CN114904528A - Ordered mesoporous nickel-based magnesium gallium spinel methanation catalyst and preparation method and application thereof - Google Patents
Ordered mesoporous nickel-based magnesium gallium spinel methanation catalyst and preparation method and application thereof Download PDFInfo
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 104
- 239000003054 catalyst Substances 0.000 title claims abstract description 69
- 239000011777 magnesium Substances 0.000 title claims abstract description 45
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 title claims abstract description 43
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 229910052733 gallium Inorganic materials 0.000 title claims abstract description 43
- 229910052749 magnesium Inorganic materials 0.000 title claims abstract description 43
- 239000011029 spinel Substances 0.000 title claims abstract description 42
- 229910052596 spinel Inorganic materials 0.000 title claims abstract description 42
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 229910017857 MgGa Inorganic materials 0.000 claims abstract description 47
- 229910052751 metal Inorganic materials 0.000 claims abstract description 27
- 239000002184 metal Substances 0.000 claims abstract description 27
- 238000011068 loading method Methods 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 22
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 239000011148 porous material Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 10
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 10
- 159000000003 magnesium salts Chemical class 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 7
- 230000032683 aging Effects 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 5
- 238000001704 evaporation Methods 0.000 claims description 4
- 239000002736 nonionic surfactant Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 230000008020 evaporation Effects 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 239000006185 dispersion Substances 0.000 abstract description 5
- 239000002245 particle Substances 0.000 abstract description 5
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 238000005245 sintering Methods 0.000 abstract description 4
- 238000005054 agglomeration Methods 0.000 abstract description 3
- 230000002776 aggregation Effects 0.000 abstract description 3
- 230000002779 inactivation Effects 0.000 abstract description 3
- 150000001722 carbon compounds Chemical class 0.000 abstract description 2
- 239000007787 solid Substances 0.000 description 19
- 239000010453 quartz Substances 0.000 description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 16
- 239000004094 surface-active agent Substances 0.000 description 15
- 239000000243 solution Substances 0.000 description 14
- 239000007789 gas Substances 0.000 description 11
- 239000011521 glass Substances 0.000 description 8
- 238000000227 grinding Methods 0.000 description 8
- 238000005303 weighing Methods 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 7
- 238000001816 cooling Methods 0.000 description 6
- CHPZKNULDCNCBW-UHFFFAOYSA-N gallium nitrate Chemical compound [Ga+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CHPZKNULDCNCBW-UHFFFAOYSA-N 0.000 description 6
- 229910052698 phosphorus Inorganic materials 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- 239000003814 drug Substances 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 239000011949 solid catalyst Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000004506 ultrasonic cleaning Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 229940044658 gallium nitrate Drugs 0.000 description 3
- 239000003345 natural gas Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- -1 F127 Chemical compound 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000000802 evaporation-induced self-assembly Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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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
- B01J23/005—Spinels
-
- 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/825—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with gallium, indium or thallium
-
- B01J35/615—
-
- B01J35/647—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
- C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
- C07C1/0425—Catalysts; their physical properties
- C07C1/043—Catalysts; their physical properties characterised by the composition
- C07C1/0435—Catalysts; their physical properties characterised by the composition containing a metal of group 8 or a compound thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
- C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
- C07C1/0425—Catalysts; their physical properties
- C07C1/0445—Preparation; Activation
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
- C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
- C10L3/08—Production of synthetic natural gas
-
- 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 an ordered mesoporous nickel-based magnesium gallium spinel methanation catalyst, a preparation method and application thereof 2 O 4 The carrier is metal Ni, and the loading amount of the metal Ni is 10-30 wt%. First MgGa 2 O 4 The catalyst has the characteristics of high temperature resistance and small thermal expansion coefficient, has strong binding force with metal, can play excellent thermal stability when being used as a carrier in a high-temperature catalyst bed layer, effectively avoids the sintering of the catalyst, and keeps good catalytic performance. Second, MgGa in the invention 2 O 4 The catalyst is an ordered mesoporous structure and has the characteristic of large specific surface area, and the ordered mesoporous structure can protect active species, play a role in limiting the domain, inhibit the agglomeration of nickel particles and the growth of carbon species and avoid the inactivation of the catalyst; and MgGa 2 O 4 The larger specific surface area is beneficial to dispersing active metal, reducing the particle size of nickel, improving the dispersion degree of nickel and further improving the catalytic activity.
Description
Technical Field
The invention relates to an ordered mesoporous nickel-based magnesium gallium spinel methanation catalyst and a preparation method and application thereof, belonging to the technical field of preparation and application of a catalyst for preparing synthetic natural gas from coal.
Background
The coal-based natural gas technology is an effective way for improving clean utilization of coal and can meet the demand of people on rapid growth of natural gas. The methanation process is a core process of the coal-to-natural gas technology, and the design and synthesis of the methanation catalyst are concerned as key points of methanation. It is known that the methanation reaction of CO is a strong exothermic reaction, and the higher temperature of a catalyst bed layer easily causes the sintering and carbon deposition of the catalyst, thereby leading to the deactivation of the catalyst. Therefore, the development of the catalyst with excellent low-temperature activity and high-temperature stability has important significance and broad prospect.
In the industry, a methanation process usually takes a supported metal type catalyst as a main component, a Ni-based catalyst is low in price and excellent in activity and can be widely applied, and meanwhile, the selection of a carrier plays a crucial role in reaction. Previous researches show that the dispersion degree of the active metal is an important factor influencing the activity of the catalyst, and the high dispersion degree can increase the area of the active metal and is beneficial to improving the catalytic activity. The carrier with the ordered mesoporous structure is an effective means for realizing high dispersion degree of active components, and the domain limitation of the carrier can effectively inhibit the agglomeration of metal and prevent the metal from being stripped by carbon deposition, thereby avoiding the sintering and carbon deposition of the catalyst and improving the stability of the catalyst. Therefore, the ordered mesoporous material has attracted much attention in the field of catalysis due to its large specific surface area and regular pore structure. Chinese patent CN110339856A discloses a mesoporous SiO 2 Molecular sieve KIT-6 is used as a carrier, and metal Ni is used as an active component to prepare a catalyst for CO methanation reaction, SiO 2 The mesoporous structure of the molecular sieve plays a role of limiting the domain and provides a larger specific surface area, which is beneficial to improving the dispersity of nickel particles and further improving the catalytic activityWhile SiO 2 The surface is inert, chemical property is inactive, and anchoring of metal particles is not facilitated, so that the nickel-based SiO 2 Catalysts have certain limitations.
Disclosure of Invention
The technical problem to be solved by the invention is to provide the ordered mesoporous nickel-based magnesium gallium spinel methanation catalyst which is strong in metal-carrier interaction force, high in dispersity and excellent in methanation high-temperature stability, and the preparation method and the application thereof.
In order to solve the technical problems, the catalyst of the invention comprises: uses metal Ni as active component, ordered mesoporous MgGa 2 O 4 Is used as a carrier, and the loading amount of metal Ni is 10-30 wt%.
The ordered mesoporous MgGa 2 O 4 The specific surface area of (A) is 200 to 500 m 2 The pore diameter is 4-10 nm.
The Ni/MgGa 2 O 4 The specific surface area of the catalyst is 260-450 m 2 (ii)/g, the pore diameter is 3.5-8 nm.
The preparation method comprises the following steps:
(1) preparation of ordered mesoporous MgGa 2 O 4
Dissolving non-ionic surfactant in solvent to obtain solution, and adding Ga (NO) 3 ) 3 •9H 2 Reacting O and magnesium salt to obtain transparent viscous liquid, aging, drying, and roasting in inert gas atmosphere to obtain ordered mesoporous MgGa 2 O 4 ；
(2) Preparation of Ni/MgGa 2 O 4 Catalyst and process for preparing same
Mixing Ni (NO) 3 ) 2 •6H 2 Dissolving O in deionized water, and adding MgGa obtained in the step (1) 2 O 4 Stirring, ultrasonic treating, evaporating in water bath to dryness in N 2 Roasting in atmosphere to obtain Ni/MgGa 2 O 4 A catalyst.
The nonionic surfactant is at least one of P123 and F127, and can be removed in the roasting process of the carrier. In the preparation process of the carrier, a surfactant is added, and an ordered mesoporous structure is formed in an evaporation-induced self-assembly mode.
The solvent in the step (1) is at least one of deionized water, methanol, ethanol and acetone.
The inert gas in the step (1) comprises at least one of argon and helium.
In the step (1), the step (c),
the aging temperature is 30-50 ℃, and the aging time is 100-140 h;
the drying temperature is 60-100 ℃, and the drying time is 8-12 h;
the flow rate of inert gas in the roasting atmosphere is 60-100 mL/min, the roasting temperature is 500-800 ℃, and the roasting time is 4-6 h;
in the step (2), the step (c),
the temperature of water bath evaporation is 60-90 ℃;
roasting atmosphere N 2 The flow rate of (A) is 60-100 mL/min; the roasting temperature is 400-600 ℃, and the roasting time is 1.5-3 h.
The magnesium salt in the step (1) is magnesium chloride or magnesium nitrate.
The molar ratio of the gallium to the magnesium in the step (1) is 1: 2.
The ordered mesoporous MgGa obtained in the step (1) 2 O 4 Namely ordered mesoporous magnesium gallium spinel.
The Ni/MgGa obtained in the step (2) 2 O 4 The catalyst is ordered mesoporous nickel-base Mg-Ga spinel catalyst.
The catalyst obtained in the step (2) has different metal Ni loading amounts according to the types of the surfactant and the magnesium salt adopted in the preparation process and the final product, and comprises the following structural forms: 10Ni/MgGa 2 O 4 -P-Cl，10Ni/MgGa 2 O 4 -F-Cl，10Ni/MgGa 2 O 4 -P-N，30Ni/MgGa 2 O 4 P-Cl, wherein, the number represents the metal loading amount, F, P represents the adopted surfactant, and Cl and N represent the adopted magnesium salt varieties.
The invention also provides application of the ordered mesoporous nickel-based magnesium gallium spinel methanation catalyst in CO methanation reaction.
The application of the ordered mesoporous nickel-based magnesium gallium spinel methanation catalyst in CO methanation reaction has the following reaction conditions: the temperature is 200-600 ℃, the pressure is 0.1-3.0 MPa, and the mass space velocity is 10000-60000 mL h −1 g −1 。
Compared with the prior art, the invention has obvious advancement and uses MgGa with high temperature resistance and small thermal expansion coefficient 2 O 4 The catalyst is synthesized by loading metal Ni on a carrier, has the characteristic of strong metal-carrier interaction force, plays an excellent thermal stability performance in a high-temperature catalyst bed layer, effectively avoids the sintering of the catalyst, and maintains good catalytic performance.
Preparation method of the invention, MgGa 2 O 4 The catalyst is an ordered mesoporous structure and has the characteristic of large specific surface area, and the ordered mesoporous structure can protect active species, play a role in limiting the domain, inhibit the agglomeration of nickel particles and the growth of carbon species and avoid the inactivation of the catalyst; and MgGa 2 O 4 The larger specific surface area is beneficial to dispersing active metal, reducing the particle size of nickel, improving the dispersion degree of nickel and further improving the catalytic activity.
The preparation method adopts a soft template method to prepare the ordered mesoporous MgGa 2 O 4 Simple process and the obtained MgGa 2 O 4 The material is a white solid, and an electron microscope picture (figure 1) shows that the material has a pore channel structure which is regularly arranged; the purity of the product is high, and XRD results (figure 2) show that the purity is 2 theta = 18.5 o ，30.5 o ，35.9 o ，37.6 o ，43.7 o ，54.2 o ，57.8 o ，63.5 o ，72.1 o ，75.2 o ，76.2 o ，80.2 o All diffraction peaks are ordered mesoporous MgGa 2 O 4 The characteristic peak of (1) and no other diffraction peak are generated, so that the structure is stable; in addition, at T =600 ℃, P =1 MPa, WHSV =15000 mL h −1 g −1 Under the condition of (1), for 10Ni/MgGa 2 O 4 The life test of the-P-Cl catalyst was carried out for 100 hours, and the reaction results are shown in Table 1, which shows that the catalyst hardly developsThe raw inactivation shows that the catalyst has excellent performance, and is an ideal method for rapidly preparing the methanation catalyst with high stability.
Drawings
The invention is further illustrated with reference to the following figures and examples:
FIG. 1 is a process for synthesizing ordered mesoporous MgGa 2 O 4 Transmission electron microscope images of (a);
FIG. 2 is a diagram of synthesis of ordered mesoporous MgGa 2 O 4 XRD pattern of (a).
Detailed Description
In order to make the objects, technical solutions and effects of the present invention more clear, the technical solutions of the present invention will be described in detail below. It should be apparent that the described embodiments are only some embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the examples given herein without any inventive step, are within the scope of the present invention.
The chemical substance materials used in the invention are as follows: gallium nitrate, magnesium chloride, magnesium nitrate, nickel nitrate, P123, F127, methanol, ethanol, acetone, deionized water, nitrogen, argon, carbon monoxide and hydrogen.
Gallium nitrate: ga (NO) 3 ) 3 ·9H 2 O 100.00 g±0.01 g
Magnesium chloride: MgCl 6 ·6H 2 O 100.00 g ±0.01 g
Magnesium nitrate: mg (NO) 3 ) 2 •6H 2 O 100.00 g ±0.01 g
Nickel nitrate: ni (NO) 3 ) 2 ·6H 2 O 100.00g±0.01 g
P123： 100.00 g±0.01 g
F127： 100.00 g±0.01 g
Methanol: CH (CH) 3 OH 1000.00 ml±0.01 ml
Ethanol: c 2 H 5 OH 1000.00 ml±0.01 ml
Acetone: CH (CH) 3 COCH 3 1000.00 ml±0.01 ml
Deionized water: h 2 O 1000.00 ml±0.01 ml
Nitrogen gas: n is a radical of 2 10000cm 3 ±100 cm 3
Argon gas: ar 10000cm 3 ±100 cm 3
Carbon monoxide: CO 10000cm 3 ±100 cm 3
Hydrogen gas: h 2 10000cm 3 ±100 cm 3
Selecting the chemical substance materials: the chemical material required by the preparation is selected and subjected to quality purity control:
gallium nitrate: solid state 98.5%
Magnesium chloride: solid state 98.5%
Magnesium nitrate: solid state 98.5%
Nickel nitrate: solid state 98.5%
P123: solid state 98.5%
F127: solid state 98.5%
Methanol: 99.5 percent of liquid
Ethanol: 99.5 percent of liquid
Acetone: 99.5 percent of liquid
Deionized water: 99.5 percent of liquid
Nitrogen gas: 99.9% of gaseous gas
Argon gas: 99.9% of gaseous gas
Carbon monoxide: 99.9% of gaseous gas
Hydrogen gas: 99.9% of gaseous gas.
Example 1
A preparation method of an ordered mesoporous nickel-based magnesium gallium spinel methanation catalyst comprises the following steps:
(1) and preparing the ordered mesoporous magnesium gallium spinel
Weighing 3.0000 g +/-0.0001 g of surfactant P123, dissolving in 30 g of ethanol, and stirring in a 35 ℃ water bath until the surfactant P123 is dissolved;
5.1148 g. + -. 0.0001 g Ga (NO) were weighed out 3 ) 3 ·9H 2 O and corresponding molar amount of MgCl 6 ·6H 2 Adding O into the solution, and continuously stirring to obtain a transparent viscous liquid;
the resulting viscous liquid was poured into a glass dish and aged in an oven at 40 ℃ for 120 h. Then transferring the glass dish to an oven at 80 ℃ for drying for 10 hours to obtain a honeycomb precursor;
taking out a sample by using a medicine spoon, grinding, putting the sample into a quartz boat, putting the quartz boat under a thermocouple of a furnace chamber of a tubular furnace, introducing Ar at the flow rate of 60 mL/min, heating the temperature from room temperature to 700 ℃ at the speed of 2 ℃/min, keeping the temperature for 5 h, cooling, taking out the sample after the temperature is reduced to room temperature to obtain white ordered mesoporous magnesium gallium spinel, collecting the white ordered mesoporous magnesium gallium spinel by using a sample bag, and storing the white ordered mesoporous magnesium gallium spinel in a dryer.
The obtained ordered mesoporous MgGa 2 O 4 Has a specific surface area of 500 m 2 G, pore diameter is 10 nm.
(2) Preparing nickel-based magnesium gallium spinel catalyst
1.096 + -0.001 g of Ni (NO) was weighed 3 ) 2 ·6H 2 Putting the O solid into a 100 mL beaker, adding 50 mL deionized water, and stirring until the O solid is completely dissolved into a nickel nitrate water solution;
weighing 2.0000 g +/-0.0001 g MgGa 2 O 4 Adding into the above solution, stirring for 30 min, transferring into ultrasonic cleaning machine, ultrasonic treating for 30 min, transferring the beaker into water bath, heating the water bath to 80 deg.C, and stirring until all liquid is completely evaporated to obtain light blue solid;
grinding the obtained sample, transferring the sample into a quartz boat, placing the quartz boat at the center of the furnace chamber of the tube furnace, and introducing N at the flow rate of 80 mL/min 2 Raising the temperature from room temperature to 550 ℃ at the speed of 2 ℃/min, keeping the temperature for 2 hours, then reducing the temperature, closing the gas after the temperature is reduced to the room temperature, taking out the sample, and obtaining the gray solid catalyst 10Ni/MgGa 2 O 4 P-Cl (10 represents the loading of metal Ni of 10 wt%, P represents P123 as a surfactant, Cl represents MgCl as a magnesium salt 6 ·6H 2 O）。
The ordered mesoporous nickel-based magnesium gallium spinel methanation catalyst obtained by the method has the metal Ni loading amount of 10 wt% and the specific surface area of 450 m 2 G, pore diameter of 8 nm.
Example 2
(1) And preparing the ordered mesoporous magnesium gallium spinel
Weighing 3.0000 g +/-0.0001 g of surfactant F127, dissolving in 30 g of methanol, and stirring in a 35 ℃ water bath until the surfactant F127 is dissolved;
5.1148 g. + -. 0.0001 g Ga (NO) were weighed out 3 ) 3 ·9H 2 O and corresponding molar amount of MgCl 6 ·6H 2 Adding O into the solution, and continuously stirring to obtain a transparent viscous liquid;
the obtained viscous liquid was poured into a glass dish and aged in an oven at 30 ℃ for 140 h. Then transferring the glass dish to a 60 ℃ oven for drying for 12 h to obtain a honeycomb precursor;
taking out a sample by using a medicine spoon, grinding, putting the sample into a quartz boat, putting the quartz boat under a thermocouple of a furnace chamber of a tubular furnace, introducing Ar at the flow rate of 80 mL/min, setting the temperature to rise from room temperature to 500 ℃ at the speed of 2 ℃/min, keeping the temperature for 6 h, cooling, taking out after the temperature is reduced to room temperature, thus obtaining white ordered mesoporous magnesium gallium spinel, collecting the white ordered mesoporous magnesium gallium spinel by using a sample bag, and storing the white ordered mesoporous magnesium gallium spinel in a dryer.
The obtained ordered mesoporous MgGa 2 O 4 Has a specific surface area of 325 m 2 (ii)/g, pore diameter is 5.3 nm.
(2) Preparing nickel-based magnesium gallium spinel catalyst
1.096 + -0.001 g of Ni (NO) was weighed 3 ) 2 ·6H 2 Putting the O solid into a 100 mL beaker, adding 50 mL deionized water, and stirring until the O solid is completely dissolved into a nickel nitrate water solution;
weighing 2.0000 g +/-0.0001 g MgGa 2 O 4 Adding into the above solution, stirring for 30 min, transferring into ultrasonic cleaning machine, ultrasonic treating for 30 min, transferring the beaker into water bath, heating the water bath to 60 deg.C, and stirring until all liquid is completely evaporated to obtain light blue solid;
grinding the obtained sample, transferring the sample into a quartz boat, placing the quartz boat at the center of the furnace chamber of the tube furnace, and introducing N at the flow rate of 80 mL/min 2 Heating from room temperature to 600 ℃ at the speed of 2 ℃/min, keeping the temperature for 1.5 h, cooling, closing the gas after the temperature is reduced to the room temperature, taking out the sample to obtain the gray solid catalyst 10Ni/MgGa 2 O 4 -F-Cl (10 represents the amount of the supported metal Ni of 10 wt%, F represents a surfactant F127, Cl represents a magnesium salt MgCl 6 ·6H 2 O）。
The ordered mesoporous nickel-based magnesium gallium spinel methanation catalyst obtained by the method has the metal Ni loading amount of 10 wt% and the specific surface area of 300 m 2 G, pore diameter of 4.5 nm.
Example 3
(1) And preparing the ordered mesoporous magnesium gallium spinel
Weighing 3.0000 g +/-0.0001 g of surfactant P123, dissolving in 30 g of ethanol, and stirring in a 35 ℃ water bath kettle until the surfactant P123 is dissolved;
5.1148 g. + -. 0.0001 g Ga (NO) were weighed out 3 ) 3 ·9H 2 O and a corresponding molar amount of Mg (NO) 3 ) 2 •6H 2 Adding O into the solution, and continuously stirring to obtain a transparent viscous liquid;
the obtained viscous liquid was poured into a glass dish and aged in an oven at 50 ℃ for 100 hours. Then transferring the glass dish to an oven at 80 ℃ for drying for 10 h to obtain a honeycomb precursor;
taking out a sample by using a medicine spoon, grinding, putting the sample into a quartz boat, placing the quartz boat under a thermocouple in a furnace chamber of a tubular furnace, introducing He at a flow rate of 60 mL/min, setting the temperature to rise from room temperature to 800 ℃ at a speed of 2 ℃/min, keeping the temperature for 4 h, cooling, taking out after the temperature is reduced to room temperature to obtain white ordered mesoporous magnesium gallium spinel, collecting by using a sample bag, and placing in a dryer for storage.
The obtained ordered mesoporous MgGa 2 O 4 Has a specific surface area of 356 m 2 (ii)/g, pore diameter is 5.9 nm.
(2) Preparing nickel-based magnesium gallium spinel catalyst
1.096 + -0.001 g of Ni (NO) was weighed 3 ) 2 ·6H 2 Putting the O solid into a 100 mL beaker, adding 50 mL deionized water, and stirring until the O solid is completely dissolved into a nickel nitrate water solution;
weighing 2.0000 g +/-0.0001 g MgGa 2 O 4 Adding into the above solution, stirring for 30 min, transferring into ultrasonic cleaning machine, ultrasonic treating for 30 min, transferring the beaker into water bath kettle, heating the water bath kettle to 90 deg.C, and stirring until all liquid is completely evaporated to obtain light blue solid;
grinding the obtained sample, transferring the sample into a quartz boat, placing the quartz boat at the center of the furnace chamber of the tube furnace, and introducing N at the flow rate of 100 mL/min 2 Heating from room temperature to 400 ℃ at the speed of 2 ℃/min, keeping the temperature for 3 hours, cooling, closing the gas after the temperature is reduced to the room temperature, taking out the sample, and obtaining the gray solid catalyst 10Ni/MgGa 2 O 4 P-N (10 represents a metal Ni loading of 10 wt%, P represents a surfactant P123, and N represents a magnesium salt Mg (NO) 3 ) 2 •6H 2 O）。
The ordered mesoporous nickel-based magnesium gallium spinel methanation catalyst obtained by the method has the metal Ni loading amount of 10 wt% and the specific surface area of 325 m 2 G, pore diameter is 5.1 nm.
Example 4
(1) And preparing the ordered mesoporous magnesium gallium spinel
Weighing 3.0000 g +/-0.0001 g of surfactant P123, dissolving in 30 g of ethanol, and stirring in a 35 ℃ water bath until the surfactant P123 is dissolved;
5.1148 g. + -. 0.0001 g Ga (NO) were weighed out 3 ) 3 ·9H 2 O and corresponding molar amount of MgCl 6 ·6H 2 Adding O into the solution, and continuously stirring to obtain a transparent viscous liquid;
the resulting viscous liquid was poured into a glass dish and aged in an oven at 40 ℃ for 120 h. Then transferring the glass dish to a drying oven at 100 ℃ for drying for 8 h to obtain a honeycomb precursor;
taking out a sample by using a medicine spoon, grinding, putting the sample into a quartz boat, placing the quartz boat under a thermocouple in a furnace chamber of a tubular furnace, introducing He at a flow rate of 60 mL/min, setting the temperature to rise from room temperature to 600 ℃ at a speed of 2 ℃/min, keeping the temperature for 5 hours, cooling, taking out after the temperature is reduced to room temperature to obtain white ordered mesoporous magnesium gallium spinel, collecting by using a sample bag, and placing in a dryer for storage.
The obtained ordered mesoporous MgGa 2 O 4 Has a specific surface area of 386 m 2 (ii)/g, pore diameter 6.1 nm.
(2) Preparing nickel-based magnesium gallium spinel catalyst
3.288 + -0.001 g of Ni (NO) were weighed 3 ) 2 ·6H 2 Placing the O solid in a 100 mL beaker, adding 50 mL of deionized water, and stirring until the O solid is completely dissolved to form a nickel nitrate aqueous solution;
weighing 2.0000 g +/-0.0001 g MgGa 2 O 4 Adding into the above solution, stirring for 30 min, transferring into ultrasonic cleaning machine, ultrasonic treating for 30 min, transferring the beaker into water bath, heating the water bath to 80 deg.C, and stirring until all liquid is completely evaporated to obtain light blue solid;
grinding the obtained sample, transferring the sample into a quartz boat, placing the quartz boat at the center of the furnace chamber of the tube furnace, and introducing N at the flow rate of 80 mL/min 2 Raising the temperature from room temperature to 550 ℃ at the speed of 2 ℃/min, keeping the temperature for 2 hours, then reducing the temperature, closing the gas after the temperature is reduced to the room temperature, taking out the sample, and obtaining the gray solid catalyst 30Ni/MgGa 2 O 4 P-Cl (30 represents the loading of the metal Ni of 30 wt%, P represents the surfactant P123, Cl represents the magnesium salt MgCl 6 ·6H 2 O）。
The load capacity of metal Ni of the ordered mesoporous nickel-based magnesium gallium spinel methanation catalyst obtained by the method is 30 wt%, and MgGa 2 O 4 Has a specific surface area of 295 m 2 Per g, pore size 4.5 nm.
Example 5
The catalyst prepared in the embodiment 1-4 is applied to a CO methanation reaction, and the specific steps are as follows: putting a proper amount of catalyst into a tabletting mould, placing on a tabletting machine, increasing the pressure to 20 MPa, pressing for 20 min, taking out the pressed sample, crushing and sieving to obtain a 40-60-mesh catalyst; 0.4 g of the pelletized catalyst was weighed and loaded into a reactor for evaluation of the methanation activity of CO. First, H was passed at a rate of 20 ml/min 2 Raising the temperature from room temperature to 550 ℃ at the speed of 2 ℃/min, keeping the temperature for 2 hours for in-situ reduction, then reducing the temperature to the reaction temperature, and switching to H 2 And carrying out CO methanation reaction on the/CO mixed gas. Reaction conditions are as follows: t = 200-600 ℃, P =1 MPa, WHSV =15000 mL h −1 g −1 The reaction results are shown in Table 2.
Claims (12)
1. An ordered mesoporous nickel-based magnesium gallium spinel methanation catalyst is characterized in that: uses metal Ni as active component, ordered mesoporous MgGa 2 O 4 The carrier is metal Ni, and the loading amount of the metal Ni is 10-30 wt%.
2. The ordered mesoporous nickel-based magnesium gallium spinel methanation catalyst of claim 1, characterized in that: the ordered mesoporous MgGa 2 O 4 The specific surface area of (a) is 300-500 m 2 The pore diameter is 4-10 nm.
3. The ordered mesoporous nickel-based magnesium gallium spinel methanation catalyst of claim 1 or 2, characterized in that: the Ni/MgGa 2 O 4 The specific surface area of the methanation catalyst is 260-450 m 2 Per g, pore diameter of 3.5～8 nm。
4. The preparation method of the ordered mesoporous nickel-based magnesium gallium spinel methanation catalyst according to any one of claims 1 to 3, is characterized by comprising the following steps:
(1) preparation of ordered mesoporous MgGa 2 O 4
Dissolving non-ionic surfactant in solvent to obtain solution, and adding Ga (NO) 3 ) 3 •9H 2 Reacting O and magnesium salt to obtain transparent viscous liquid, aging, drying, and roasting in inert gas atmosphere to obtain ordered mesoporous MgGa 2 O 4 ；
(2) Preparation of Ni/MgGa 2 O 4 Catalyst and process for producing the same
Mixing Ni (NO) 3 ) 2 •6H 2 Dissolving O in deionized water, and adding MgGa obtained in the step (1) 2 O 4 Stirring, ultrasonic treating, evaporating in water bath to dryness in N 2 Roasting in atmosphere to obtain Ni/MgGa 2 O 4 A catalyst.
5. The preparation method of the ordered mesoporous nickel-based magnesium gallium spinel methanation catalyst according to claim 4, characterized by comprising the following steps: the nonionic surfactant is at least one of P123 and F127.
6. The preparation method of the ordered mesoporous nickel-based magnesium gallium spinel methanation catalyst according to claim 4, characterized in that: the solvent in the step (1) is at least one of deionized water, methanol, ethanol and acetone.
7. The preparation method of the ordered mesoporous nickel-based magnesium gallium spinel methanation catalyst according to claim 4, characterized in that: the inert gas in the step (1) comprises at least one of argon and helium.
8. The preparation method of the ordered mesoporous nickel-based magnesium gallium spinel methanation catalyst according to claim 4, characterized in that: in the step (1), the raw material is processed,
the aging temperature is 30-50 ℃, and the aging time is 100-140 h;
the drying temperature is 60-100 ℃, and the drying time is 8-12 h;
the flow rate of inert gas in the roasting atmosphere is 60-100 mL/min, the roasting temperature is 500-800 ℃, and the roasting time is 4-6 h;
in the step (2), the step (c),
the temperature of water bath evaporation is 60-90 ℃;
roasting atmosphere N 2 The flow rate of (A) is 60-100 mL/min; the roasting temperature is 400-600 ℃, and the roasting time is 1.5-3 h.
9. The preparation method of the ordered mesoporous nickel-based magnesium gallium spinel methanation catalyst according to claim 4, characterized in that: the magnesium salt in the step (1) is magnesium chloride or magnesium nitrate.
10. The preparation method of the ordered mesoporous nickel-based magnesium gallium spinel methanation catalyst according to claim 4, characterized in that: the molar ratio of the gallium to the magnesium in the step (1) is 1: 2.
11. Use of the ordered mesoporous nickel-based magnesium gallium spinel methanation catalyst of any one of claims 1 to 3 in a CO methanation reaction.
12. The application of the ordered mesoporous nickel-based magnesium gallium spinel methanation catalyst of claim 11 in CO methanation reaction is characterized in that: the temperature is 200-600 ℃, the pressure is 0.1-3.0 MPa, and the mass space velocity is 10000-60000 mL h −1 g −1 。
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| CN111229235A (en) * | 2020-03-09 | 2020-06-05 | 上海交通大学 | NiO/MgAl2O4Catalyst, preparation method and application thereof |
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| CN106881086A (en) * | 2015-12-12 | 2017-06-23 | 中国科学院大连化学物理研究所 | The preparation of gallate spinel supported nanometer gold catalyst and catalyst and application |
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