CN109225229A - A kind of Ni@SiO2The preparation method of catalyst with core-casing structure and its application in methane reforming with carbon dioxide - Google Patents
A kind of Ni@SiO2The preparation method of catalyst with core-casing structure and its application in methane reforming with carbon dioxide Download PDFInfo
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 46
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 239000003054 catalyst Substances 0.000 title claims abstract description 32
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 22
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000002407 reforming Methods 0.000 title claims abstract description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 64
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000002245 particle Substances 0.000 claims abstract description 13
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 5
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 5
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 5
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 5
- 239000000377 silicon dioxide Substances 0.000 claims abstract 5
- 239000000243 solution Substances 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 25
- KDXKERNSBIXSRK-YFKPBYRVSA-N L-lysine Chemical compound NCCCC[C@H](N)C(O)=O KDXKERNSBIXSRK-YFKPBYRVSA-N 0.000 claims description 22
- 239000004472 Lysine Substances 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 12
- 235000019766 L-Lysine Nutrition 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 9
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 9
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical group [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 9
- -1 polyoxyethylene Polymers 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical group CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 5
- 238000011084 recovery Methods 0.000 claims description 5
- 239000004094 surface-active agent Substances 0.000 claims description 5
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 3
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 claims description 2
- 230000003301 hydrolyzing effect Effects 0.000 claims description 2
- 235000018977 lysine Nutrition 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000002105 nanoparticle Substances 0.000 claims description 2
- 238000000643 oven drying Methods 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 2
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 15
- 238000011161 development Methods 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 239000010953 base metal Substances 0.000 abstract description 2
- 238000005516 engineering process Methods 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- 239000007789 gas Substances 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 239000000839 emulsion Substances 0.000 description 6
- 239000006210 lotion Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 238000007789 sealing Methods 0.000 description 6
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- KDRIEERWEFJUSB-UHFFFAOYSA-N carbon dioxide;methane Chemical compound C.O=C=O KDRIEERWEFJUSB-UHFFFAOYSA-N 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- FDCJDKXCCYFOCV-UHFFFAOYSA-N 1-hexadecoxyhexadecane Chemical compound CCCCCCCCCCCCCCCCOCCCCCCCCCCCCCCCC FDCJDKXCCYFOCV-UHFFFAOYSA-N 0.000 description 3
- 241001104043 Syringa Species 0.000 description 3
- 235000004338 Syringa vulgaris Nutrition 0.000 description 3
- 239000003345 natural gas Substances 0.000 description 3
- VIKNJXKGJWUCNN-XGXHKTLJSA-N norethisterone Chemical compound O=C1CC[C@@H]2[C@H]3CC[C@](C)([C@](CC4)(O)C#C)[C@@H]4[C@@H]3CCC2=C1 VIKNJXKGJWUCNN-XGXHKTLJSA-N 0.000 description 3
- 238000011017 operating method Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000006057 reforming reaction Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 241000607479 Yersinia pestis Species 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 150000001722 carbon compounds Chemical class 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- VDGJOQCBCPGFFD-UHFFFAOYSA-N oxygen(2-) silicon(4+) titanium(4+) Chemical compound [Si+4].[O-2].[O-2].[Ti+4] VDGJOQCBCPGFFD-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
Classifications
-
- 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
-
- B01J35/23—
-
- B01J35/393—
-
- B01J35/398—
-
- B01J35/51—
-
- 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
-
- 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 belongs to usings energy source and field of environmental technology, specifically provide a kind of Ni@SiO2The preparation method of catalyst with core-casing structure and its application in methane reforming with carbon dioxide.The catalyst is using nano nickel particles as kernel, and silica spheres are the catalyst with core-casing structure of shell.Wherein the mass percent of nickel is 3-6wt%, and for nickel particle having a size of 1-4nm, the mass percent of silica is 97-94wt%, and silica spheres diameter dimension is 25-35nm.It can achieve 88% applied to the preferable activity of performance, 750 DEG C of methane conversions in the reaction of methane and carbon dioxide dry reforming, carbon dioxide conversion can achieve 93%, and catalytic activity, which is able to maintain, to be stablized 2500 minutes or more.Catalyst cost is greatly lowered using base metal nickel as activated centre in catalyst, and operation is simple, there is good development prospect in the industrial production.
Description
Technical field
The invention belongs to usings energy source and field of environmental technology, are related to a kind of preparation of Ni@SiO2 catalyst with core-casing structure
Method and its application in methane reforming with carbon dioxide.
Technical background
Methane is the main component of natural gas and shale gas, and compared to fossil energies such as coal and petroleum, source is more extensive,
Global reserves are bigger and burning more clean and environmental protection.As the natural gas resources such as seabed combustible ice are largely excavated successively, this kind of money
Source is paid close attention to and is paid attention to by people, and Devoting Major Efforts To Developing has become countries in the world improvement environment using this resource and maintains sustainable
The optimal selection of development.However the stability of methane thermodynamically makes its activation and conversion still remain bigger difficulty,
The conversion of methane and using project by it is internationally recognized for be 21st century world energy sources and organic development key problem.Dioxy
Change the final product that carbon burns as carbon compound, and is difficult to the small molecule activated.In recent years, carbon dioxide gas discharge amount by
Year is incremented by, and destroys the gas balance in atmosphere, and serious greenhouse effects, tellurian pest and disease damage is caused to increase, on sea level
Liter, Marine Storm Genesis increase, and seriously threaten the sustainable and healthy development of the mankind.By carbon dioxide and methane while catalytic cracking
Standby synthesis gas, can not only Reasonable Utilization of Natural Gas resource, while significantly reducing the discharge of greenhouse gases, can also directly utilize
The liquid fuels such as petroleum and diesel oil are prepared through Fischer-Tropsch synthesis.Therefore methane carbon dioxide reformation catalysis is reacted to current energy
One of source and the hot topic of environmental catalysis area research.
Ni catalyst is to study widest methane reforming with carbon dioxide catalyst at present, it is with higher activity and
Selectivity.Compared to noble metal catalyst Ru, Pt, Pd is studied before, the sources such as Ir are more extensive, and price is cheaper, more suitable
Industrial required mass production is answered, but inevitably forms carbon deposit during the reaction, carbon deposit blocking catalysis when serious
Agent duct covers surface metal active sites, leads to catalyst inactivation.So the Ni catalyst with good prospects for commercial application is not
It requires nothing more than methanation activity height and stability is good, while should have preferable coking resistivity.And methane carbon dioxide reformation is anti-
It should be a high-temperature catalytic reaction, higher reaction temperature will lead to active component particles sintering, this is also to reduce catalyst performance
It can a big key reason.Therefore carbon distribution deposition and Ni particle Sintering Problem become studies the difficult point that must be solved at present.
Summary of the invention
Aiming at the problems existing in the prior art, the one kind that is designed to provide of invention is applied to methane carbon dioxide reformation
The Ni@SiO of reaction2The preparation method of catalyst with core-casing structure.The catalyst is using superfine nano particle nickel as core, titanium dioxide
Silicon is the spherical structure catalyst of shell, and wherein the mass percent of nickel particle is 3-6wt%, particle size 1-4nm；Two
Siliconoxide mass percentage is 97-94wt%, particle size 25-35nm.
Ni@SiO of the invention2The preparation method of catalyst with core-casing structure, comprising the following steps:
(1) nickel source solution, surfactant and hexamethylene are uniformly mixed, obtain mixed solution a；
(2) the resulting mixed solution a of step (1) is put into water-bath, addition hydrazine hydrate progress first time stirring, then by
Silicon source is added dropwise in drop, carries out second and stirs, obtains mixed solution b；
(3) the resulting mixed solution b of step (2) is slowly dropped into L-lysine solution, is placed in water-bath and hydrolyzes, controlled
Stirring rate processed, and kept for certain time, product after must hydrolyzing, oven drying is then placed in Muffle furnace and carries out under air
Calcining, obtains grey powder；
(4) the calcined grey powder of step (3) is obtained into product by hydrogen reducing.
In step (1), nickel source is nickel nitrate solution, concentration 0.5-1mol/L；The volume of hexamethylene and nickel nitrate solution
Than for 15:0.5；The surfactant is polyoxyethylene cetyl ether, and surface is living in n=10,15 or 20, mixed solution a
Property agent concentration 0.1-0.5mol/L.
In step (2), hydrazine hydrate mass percentage concentration is 80%, and additional amount adds with nickel nitrate in nickel source in step (1)
The molar ratio for entering amount is 20:1；Silicon source is tetraethyl orthosilicate, and the molar ratio of additional amount and hydrazine hydrate additional amount is 94:100.
In step (2), constant 45-55 DEG C of water-bath thermostatic control, first time mixing time is 20-30min, is stirred for the second time
Mixing the time is 40-60min, and dropwise addition process remains a constant speed.
In step (3), the PH of lysine solution is 9-10, the molar ratio of silicon source additional amount in additional amount and step (2)
When being added dropwise to mixed solution b in L-lysine solution for 0.02:1., control drop rate is 0.1-0.5mL/min, water-bath
Temperature is 60 DEG C, and in 500-1000r/min, keeping constant revolving speed mixing time is 3-4h for stirring rate control.
In step (3), 90-110 DEG C of baking oven dry 12-24h is used after mixture is taken out, Muffle furnace is at 500-700 DEG C
2h is calcined, heating rate is 1-2 centigrade per minute.
In step (4), the grey powder restores at 750 DEG C by hydrogen, recovery time 30min；Heating rate
For 1-5 DEG C/min.
By Ni@SiO prepared by the present invention2Catalyst with core-casing structure is for the purposes in methane reforming with carbon dioxide.
The invention has the benefit that
(1) by Ni@SiO prepared by the present invention2Catalyst with core-casing structure, using base metal nickel as activated centre, significantly
Catalyst cost is reduced, and operation is simple, there is good development prospect in the industrial production.
(2) catalyst prepared by the present invention is applied to show preferable activity in methane reforming with carbon dioxide, 750
DEG C methane conversion can achieve 88%, and carbon dioxide conversion can achieve 93%, and catalytic activity is able to maintain stabilization
2500min or more.
Detailed description of the invention
A-c is according to the transmission electron microscope picture (TEM) of gained sample after the operation of example 1-3 operating procedure in Fig. 1, and d is to implement
TEM figure under the 50nm of example 1.
Fig. 2 is the size distribution plot of nickel particle in gained sample after being operated according to example 1-3 operating procedure.
Fig. 3 is to be operated to obtain sample Ni SiO2-500, Ni SiO2-600Ni SiO2- according to example 1-3 embodiment
700, the temperature performance figure applied to methane reforming with carbon dioxide.
Fig. 4 is that gained sample Ni SiO2-500, Ni SiO2-600, Ni SiO2- are operated according to example 1-3 embodiment
700 are applied to the stability test in methane reforming with carbon dioxide under 750 degree of hot conditions.
Specific embodiment
With reference to the accompanying drawing, specific embodiment of the present invention operation is further described.Example implementation is with this hair
It is carried out under the premise of bright, gives specific embodiment and detailed operating procedure.
Embodiment 1:
A. 0.005 mole of polyoxyethylene (n=20) cetyl ether is mixed with 15 milliliters of hexamethylenes, in 40 DEG C of water-baths
Middle uniform stirring forms white emulsion.
B. the nickel nitrate solution that 0.5 milliliter of concentration is 1 mole every liter is added dropwise into white emulsion, stirs evenly, lotion is in
Light green color.
C. water bath temperature is promoted to 50 degree, 0.6 milli of hydrazine hydrate that concentration is percent 80 is slowly added dropwise into solution
It rises.Sealing stirring 20 minutes.Form lilac lotion.
B. it keeps temperature-resistant, 2.1 milliliters of tetraethyl orthosilicates, sealing stirring 40 minutes is slowly added dropwise into solution.
D. 0.001 mole of L-lysine is dissolved in 139 milliliters of water, 26.2 milliliters of L-lysine solution is taken to be put into 60 degree
In water-bath, step b acquired solution is slowly added dropwise dropwise into whole wherein.Controlling time for adding is 30 minutes, and stirring is equal
Even, rotor speed 700r/min then keeps constant temperature perseverance revolving speed to stir 4 hours.
E. solution is put into 100 degree of baking ovens dry 24 hours and is taken out.
F. sample is put into Muffle furnace, 500 degree of 2 hours of calcining, heating rate is 1 degree every point.
G. gained sample is restored in hydrogen nitrogen mixed gas, hydrogen flow rate 5ml/min, nitrogen flow rate 20ml/min.
Reduction temperature is 750 degree, the recovery time 30 minutes.Gained sample is denoted as Ni@SiO2-500.
Embodiment 2:
A. 0.005 mole of polyoxyethylene (n=20) cetyl ether is mixed with 15 milliliters of hexamethylenes, in 40 degree of water-baths
Middle uniform stirring forms white emulsion.
B. the nickel nitrate solution that 0.5mL concentration is 1 mole every liter is added dropwise into white emulsion, stirs evenly, lotion is in shallow
Green.
C. water bath temperature is promoted to 50 degree, 0.6 milli of hydrazine hydrate that concentration is percent 80 is slowly added dropwise into solution
It rises.Sealing stirring 20 minutes.Form lilac lotion.
D. it keeps temperature-resistant, 2.1 milliliters of tetraethyl orthosilicates, sealing stirring 40 minutes is slowly added dropwise into solution.
E. 0.001 mole of L-lysine is dissolved in 139 milliliters of water, 26.2 milliliters of L-lysine solution is taken to be put into 60 degree
In water-bath, step b acquired solution is slowly added dropwise dropwise into whole wherein.Controlling time for adding is 30 minutes, and stirring is equal
Even, rotor speed is 700 rpms, then constant temperature perseverance revolving speed is kept to stir 4 hours.
F. solution is put into 100 degree of baking ovens dry 24 hours and is taken out.
G. sample is put into Muffle furnace and is roasted, maturing temperature is 600 degree, 2 hours of duration, heating rate
Per minute for 1 degree.
H. gained sample is restored in hydrogen nitrogen respectively, hydrogen flow rate is 5 milliliters per minute, and nitrogen flow rate is 20 millis
Liter Per Minute.Reduction temperature is 750 degree, the recovery time 30 minutes.Gained sample is denoted as Ni@SiO2-600
Embodiment 3:
A. 0.005 mole of polyoxyethylene (n=20) cetyl ether is mixed with 15 milliliters of hexamethylenes, in 40 degree of water-baths
Middle uniform stirring forms white emulsion.
B. the nickel nitrate solution that 0.5 milliliter of concentration is 1 mole every liter is added dropwise into white emulsion, stirs evenly, lotion is in
Light green color.
C. water bath temperature is promoted to 50 degree, 0.6 milli of hydrazine hydrate that concentration is percent 80 is slowly added dropwise into solution
It rises.Sealing stirring 20 minutes.Form lilac lotion.
D. it holds temperature-resistant, is slowly added dropwise 2.1 milliliters of tetraethyl orthosilicates into solution, sealing stirring 40 minutes.
E. 0.001 mole of L-lysine is dissolved in 139 milliliters of water, 26.2 milliliters of L-lysine solution is taken to be put into 60 degree
In water-bath, step b acquired solution is slowly added dropwise dropwise into whole wherein.Controlling time for adding is 30 minutes, and stirring is equal
Even, rotor speed is 700 rpms, then constant temperature perseverance revolving speed is kept to stir 4 hours.
F. solution is put into 100 degree of baking ovens dry 24 hours and is taken out.
G. sample is put into Muffle furnace and is roasted, maturing temperature is 700 degree, 2 hours of duration, heating rate
Per minute for 1 degree.
H. gained sample is restored in hydrogen nitrogen respectively, hydrogen flow rate is 5 milliliters per minute, and nitrogen flow rate is 20 millis
Liter Per Minute reduction temperature is 750 degree, the recovery time 30 minutes.Gained sample is denoted as Ni@SiO2-700
The available similar core-shell structure of Ni@SiO2 catalyst of difference maturing temperature as shown in Figure 1.
Nickel particle size is in 1-4nm in Ni@SiO2 catalyst with core-casing structure as shown in Figure 2.The maturing temperature of sample is higher,
The size of active component nickel particle is bigger.
Embodiment 4:
Temperature performance applied to CO 2 reforming reaction is studied
With in atmospheric fixed bed microreactor (internal diameter 8mm), it is put into 50mg catalyst, leads to unstripped gas CH4, CO2,
(CH4/CO2=1).CH4, CO2 flow velocity are 15ml/min, and air speed is 36000ml/ (g h).Unstripped gas uses gas by fixed bed
Phase chromatography analyzes synthesis gas after reaction through row.Under 600 degree, 650 degree, 700 degree, 750 degree, respectively by gained in example 1-3
Three samples detect each component gas content after reaction respectively, and then evaluate under different maturing temperatures catalyst in carbon dioxide weight
Temperature performance in whole reaction.
As shown in Figure 3, the sample Ni@SiO2-600 under different calcination temperatures is at different temperatures to carbon dioxide methane
Show higher conversion ratio.In contrast, sample Ni@SiO2-500, Ni@SiO2-700 performance is poor.
Embodiment 5:
Stability test applied to carbon dioxide methane reforming reaction
With in atmospheric fixed bed microreactor (internal diameter 8mm), it is put into 50mg catalyst, leads to unstripped gas CH4, CO2,
(CH4/CO2=1).CH4, CO2 flow velocity are 15ml/min, and air speed is 36000ml/ (g h).Unstripped gas uses gas by fixed bed
Phase chromatography analyzes synthesis gas after reaction.Gained sample in example 1 is reacted 2500 minutes under 750 degree respectively, is tracked
Each component situation of change in product anyway is detected, determines whether the catalyst keeps stable in catalytic performance at longer time.
As shown in figure 4, sample Ni@SiO2-700 stability is best, Ni@SiO2-600, Ni@SiO2-500 degree takes second place.
Above embodiments are only the several embodiments described in the present invention, and description is more specific in detail, but cannot not
Therefore understands that limiting range for patent of the invention.It should be pointed out that for those of ordinary skill in the art, not
Under the premise of being detached from present inventive concept, various modifications and improvements can be made, belongs to the scope of the present invention, therefore this hair
Bright scope of patent protection should be determined by the appended claims.
Claims (9)
1. a kind of Ni@SiO2Catalyst with core-casing structure, which is characterized in that using superfine nano particle nickel as core, silica is shell
The spherical structure catalyst of layer, wherein the mass percent of nickel particle is 3-6wt%, particle size 1-4nm；Silica
Mass percent is 97-94wt%, particle size 25-35nm.
2. Ni@SiO according to claim 12The preparation method of catalyst with core-casing structure, which is characterized in that including following step
It is rapid:
(1) nickel source solution, surfactant and hexamethylene are uniformly mixed, obtain mixed solution a；
(2) the resulting mixed solution a of step (1) is put into water-bath, hydrazine hydrate is added and carries out first time stirring, then drips dropwise
Add silicon source, carries out second and stir, obtain mixed solution b；
(3) the resulting mixed solution b of step (2) is slowly dropped into L-lysine solution, is placed in water-bath and hydrolyzes, control is stirred
Rate to be mixed, and is kept for certain time, product after must hydrolyzing, oven drying is then placed in Muffle furnace and is calcined under air,
Obtain grey powder；
(4) the calcined grey powder of step (3) is obtained into product by hydrogen reducing.
3. according to preparation method described in right 2, which is characterized in that in step (1), nickel source is nickel nitrate solution, and concentration is
0.5-1mol/L；The volume ratio of hexamethylene and nickel nitrate solution is 15:0.5；The surfactant is polyoxyethylene cetyl
Base ether, surfactant concentration 0.1-0.5mol/L in n=10,15 or 20, mixed solution a.
4. preparation method according to claim 2, which is characterized in that in step (2), hydrazine hydrate mass percentage concentration is
80%, the molar ratio of nickel nitrate additional amount is 20:1 in nickel source in additional amount and step (1)；Silicon source is tetraethyl orthosilicate,
The molar ratio of its additional amount and hydrazine hydrate additional amount is 94:100.
5. according to preparation method described in right 2, which is characterized in that in step (2), constant 45-55 DEG C of water-bath thermostatic control,
First time mixing time is 20-30min, and second of mixing time is 40-60min, and dropwise addition process remains a constant speed.
6. according to preparation method described in right 2, which is characterized in that in step (3), the PH of lysine solution is 9-10, is added
When the molar ratio for entering silicon source additional amount in amount and step (2) is that mixed solution b is added dropwise in L-lysine solution by 0.02:1.,
Control drop rate is 0.1-0.5mL/min, and water bath temperature is 60 DEG C, and stirring rate control is kept in 500-1000r/min
Constant rotational speed mixing time is 3-4h.
7. according to preparation method described in right 2, which is characterized in that in step (3), baking oven 90- is used after mixture is taken out
110 DEG C of dry 12-24h, for Muffle furnace in 500-700 DEG C of calcining 2h, heating rate is 1-2 centigrade per minute.
8. according to preparation method described in right 2, which is characterized in that in step (4), the grey powder is by hydrogen 750
It is restored at DEG C, recovery time 30min；Heating rate is 1-5 DEG C/min.
9. by Ni@SiO described in claim 12Catalyst with core-casing structure is for the purposes in methane reforming with carbon dioxide.
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