- Al2O3Basalis, positioned at γ-Al2O3Ni nanoparticle layers on basalis, and the inertia on Ni nanoparticle layers Al2O3Film.
Due to substrate γ-Al2O3With high-specific surface area, Ni nano-particles can be with high dispersive, so being lived with high catalysis Property.Meanwhile plate inertia Al on high dispersive Ni nano-particles2O3Film, form a kind of sandwich of sandwich-like, make Ni nano-particles can also keep stable under 800 DEG C of reaction temperature, and 400h non-inactivations are used continuously.
Described inertia Al2O3The number of plies of film is 1-100 layers, preferably 40-80 layers.
Described high heat stability Al2O3/Ni/Al2O3The preparation method of sandwich catalyst, comprises the following steps：
1) Ni salt is loaded on the alumina support by infusion process, prepares Ni/Al2O3Loaded catalyst；
2) aluminum oxide film is deposited in Ni/Al by the atomic deposition precipitation method (ALD)2O3On loaded catalyst, obtain Al2O3/Ni/Al2O3Sandwich catalyst.
Inertia Al is controlled by modulation number of deposition cycles2O3The number of plies of film, the present invention in obtained Al2O3/Ni/ Al2O3Inertia Al in sandwich catalyst2O3The number of plies of film is 1-100 layers, preferably 40-80 layers.
Step 1) prepares Ni/Al2O3The specific method of loaded catalyst is as follows：
Ni saline solutions are immersed in γ-Al2O3On carrier stand 8-24 hours, 80-100 DEG C drying after, then with 2-5 DEG C/ Min heating rate rises to 800-900 DEG C, and keeps 3-4h, prepares Ni/Al2O3Loaded catalyst.
Described Ni salt includes NiCl2·6H2O and Ni (NO3)2·6H2O。
Described Ni salt and γ-Al2O3The molal weight ratio of carrier is 0.6~0.7mmol:1g, preferably 0.681mmol: 1g, now, prepare the Ni/Al that Ni contents are 4wt%2O3Loaded catalyst, it is named as 4NiAl.
Step 2) prepares Al2O3/Ni/Al2O3The specific method of sandwich catalyst is as follows：
Using trimethyl aluminium and water as reaction source, substrate uses K9 glass and JGSl quartz glass, is precipitated by atomic deposition Method, in Ni/Al2O3Loaded catalyst surface deposition 1-100 layers Al2O3Film, Al is made2O3/Ni/Al2O3Sandwich is catalyzed Agent.
In step 2), the condition of atomic deposition precipitation is：Depositing temperature is set in 200 DEG C, and reaction chamber operating pressure is kept 40Pa。
Al of the present invention2O3/Ni/Al2O3Sandwich catalyst is used for CH4-CO2In reforming reaction, have high living Property and catalytic stability it is high, have wide practical use.
Compared with prior art, present invention atomic layer deposition method is in Ni/Al2O3The surface of loaded catalyst is formed not The Al of stack pile2O3Film, obtain sandwich catalyst, internal layer Al2O3Carrier and outer layer Al2O3The good protection of film is simultaneously steady Ni nanometer examples are determined, have prevented its sintering of reuniting, so as to suppress the carbon distribution in course of reaction and poisoning etc., made catalyst display high Heat endurance, while there is high activity, in CH4-CO2Before reforming reaction and other high temperature heat catalysises have good application Scape.By the Al of different-thickness2O3The sandwich catalyst of film is used for CH4-CO2Reforming reaction, shown under 800 DEG C of high temperature High thermal stability, stable reaction can be made to run 400h, CH4And CO2Conversion ratio more than 90%, and H2Exist with CO selectivity More than 99%, CO/H2Value 1 or so.Different ALD layer numbers have a great influence to reaction stability, and film is thicker, and stability is got over It is good, but thickness is too high causes catalytic activity to decline.
Brief description of the drawings
Fig. 1 is the transmission electron microscope pattern of the gained 4NiAl-40ALD catalyst of embodiment 2.
Fig. 2 is the transmission electron microscope pattern of the gained 4NiAl-80ALD catalyst of embodiment 3.
Fig. 3 is the temperature programmed reduction spectrum of support type and sandwich catalyst.
Fig. 4 is the x-ray photoelectron power spectrum of support type and sandwich catalyst.
Fig. 5 is the CH of support type and sandwich catalyst4-CO2Reforming reaction expression activitiy.
Fig. 6 is the CH of support type and sandwich catalyst4-CO2Reforming reaction stability compares.
Fig. 7 is the thermogravimetric analysis spectrum after support type and sandwich catalyst reaction.
Fig. 8 is the transmission electron microscope pattern before 4NiAl catalyst reactions.
Fig. 9 is 4NiAl catalyst reactions 10h transmission electron microscope pattern.
Figure 10 is the transmission electron microscope pattern before 4NiAl-40ALD catalyst reactions.
Figure 11 is the transmission electron microscope pattern after 4NiAl-40ALD catalyst reactions 70h.
Figure 12 is the transmission electron microscope pattern before 4NiAl-80ALD catalyst reactions.
Figure 13 is the transmission electron microscope pattern after 4NiAl-80ALD catalyst reactions 400h.
Embodiment
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.
Embodiment 1
0.169g NiCl will be contained2·6H2The O aqueous solution is immersed in 1.0g γ-Al2O3Stood overnight on carrier, in baking oven Dried at interior 100 DEG C, then 800 DEG C are risen to 2 DEG C/min heating rate, and keep 4h, prepare Ni/Al2O3Supported catalyst Agent, it is named as 4NiAl.
Embodiment 2
Using trimethyl aluminium (TMA) and water as reaction source, depositing temperature is set in 200 DEG C, and reaction chamber operating pressure keeps 0.3Substrate uses a diameter of 30mm, and thickness is 2mm K9 glass and JGSl quartz glass.On this condition, in the gained of embodiment 1 Ni/Al2O3Loaded catalyst surface deposits 40 layers of Al2O3Film, 40-Al is made2O3/Ni/Al2O3Sandwich catalyst, life Entitled 4NiAl-40ALD catalyst.
Embodiment 3
Using trimethyl aluminium (TMA) and water as reaction source, depositing temperature is set in 200 DEG C, and reaction chamber operating pressure keeps 0.3Substrate uses a diameter of 30mm, and thickness is 2mm K9 glass and JGSl quartz glass.On this condition, in the institute of embodiment 1 Obtain Ni/Al2O3Loaded catalyst surface deposits 80 layers of Al2O3Film, 80-Al is made2O3/Ni/Al2O3Sandwich catalyst, It is named as 4NiAl-80ALD catalyst.
From Fig. 1,2, bar-shaped γ-Al2O3Carrier surface covers one layer of Al2O3Film, 4NiAl-40ALD catalyst The Al of middle surface covering2O3Film thickness about 4nm, and the Al of 4NiAl-80ALD catalyst surfaces covering2O3Film thickness is about For 8nm.
It can be seen by Fig. 3 TPR collection of illustrative plates, NiO reduction peak moves to high-temperature region in 4NiAl-80ALD, because table Face covers Al2O3After film, the temperature that NiO is experienced can be less than detection temperature, and not cover Al2O3During film, the temperature experienced Degree is identical with detection temperature.Fig. 4 XPS collection of illustrative plates also illustrates that surface covers Al simultaneously2O3After film, cause Ni in 4NiAl-40ALD Peak is also weaker than 4NiAl, and Ni peaks are wholly absent in 4NiAl-80ALD.
Embodiment 4
CH4-CO2Thermal reforming reaction experiment：
Before reaction, first by embodiment 2,3 gained catalyst respectively in 100mL/min H2In with 2 DEG C/min speed liter Temperature is to reduction temperature, constant temperature reduction 1h, then gas is switched into N2, in N2Reaction temperature is risen to 2 DEG C/min speed in atmosphere Degree, reaction temperature=800 DEG C.It is CH to introduce proportioning4:CO2:N2=1:1:1 unstripped gas, gas flow are measured by mass flow Amount and control, GHSV=600LgM -1·h-1.Enter reactor after the preheated device preheating of reacting gas, reaction end gas is water cooled After solidifying, gas-liquid separator separates analysis is sampled with Agilent-7890B type gas-chromatographies.Chromatographic condition is：TCD is detected Device, TDX-01 carbon molecular sieve packed columns, using temperature programming, heating rate 20K/min, initial temperature 323K, final temperature 373K, keep 10min。
The calculating of each component uses area normalization method, calculation formula：
In formula：Ai- peak area；fi- correction factor.
According to product analysis result, the conversion ratio for calculating methane and carbon dioxide is as follows：
From Fig. 5,6 activity data, the Ni catalyst initial reaction activity prepared by three kinds is similar, but heat endurance It is widely different.4NiAl-80ALD is after 400h is reacted, and conversion ratio does not have significant change, and 4NiAl-40ALD is in reaction 20h Activity keeps constant, but reacts 60h again, CH4And CO2Conversion ratio have dropped about 60%, without Al2O3Film covering Just there occurs obvious inactivation in reaction 10h by 4NiAl.
From Fig. 7 and table 1, the carbon deposition rate of three kinds of catalyst differs greatly, depositing Al2O3The number of plies is more, carbon distribution speed Rate is smaller, illustrates catalyst surface depositing Al2O3Film can effectively improve the anti-carbon deposition ability of catalyst.
The carbon deposition rate of the support type of table 1 and sandwich catalyst compares
Can more intuitively it be found by Fig. 8-13, after 10h is reacted, obvious reunion occurs 4NiAl catalyst for Ni particles, and has product Carbon produces.4NiAl-40ALD catalyst is also there occurs similar phenomenon after 70h is reacted, and 4NiAl-80ALD catalyst is reacting In 400h, Ni particles are basically unchanged.Can be it has further been observed, plating Al in catalyst surface from TEM shape appearance figures2O3Film can have Effect improves heat endurance.
Embodiment 5
A kind of high heat stability Al2O3/Ni/Al2O3Sandwich catalyst, is the sandwich of sandwich-like, including γ- Al2O3Basalis, positioned at γ-Al2O3Ni nanoparticle layers on basalis, and the inertia on Ni nanoparticle layers Al2O3Film.In the present embodiment, inertia Al2O3The number of plies of film is 40 layers.
High heat stability Al2O3/Ni/Al2O3The preparation method of sandwich catalyst, comprises the following steps：
Step 1) prepares Ni/Al2O3Loaded catalyst：
By Ni salt NiCl2·6H2O and Ni (NO3)2·6H2The O aqueous solution is immersed in γ-Al2O38 hours are stood on carrier, 80 After DEG C drying, then with 2 DEG C/min heating rate 800 DEG C are risen to, and keep 4h, prepare Ni/Al2O3Loaded catalyst, its In, Ni salt and γ-Al2O3The molal weight ratio of carrier is 0.6mmol:1g.
Step 2) prepares Al2O3/Ni/Al2O3Sandwich catalyst：
Using trimethyl aluminium and water as reaction source, substrate uses a diameter of 30mm, the K9 glass and JGSl quartz that thickness is 2mm Glass, the condition of atomic deposition precipitation are：Depositing temperature is set in 200 DEG C, and reaction chamber operating pressure keeps 40Pa, passes through atom Deposition-precipitation method, inertia Al is controlled by modulation number of deposition cycles2O3The number of plies of film, in Ni/Al2O3Supported catalyst Agent surface deposits 40 layers of Al2O3Film, Al is made2O3/Ni/Al2O3Sandwich catalyst.
Al in the present embodiment2O3/Ni/Al2O3Sandwich catalyst is used for CH4-CO2In reforming reaction, there is high activity And catalytic stability is high, has wide practical use.
Embodiment 6
A kind of high heat stability Al2O3/Ni/Al2O3Sandwich catalyst, is the sandwich of sandwich-like, including γ- Al2O3Basalis, positioned at γ-Al2O3Ni nanoparticle layers on basalis, and the inertia on Ni nanoparticle layers Al2O3Film.In the present embodiment, inertia Al2O3The number of plies of film is 80 layers.
High heat stability Al2O3/Ni/Al2O3The preparation method of sandwich catalyst, comprises the following steps：
Step 1) prepares Ni/Al2O3Loaded catalyst：
By Ni salt NiCl2·6H2O and Ni (NO3)2·6H2The O aqueous solution is immersed in γ-Al2O312 hours are stood on carrier, After 90 DEG C of drying, then with 3 DEG C/min heating rate 840 DEG C are risen to, and keep 3.5h, prepare Ni/Al2O3Supported catalyst Agent, wherein, Ni salt and γ-Al2O3The molal weight ratio of carrier is 0.7mmol:1g.
Step 2) prepares Al2O3/Ni/Al2O3Sandwich catalyst：
Using trimethyl aluminium and water as reaction source, substrate uses a diameter of 30mm, the K9 glass and JGSl quartz that thickness is 2mm Glass, the condition of atomic deposition precipitation are：Depositing temperature is set in 200 DEG C, and reaction chamber operating pressure keeps 40Pa, passes through atom Deposition-precipitation method, inertia Al is controlled by modulation number of deposition cycles2O3The number of plies of film, in Ni/Al2O3Supported catalyst Agent surface deposits 80 layers of Al2O3Film, Al is made2O3/Ni/Al2O3Sandwich catalyst.
Al in the present embodiment2O3/Ni/Al2O3Sandwich catalyst is used for CH4-CO2In reforming reaction, there is high activity And catalytic stability is high, has wide practical use.
Embodiment 7
A kind of high heat stability Al2O3/Ni/Al2O3Sandwich catalyst, is the sandwich of sandwich-like, including γ- Al2O3Basalis, positioned at γ-Al2O3Ni nanoparticle layers on basalis, and the inertia on Ni nanoparticle layers Al2O3Film.In the present embodiment, inertia Al2O3The number of plies of film is 100 layers.
High heat stability Al2O3/Ni/Al2O3The preparation method of sandwich catalyst, comprises the following steps：
Step 1) prepares Ni/Al2O3Loaded catalyst：
By Ni salt NiCl2·6H2O and Ni (NO3)2·6H2The O aqueous solution is immersed in γ-Al2O318 hours are stood on carrier, After 95 DEG C of drying, then with 4 DEG C/min heating rate 870 DEG C are risen to, and keep 3.5h, prepare Ni/Al2O3Supported catalyst Agent, wherein, Ni salt and γ-Al2O3The molal weight ratio of carrier is 0.6mmol:1g.
Step 2) prepares Al2O3/Ni/Al2O3Sandwich catalyst：
Using trimethyl aluminium and water as reaction source, substrate uses a diameter of 30mm, the K9 glass and JGSl quartz that thickness is 2mm Glass, the condition of atomic deposition precipitation are：Depositing temperature is set in 200 DEG C, and reaction chamber operating pressure keeps 40Pa, passes through atom Deposition-precipitation method, inertia Al is controlled by modulation number of deposition cycles2O3The number of plies of film, in Ni/Al2O3Supported catalyst Agent surface deposits 100 layers of Al2O3Film, Al is made2O3/Ni/Al2O3Sandwich catalyst.
Al in the present embodiment2O3/Ni/Al2O3Sandwich catalyst is used for CH4-CO2In reforming reaction, there is high activity And catalytic stability is high, has wide practical use.
Embodiment 8
A kind of high heat stability Al2O3/Ni/Al2O3Sandwich catalyst, is the sandwich of sandwich-like, including γ- Al2O3Basalis, positioned at γ-Al2O3Ni nanoparticle layers on basalis, and the inertia on Ni nanoparticle layers Al2O3Film.In the present embodiment, inertia Al2O3The number of plies of film is 60 layers.
High heat stability Al2O3/Ni/Al2O3The preparation method of sandwich catalyst, comprises the following steps：
Step 1) prepares Ni/Al2O3Loaded catalyst：
By Ni salt NiCl2·6H2O and Ni (NO3)2·6H2The O aqueous solution is immersed in γ-Al2O324 hours are stood on carrier ,- After 100 DEG C of drying, then with 5 DEG C/min heating rate 900 DEG C are risen to, and keep 3h, prepare Ni/Al2O3Supported catalyst Agent, wherein, Ni salt and γ-Al2O3The molal weight ratio of carrier is 0.7mmol:1g.
Step 2) prepares Al2O3/Ni/Al2O3Sandwich catalyst：
Using trimethyl aluminium and water as reaction source, substrate uses a diameter of 30mm, the K9 glass and JGSl quartz that thickness is 2mm Glass, the condition of atomic deposition precipitation are：Depositing temperature is set in 200 DEG C, and reaction chamber operating pressure keeps 40Pa, passes through atom Deposition-precipitation method, inertia Al is controlled by modulation number of deposition cycles2O3The number of plies of film, in Ni/Al2O3Supported catalyst Agent surface deposits 60 layers of Al2O3Film, Al is made2O3/Ni/Al2O3Sandwich catalyst.
Al in the present embodiment2O3/Ni/Al2O3Sandwich catalyst is used for CH4-CO2In reforming reaction, there is high activity And catalytic stability is high, has wide practical use.
The above-mentioned description to embodiment is understood that for ease of those skilled in the art and using invention. Person skilled in the art obviously can easily make various modifications to these embodiments, and described herein general Principle is applied in other embodiment without by performing creative labour.Therefore, the invention is not restricted to above-described embodiment, ability Field technique personnel do not depart from improvement that scope made and modification all should be the present invention's according to the announcement of the present invention Within protection domain.

Claims (10)

  1. A kind of 1. high heat stability Al2O3/Ni/Al2O3Sandwich catalyst, it is characterised in that it is the sandwich of sandwich-like, Including γ-Al2O3Basalis, positioned at γ-Al2O3Ni nanoparticle layers on basalis, and on Ni nanoparticle layers Inertia Al2O3Film.
  2. 2. high heat stability Al according to claim 12O3/Ni/Al2O3Sandwich catalyst, it is characterised in that described Inertia Al2O3The number of plies of film is 1-100 layers, preferably 40-80 layers.
  3. 3. high heat stability Al as claimed in claim 12O3/Ni/Al2O3The preparation method of sandwich catalyst, its feature exist In comprising the following steps：
    1) Ni salt is loaded on the alumina support by infusion process, prepares Ni/Al2O3Loaded catalyst；
    2) aluminum oxide film is deposited in Ni/Al by the atomic deposition precipitation method2O3On loaded catalyst, Al is obtained2O3/Ni/ Al2O3Sandwich catalyst.
  4. 4. high heat stability Al according to claim 32O3/Ni/Al2O3The preparation method of sandwich catalyst, its feature It is, inertia Al is controlled by modulation number of deposition cycles2O3The number of plies of film.
  5. 5. high heat stability Al according to claim 32O3/Ni/Al2O3The preparation method of sandwich catalyst, its feature It is, step 1) prepares Ni/Al2O3The specific method of loaded catalyst is as follows：
    Ni saline solutions are immersed in γ-Al2O38-24 hours are stood on carrier, after 80-100 DEG C of drying, then with 2-5 DEG C/min Heating rate rise to 800-900 DEG C, and keep 3-4h, prepare Ni/Al2O3Loaded catalyst.
  6. 6. high heat stability Al according to claim 52O3/Ni/Al2O3The preparation method of sandwich catalyst, its feature It is, described Ni salt includes NiCl2·6H2O and Ni (NO3)2·6H2O。
  7. 7. high heat stability Al according to claim 52O3/Ni/Al2O3The preparation method of sandwich catalyst, its feature It is, described Ni salt and γ-Al2O3The molal weight ratio of carrier is 0.6~0.7mmol:1g.
  8. 8. high heat stability Al according to claim 32O3/Ni/Al2O3The preparation method of sandwich catalyst, its feature It is, step 2) prepares Al2O3/Ni/Al2O3The specific method of sandwich catalyst is as follows：
    Using trimethyl aluminium and water as reaction source, substrate uses K9 glass and JGSl quartz glass, by the atomic deposition precipitation method, Ni/Al2O3Loaded catalyst surface deposition 1-100 layers Al2O3Film, Al is made2O3/Ni/Al2O3Sandwich catalyst.
  9. 9. high heat stability Al according to claim 82O3/Ni/Al2O3The preparation method of sandwich catalyst, its feature It is, in step 2), the condition of atomic deposition precipitation is：Depositing temperature is set in 200 DEG C, and reaction chamber operating pressure is kept 40Pa。
  10. 10. high heat stability Al as claimed in claim 12O3/Ni/Al2O3The application of sandwich catalyst, it is characterised in that Described Al2O3/Ni/Al2O3Sandwich catalyst is used for CH4-CO2In reforming reaction.
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