WO2018175827A1 - Method for preparing nickle/aluminum spinel-coated aluminum oxide - Google Patents
Method for preparing nickle/aluminum spinel-coated aluminum oxide Download PDFInfo
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- WO2018175827A1 WO2018175827A1 PCT/US2018/023919 US2018023919W WO2018175827A1 WO 2018175827 A1 WO2018175827 A1 WO 2018175827A1 US 2018023919 W US2018023919 W US 2018023919W WO 2018175827 A1 WO2018175827 A1 WO 2018175827A1
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- powder
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- ai2o3
- ai2o3 powder
- nickel
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- 238000000034 method Methods 0.000 title claims abstract description 54
- 229910052596 spinel Inorganic materials 0.000 title abstract description 18
- 239000011029 spinel Substances 0.000 title abstract description 18
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 title abstract description 15
- 229910052782 aluminium Inorganic materials 0.000 title abstract description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title abstract description 8
- 239000000843 powder Substances 0.000 claims abstract description 119
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 64
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 29
- 238000005245 sintering Methods 0.000 claims abstract description 25
- 239000011248 coating agent Substances 0.000 claims abstract description 18
- 238000000576 coating method Methods 0.000 claims abstract description 18
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 32
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 claims description 23
- 239000002245 particle Substances 0.000 claims description 18
- 239000012736 aqueous medium Substances 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 9
- 238000007873 sieving Methods 0.000 claims description 9
- 238000000643 oven drying Methods 0.000 claims description 8
- 238000004513 sizing Methods 0.000 claims description 4
- 238000002955 isolation Methods 0.000 claims description 2
- 239000002609 medium Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 26
- 239000000243 solution Substances 0.000 abstract description 21
- 239000002131 composite material Substances 0.000 abstract description 9
- 239000002052 molecular layer Substances 0.000 abstract description 3
- 239000007864 aqueous solution Substances 0.000 abstract description 2
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 18
- 229910052593 corundum Inorganic materials 0.000 description 16
- 239000007791 liquid phase Substances 0.000 description 13
- 238000007792 addition Methods 0.000 description 9
- 239000010431 corundum Substances 0.000 description 6
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 6
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000005119 centrifugation Methods 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 229910000480 nickel oxide Inorganic materials 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 3
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000001099 ammonium carbonate Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000005049 combustion synthesis Methods 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- -1 Nickel aluminate Chemical class 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000002902 bimodal effect Effects 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052566 spinel group Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
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- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/628—Coating the powders or the macroscopic reinforcing agents
- C04B35/62802—Powder coating materials
- C04B35/62805—Oxide ceramics
- C04B35/62813—Alumina or aluminates
-
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- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
- C01F7/021—After-treatment of oxides or hydroxides
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
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- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
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- C04B2235/763—Spinel structure AB2O4
Definitions
- This application is directed to methods for preparing nickel/aluminum spinel- coated aluminum oxide, the materials obtained by the methods, and uses thereof.
- a spinel-type composite metal oxide is a complex oxide formed by combining two or more metal oxides, and has a chemical formula which can be written as AB2O4 or ABCO4.
- AB204-type spinels have cubic crystal systems, with a face-centered cubic lattice, wherein O 2 is face-centered cubic close packed (CPP).
- Nickel aluminate is a spinel material containing a transition metal ion (Ni). It is a narrow-bandgap semiconductor, and has advantages such as good visible light absorption properties, catalytic properties, and resistance to acids and alkalis.
- AI2O4 ceramic-metal composite materials have very high conductivity, and may be used in the aluminum electrolysis industry as inert anode materials.
- a known method for synthesizing NiAl204-coated alumina is ball milling NiO powder and AI2O3 powder, followed by oven-drying and heat treatment.
- the powder obtained by that method is a mixed powder of N1AI2O4 and NiO in a non-stoichiometric ratio, the components being (Nii -x Al204-x'xNiO).
- the value of x is gradually reduced by raising the preheating temperature, so as to obtain the corresponding N1AI2O4 powder.
- the control of preheating temperature in the method is not precise, and the rate of temperature increase has a significant influence on the product, so the purity of the AI2O4 obtained is low.
- the preparation of the nano structured NiAl204-coated AI2O3 has high energy consumption, and relies on complex steps. Moreover, in the case of the liquid- phase combustion synthesis method, component control is difficult, and purity is low. There accordingly remains a need in the art for new methods for the preparation of nanostructured NiAl 2 04-coated AI2O3.
- a method for preparing a NiAhC ⁇ -coated AI2O3 powder comprising: contacting an uncoated AI2O3 powder with N1SO4 and H4HCO3 in an aqueous medium to provide an AI2O3 powder coated with a composition comprising nickel; and sintering the AI2O3 powder coated with a composition comprising nickel at a temperature and for a time effective to provide the Ni AhC ⁇ -coated AI2O3 powder.
- a method for preparing a nano-NiAhC ⁇ -coated AI2O3 powder comprises:
- AI2O3 powder is dispersed in deionized water, and using nickel sulfate and ammonium bicarbonate as starting materials, the surface of the AI2O3 powder is uniformly coated with NiC03'2Ni(OH)2'2H20 by a liquid-phase reaction method, with the nano-layer thickness being regulated by controlling the nickel sulfate content, and after centrifugal separation, the powder is oven-dried and sieved, wherein the reaction equation is as follows:
- the mixed powder is sintered, wherein during sintering,
- N1CO3 2Ni(OH)2 2H2O is decomposed into nano nickel oxide, then nickel oxide reacts with AI2O3 to produce nano AI2O4, the inverse equations being as follows:
- the sintered powder is sieved to obtain nano-Ni AhC ⁇ -coated AI2O3 powder.
- Another embodiment is a NiAhC ⁇ -coated AI2O3 made by the above-described methods.
- FIG. 1 is an X-ray diffraction (XRD) spectrum of Example 1 wherein (a) is the original AI2O3 powder and (b) is NiAb04-coated powder.
- FIG. 2 is a scanning electron microscope (SEM) image showing the overall morphology of the NiAhC ⁇ -coated AI2O3 powder obtained in Example 1.
- FIG. 3 is an SEM image showing the local morphology of the NiAhC ⁇ -coated AI2O3 powder obtained in Example 1, and shows that AI2O4 is uniformly distributed on the surface of the AI2O3.
- the technical solution includes dispersing an AI2O3 powder in an aqueous medium; and contacting the dispersed AI2O3 powder with nickel sulfate and ammonium bicarbonate to provide a surface coating comprising nickel carbonate.
- the thickness of the surface coating can be controlled by adjusting the nickel sulfate content.
- the coated AI2O3 powder is then separated from the liquid phase, dried, and optionally sized.
- the dried, optionally sized powder is then sintered at a temperature effective to provide to provide a nanosized N1AI2O4 coating on the AI2O3 powder.
- the NiAkC ⁇ -coated AI2O3 powder can then be optionally sized again.
- AI2O3 powder, nickel sulfate (N1SO4), and ammonium bicarbonate (NH4HCO3) are contacted in an aqueous medium.
- the AI2O3 powder comprises particles that can be of any shape, for example spherical, plate-shaped, irregular, or a combination comprising at least one of the foregoing. In an embodiment the powder is approximately spherical.
- the particle size can be monomodal, bimodal, or higher, or a distribution of sizes. The average largest particle size can vary widely, for example from 10 nanometers (nm) to 1 millimeter (mm), or from 50 nm to 500 micrometers ( ⁇ ), or from 100 nm to 100 ⁇ .
- the average largest particle size is from 500 nm to 50 ⁇ , or from 750 nm to 1.25 ⁇ .
- the AI2O3 powder can have an average largest particle size of 0.8 to 1.2 ⁇ , or 0.9 to 1.1 ⁇ , or 1 ⁇ .
- the aqueous medium comprises water, preferably deionized water.
- the aqueous medium can contain only water, or can further comprise a water-miscible organic solvent, for example ethanol, isopropanol, dimethylsulfoxide, dimethyl formamide, and the like.
- the water-miscible organic solvent can comprise 1 to 80 volume percent (vol. %) of the total volume of the aqueous solution, for example 2 to 70 vol.%, or 5 to 50 vol.%, or 5 to 40 vol.%, or 10 to 30 vol.% of the total volume of the aqueous medium.
- the liquid-phase reaction system is maintained for a period of time and at a temperature effective to provide a coating on the AI2O3 powder.
- the liquid- phase reaction system can be stirred for 30 minutes to 10 hours, or 1 hour to 5 hours.
- the temperature of the liquid-phase reaction system can be maintained at 10 to 50°C, for example at 20 to 25°C. In an embodiment, the temperature is ambient temperature to minimize energy costs.
- Reaction of the starting materials provides a product where the the surface of the AI2O3 powder is uniformly coated with a composition comprising nickel.
- the coating comprises nickel carbonate (N1CO3).
- the composition can further comprise various oxides or hydroxides of nickel, for example nickel hydroxide (2Ni(OH)2).
- the coating composition can comprise
- NiC03'2Ni(OH)2'2H20 formed in a liquid-phase reaction.
- the reaction equation can be as shown in Equation 1.
- the thickness of the layer formed can be regulated by controlling the nickel sulfate content of the liquid-phase reaction system.
- the layer can be a nano-layer having a thickness of 1 to 500 nm, or 2 to 250 nm, or 3 to 100 nm.
- the thickness can be uniform, for example varying by less than 20% on a given particle, or varying by less than 10%.
- the nickel-coated AI2O3 powder can be isolated from the aqueous medium, for example by filtration or or centrifugal separation.
- the nickel-coated AI2O3 powder can be dried, for example in an oven or under a flow of hot air.
- the size ranges of powders after drying can correspond approximately to the size of the starting aluminum powders.
- the nickel-coated AI2O3 powder can have can have an average particle size of less than 300 micrometers, most preferably less than 60 micrometers, or less than 40 micrometers, or less than 30 micrometers, for example 1 to 40 micrometers, or 1 to 30 micrometers.
- the dried nickel-coated AI2O3 powder can then be sieved to isolate particles of more uniform size.
- a variety of sizes or ranges of sizes can be used.
- the particles are sieved to a size of less than 50 micrometers, or less than 35 micrometers, or less than 20 micrometers, for example 1 to 25 micrometers, or 1 to 20 micrometers.
- the nickel-coated AI2O3 powder can then be sintered to provide the NiAl 2 0 4 - coated AI2O3 powder.
- the NiAl 2 0 4 coating thus obtained is nano structured. Without be being bound by theory, it is believed that the
- N1CO3 2Ni(OH)2 2H2O coating is decomposed into nickel oxide as shown in Equation (2); then the nickel oxide reacts with AI2O3 to produce AI2O4, as shown in Equation (3).
- Sintering can be by methods known in the art.
- the nickel-coated AI2O3 powder can be loaded into a corundum crucible and heated at a rate of temperature increase of 5 to 10°C/minute, followed by heating at 1150 to 1350°C for 1 to 3 hours.
- Sintering can be conducted in air or under an inert atmosphere.
- the NiAhC ⁇ -coated AI2O3 powder can be sieved to provide a powder of more uniform particle size.
- the powder can have an average particle size of less than less than 25 micrometers, or less than 15 micrometers, or less than 10 micrometers, for example 1 to 15 micrometers, or 1 to 10 micrometers.
- the present invention provides a method for preparing a nickel-aluminum-spinel-coated aluminum oxide powder material having simple operations and high reproducibility.
- the methods provide a dense and uniform coating of nickel-aluminum- spinel on the surface of the aluminum oxide, with uniform grain sizes.
- the method is safe and reliable, requires less energy, and saves space.
- the rate of temperature increase is high, the sintering temperature is low, the surface is coated uniformly, the reaction time is shortened, and the preparation cost is low.
- the nickel/aluminum-spinel-coated aluminum oxide powder prepared as described herein can be used in a variety of applications, for example as catalytic materials and as high-temperature thermosensitive materials.
- the powder obtained is loaded into a corundum crucible and sintered, causing the N1CO3 2Ni(OH)2 2H2O to decompose to give an NiO-coated AI2O3 powder; NiO then reacts with AI2O3 to obtain nickel-aluminum-spinel; the rate of temperature increase is 5°C/min, the sintering
- the temperature is 1200°C, and the temperature is maintained for 2 h.
- the sintered powder is sieved, to obtain a nickel-aluminum-spinel-coated aluminum oxide composite material.
- FIG. 1 at (a) The XRD spectrum of alumina is shown in FIG. 1 at (a), and the XRD spectrum of the alumina after coating is shown in FIG. 1 at (b).
- FIG. 2 is an SEM image of the powder of Example 1 showing the overall morphology of the NiAkC ⁇ -coated AI2O3 powder obtained in Example 1.
- FIG. 3 is an SEM image showing the local morphology of the NiAkC ⁇ -coated AI2O3 powder obtained in Example 1.
- FIGS. 2 and 3; these show that the NiAl 2 0 4 prepared in Example 1 is uniformly distributed on the surface of the AI2O3.
- AI2O3 powder of average particle size 50 ⁇ is weighed out, and put into 300 ml of deionized water and 1.5 mol/L H4HCO3 solution; an N1SO4 solution is added dropwise while stirring magnetically, wherein the total duration of the dropwise addition and reaction is 2 h, to give a solution with a pH of 7. After the reaction, centrifugation and water- washing are performed, then oven-drying and sieving are performed to obtain an AI2O3 powder coated with N1CO3 2Ni(OH) 2 2H 2 0.
- the powder obtained is loaded into a corundum crucible and sintered, causing the N1CO3 2Ni(OH) 2 2H 2 0 to decompose to give an NiO-coated Al 2 03 powder; NiO then reacts with Al 2 03 to obtain nickel-aluminum-spinel; the rate of temperature increase is 8°C/min, the sintering temperature is 1300°C, and the temperature is maintained for 2 h.
- the sintered powder is sieved, to obtain a nickel- aluminum-spinel-coated aluminum oxide composite material.
- the powder obtained is loaded into a corundum crucible and sintered, causing the N1CO3 2Ni(OH) 2 2H 2 0 to decompose to give an NiO-coated Al 2 03 powder; NiO then reacts with Al 2 03 to obtain nickel-aluminum-spinel; the rate of temperature increase is 5°C/min, the sintering temperature is 1200°C, and the temperature is maintained for 2 h.
- the sintered powder is sieved, to obtain a nickel- aluminum-spinel-coated aluminum oxide composite material.
- the powder obtained is loaded into a corundum crucible and sintered, causing the N1CO3 2Ni(OH) 2 2H 2 0 to decompose to give an NiO-coated Al 2 03 powder; NiO then reacts with Al 2 03 to obtain nickel-aluminum-spinel; the rate of temperature increase is 5°C/min, the sintering temperature is 1300°C, and the temperature is maintained for 2 h.
- the sintered powder is sieved, to obtain a nickel- aluminum-spinel-coated aluminum oxide composite material.
- the temperature is 1250°C, and the temperature is maintained for 2 h.
- the sintered powder is sieved, to obtain a nickel-aluminum-spinel-coated aluminum oxide composite material.
- compositions and methods disclosed herein are further illustrated by the following aspects, which are non-limiting:
- a method for preparing a NiAkC ⁇ -coated AI2O3 powder comprising: contacting an uncoated AI2O3 powder with N1SO4 and H4HCO3 in an aqueous medium to provide an AI2O3 powder coated with a composition comprising nickel; and sintering the AI2O3 powder coated with a composition comprising nickel at a temperature and for a time effective to provide the NiAkC ⁇ -coated AI2O3 powder.
- Aspect 2 The method according to aspect 1, further comprising isolating the AI2O3 powder coated with a composition comprising nickel before sintering.
- Aspect 3 The method according to aspect 2, further comprising sizing the the AI2O3 powder coated with a composition comprising nickel after isolation and before sintering.
- Aspect 4 The method according to any one or more of aspects 1 to 3, further comprising sizing the NiAkC ⁇ -coated AI2O3 powder.
- Aspect 5 The method according to aspect 1, comprising: dispersing the uncoated AI2O3 powder in deionized water; adding NH4HCO3 and N1SO4 to the uncoated AI2O3 powder to provide a coating on the surface of the AI2O3 powder, wherein the coating comprises nickel; separating the nickel-coated AI2O3 powder from the deionized water; oven- drying the separated AI2O3 powder; sieving the dried AI2O3 powder; sintering the sieved AI2O3 powder to provide the NiAhC ⁇ -coated AI2O3 powder; and optionally, sieving the sintered Ni AhC ⁇ -coated AI2O3 powder.
- Aspect 6 The method according to any one or more of aspects 1 to 5, wherein the coating comprises nickel comprises NiC03'2Ni(OH)2'2H20.
- Aspect 7 The method according to any one or more of aspects 1 to 6, wherein the N1AI2O4 coating is nano structured.
- Aspect 8 The method according to any one or more of aspects 1 to 7, wherein the uncoated AI2O3 powder has a particle size of 10 nanometers to 1 millimeter, preferably 1 to 100 ⁇ .
- Aspect 9 The method according to any one or more of aspects 1 to 8, wherein the aqueous medium medium is deionized water or a water/ethanol solution.
- Aspect 10 The method according to any one or more of aspects 1 to 9, comprising combining the uncoated AI2O3 powder and the NH4HCO3; then adding the N1SO4, preferably adding the H4HCO3 dropwise.
- Aspect 11 The method according to any one or more of aspects 1 to 10, wherein the pH of the aqueous medium is 7 to 8.
- Aspect 12 The method according to any one or more of aspects 1 to 11, wherein a rate of temperature increase of sintering is 5 to 10°C/min, the sintering temperature is 1150 to 1350°C, and the temperature is maintained for 1 to 3 hours.
- a NiAhC ⁇ -coated AI2O3 powder prepared by any one or more of the methods of aspects 1 to 12.
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Abstract
A method for preparing a nickel/aluminum spinel-coated aluminum oxide composite material includes coating the surface of an aluminum oxide powder with a nano-layer of NiO in an aqueous solution by a solution reaction method; and sintering the NiO-coated aluminum oxide powder to provide the spinel-coated aluminum oxide composite material.
Description
METHOD FOR PREPARING NICKLE/ ALUMINUM SPINEL-COATED ALUMINUM
OXIDE
BACKGROUND
[0001] This application is directed to methods for preparing nickel/aluminum spinel- coated aluminum oxide, the materials obtained by the methods, and uses thereof.
[0002] A spinel-type composite metal oxide is a complex oxide formed by combining two or more metal oxides, and has a chemical formula which can be written as AB2O4 or ABCO4. AB204-type spinels have cubic crystal systems, with a face-centered cubic lattice, wherein O2 is face-centered cubic close packed (CPP).
[0003] Nickel aluminate ( AI2O4) is a spinel material containing a transition metal ion (Ni). It is a narrow-bandgap semiconductor, and has advantages such as good visible light absorption properties, catalytic properties, and resistance to acids and alkalis.
Moreover, AI2O4 ceramic-metal composite materials have very high conductivity, and may be used in the aluminum electrolysis industry as inert anode materials.
[0004] A known method for synthesizing NiAl204-coated alumina (AI2O3) is ball milling NiO powder and AI2O3 powder, followed by oven-drying and heat treatment.
However, this process has a long cycle, generally requiring several hundred hours, and and high energy consumption. During preparation, the chemical reaction in which AI2O4 is synthesized can only be realized slowly at a temperature of as high as 1600°C. LIU Tao et al. have described a high-temperature oxidation method to prepare an AI2O3 composite powder coated with a nanosized AI2O4 layer. The surface of the AI2O3 was chemically plated with Ni first, then subjected to high-temperature oxidizing treatment at 1350°C or higher to obtain the corresponding powder. The method is complex and multi-step, with a high heat- treatment temperature. Another method for preparing NiAl204-coated AI2O3 is a liquid-phase combustion synthesis method. The powder obtained by that method is a mixed powder of N1AI2O4 and NiO in a non-stoichiometric ratio, the components being (Nii-xAl204-x'xNiO). The value of x is gradually reduced by raising the preheating temperature, so as to obtain the corresponding N1AI2O4 powder. The control of preheating temperature in the method is not precise, and the rate of temperature increase has a significant influence on the product, so the purity of the AI2O4 obtained is low.
[0005] In summary, the preparation of the nano structured NiAl204-coated AI2O3 has high energy consumption, and relies on complex steps. Moreover, in the case of the liquid- phase combustion synthesis method, component control is difficult, and purity is low. There
accordingly remains a need in the art for new methods for the preparation of nanostructured NiAl204-coated AI2O3.
SUMMARY
[0006] In an embodiment, a method for preparing a NiAhC^-coated AI2O3 powder, the method comprising: contacting an uncoated AI2O3 powder with N1SO4 and H4HCO3 in an aqueous medium to provide an AI2O3 powder coated with a composition comprising nickel; and sintering the AI2O3 powder coated with a composition comprising nickel at a temperature and for a time effective to provide the Ni AhC^-coated AI2O3 powder.
[0007] In a preferred embodiment, a method for preparing a nano-NiAhC^-coated AI2O3 powder comprises:
first, AI2O3 powder is dispersed in deionized water, and using nickel sulfate and ammonium bicarbonate as starting materials, the surface of the AI2O3 powder is uniformly coated with NiC03'2Ni(OH)2'2H20 by a liquid-phase reaction method, with the nano-layer thickness being regulated by controlling the nickel sulfate content, and after centrifugal separation, the powder is oven-dried and sieved, wherein the reaction equation is as follows:
3 SO4+6 H4HCO3→NiC03 2Ni(OH)2 2H20 I +( H4)2S04+5C02†;
secondly, the mixed powder is sintered, wherein during sintering,
N1CO3 2Ni(OH)2 2H2O is decomposed into nano nickel oxide, then nickel oxide reacts with AI2O3 to produce nano AI2O4, the inverse equations being as follows:
N1CO3 2Ni(OH)2 2H20→ 3 O +4H20†+C02†
AI2O3 +N1O →NiAl204; and
thirdly, the sintered powder is sieved to obtain nano-Ni AhC^-coated AI2O3 powder.
[0008] Another embodiment is a NiAhC^-coated AI2O3 made by the above-described methods.
[0009] The embodiments are further described with reference to the following Figures, Detailed Description, and Examples.
BRIEF DESCRIPTION OF THE FIGURES
[0010] The embodiments are further illustrated by the following Figures, in which:
[001 1] FIG. 1 is an X-ray diffraction (XRD) spectrum of Example 1 wherein (a) is the original AI2O3 powder and (b) is NiAb04-coated powder.
[0012] FIG. 2 is a scanning electron microscope (SEM) image showing the overall morphology of the NiAhC^-coated AI2O3 powder obtained in Example 1.
[0013] FIG. 3 is an SEM image showing the local morphology of the NiAhC^-coated AI2O3 powder obtained in Example 1, and shows that AI2O4 is uniformly distributed on the surface of the AI2O3.
DETAILED DESCRIPTION
[0014] Described herein is a liquid-phase reaction method for preparing a
nickel/aluminum spinel-coated aluminum oxide. To solve the abovementioned technical drawbacks, the technical solution includes dispersing an AI2O3 powder in an aqueous medium; and contacting the dispersed AI2O3 powder with nickel sulfate and ammonium bicarbonate to provide a surface coating comprising nickel carbonate. The thickness of the surface coating can be controlled by adjusting the nickel sulfate content. The coated AI2O3 powder is then separated from the liquid phase, dried, and optionally sized. The dried, optionally sized powder is then sintered at a temperature effective to provide to provide a nanosized N1AI2O4 coating on the AI2O3 powder. The NiAkC^-coated AI2O3 powder can then be optionally sized again.
[0015] In particular, AI2O3 powder, nickel sulfate (N1SO4), and ammonium bicarbonate (NH4HCO3) are contacted in an aqueous medium. The AI2O3 powder comprises particles that can be of any shape, for example spherical, plate-shaped, irregular, or a combination comprising at least one of the foregoing. In an embodiment the powder is approximately spherical. The particle size can be monomodal, bimodal, or higher, or a distribution of sizes. The average largest particle size can vary widely, for example from 10 nanometers (nm) to 1 millimeter (mm), or from 50 nm to 500 micrometers (μιη), or from 100 nm to 100 μιη. In an embodiment the average largest particle size is from 500 nm to 50 μιτι, or from 750 nm to 1.25 μιη. For example, the AI2O3 powder can have an average largest particle size of 0.8 to 1.2 μιτι, or 0.9 to 1.1 μιτι, or 1 μιη.
[0016] The aqueous medium comprises water, preferably deionized water. The aqueous medium can contain only water, or can further comprise a water-miscible organic solvent, for example ethanol, isopropanol, dimethylsulfoxide, dimethyl formamide, and the like. When present, the water-miscible organic solvent can comprise 1 to 80 volume percent (vol. %) of the total volume of the aqueous solution, for example 2 to 70 vol.%, or 5 to 50 vol.%, or 5 to 40 vol.%, or 10 to 30 vol.% of the total volume of the aqueous medium.
[0017] The AI2O3 powder and N1SO4, and H4HCO3 starting materials can be added to the aqueous medium in any order, or even simultaneously to provide a liquid-phase reaction system. For example, the AI2O3 powder can be dispersed in aqueous medium, followed by the addition of H4HCO3 and then and N1SO4. Alternatively, the H4HCO3 can be dissolved in the aqueous medium, followed by the addition of the AI2O3 powder and then the N1SO4 to provide the liquid-phase reaction system. The additions can be with agitation, for example stirring. Preferably, the the pH of the liquid-phase reaction system is maintained at 6 to 9, preferably at 7 to 8. The pH of the reaction can be adjusted by adjusting the rate of addition of the N1SO4.
[0018] The liquid-phase reaction system is maintained for a period of time and at a temperature effective to provide a coating on the AI2O3 powder. For example, the liquid- phase reaction system can be stirred for 30 minutes to 10 hours, or 1 hour to 5 hours. The temperature of the liquid-phase reaction system can be maintained at 10 to 50°C, for example at 20 to 25°C. In an embodiment, the temperature is ambient temperature to minimize energy costs.
[0019] Reaction of the starting materials provides a product where the the surface of the AI2O3 powder is uniformly coated with a composition comprising nickel. Without being bound by theory, it is believed that the coating comprises nickel carbonate (N1CO3). The composition can further comprise various oxides or hydroxides of nickel, for example nickel hydroxide (2Ni(OH)2). For example, the coating composition can comprise
NiC03'2Ni(OH)2'2H20 formed in a liquid-phase reaction. The reaction equation can be as shown in Equation 1.
3 SO4+6 H4HCO3 → N1CO3 2Ni(OH)2 2H20 I +( H4)2S04+5C02† (Eq. 1)
[0020] The thickness of the layer formed can be regulated by controlling the nickel sulfate content of the liquid-phase reaction system. In an embodiment, the layer can be a nano-layer having a thickness of 1 to 500 nm, or 2 to 250 nm, or 3 to 100 nm. The thickness can be uniform, for example varying by less than 20% on a given particle, or varying by less than 10%.
[0021] The nickel-coated AI2O3 powder can be isolated from the aqueous medium, for example by filtration or or centrifugal separation. The nickel-coated AI2O3 powder can be dried, for example in an oven or under a flow of hot air. The size ranges of powders after
drying can correspond approximately to the size of the starting aluminum powders. In a preferred embodiment, the nickel-coated AI2O3 powder can have can have an average particle size of less than 300 micrometers, most preferably less than 60 micrometers, or less than 40 micrometers, or less than 30 micrometers, for example 1 to 40 micrometers, or 1 to 30 micrometers.
[0022] The dried nickel-coated AI2O3 powder can then be sieved to isolate particles of more uniform size. A variety of sizes or ranges of sizes can be used. In an embodiment, the particles are sieved to a size of less than 50 micrometers, or less than 35 micrometers, or less than 20 micrometers, for example 1 to 25 micrometers, or 1 to 20 micrometers.
[0023] The nickel-coated AI2O3 powder can then be sintered to provide the NiAl204- coated AI2O3 powder. In a preferred embodiment, the NiAl204 coating thus obtained is nano structured. Without be being bound by theory, it is believed that the
N1CO3 2Ni(OH)2 2H2O coating is decomposed into nickel oxide as shown in Equation (2); then the nickel oxide reacts with AI2O3 to produce AI2O4, as shown in Equation (3).
N1CO3 2Ni(OH)2 2H20 → 3 O +4H20†+C02† (Eq. 2)
AI2O3 +NiO → AI2O4 (Eq. 3)
[0024] Sintering can be by methods known in the art. For example the nickel-coated AI2O3 powder can be loaded into a corundum crucible and heated at a rate of temperature increase of 5 to 10°C/minute, followed by heating at 1150 to 1350°C for 1 to 3 hours.
Sintering can be conducted in air or under an inert atmosphere.
[0025] After sintering the NiAhC^-coated AI2O3 powder can be sieved to provide a powder of more uniform particle size. For example, the powder can have an average particle size of less than less than 25 micrometers, or less than 15 micrometers, or less than 10 micrometers, for example 1 to 15 micrometers, or 1 to 10 micrometers.
[0026] Compared with the prior art, the present invention provides a method for preparing a nickel-aluminum-spinel-coated aluminum oxide powder material having simple operations and high reproducibility. The methods provide a dense and uniform coating of nickel-aluminum- spinel on the surface of the aluminum oxide, with uniform grain sizes. Moreover, the method is safe and reliable, requires less energy, and saves space. During preparation by sintering, the rate of temperature increase is high, the sintering temperature is
low, the surface is coated uniformly, the reaction time is shortened, and the preparation cost is low.
[0027] The nickel/aluminum-spinel-coated aluminum oxide powder prepared as described herein can be used in a variety of applications, for example as catalytic materials and as high-temperature thermosensitive materials.
[0028] The various embodiments are further illustrated by the following particular examples.
EXAMPLES
Example 1
[0029] First, 4.5 g of AI2O3 powder of average particle size 1 μιη is weighed out, and dispersed into 300 ml of deionized water and 1.5 mol/L H4HCO3 solution; an N1SO4 solution is added dropwise while stirring magnetically, wherein the total duration of the dropwise addition and reaction is 2 hours (h), to give a solution with a pH of 8. After the reaction, centrifugation and water-washing are performed, then oven-drying and sieving are performed to obtain an AI2O3 powder coated with N1CO3 2Ni(OH)2 2H2O. The powder obtained is loaded into a corundum crucible and sintered, causing the N1CO3 2Ni(OH)2 2H2O to decompose to give an NiO-coated AI2O3 powder; NiO then reacts with AI2O3 to obtain nickel-aluminum-spinel; the rate of temperature increase is 5°C/min, the sintering
temperature is 1200°C, and the temperature is maintained for 2 h. The sintered powder is sieved, to obtain a nickel-aluminum-spinel-coated aluminum oxide composite material.
[0030] The XRD spectrum of alumina is shown in FIG. 1 at (a), and the XRD spectrum of the alumina after coating is shown in FIG. 1 at (b).
[0031] The XRD spectrum of FIG. 1 shows that NiAl204 material is prepared under the conditions of Example 1.
[0032] FIG. 2 is an SEM image of the powder of Example 1 showing the overall morphology of the NiAkC^-coated AI2O3 powder obtained in Example 1. FIG. 3 is an SEM image showing the local morphology of the NiAkC^-coated AI2O3 powder obtained in Example 1. FIGS. 2 and 3; these show that the NiAl204 prepared in Example 1 is uniformly distributed on the surface of the AI2O3.
Example 2
[0033] 4.5 g of AI2O3 powder of average particle size 50 μιη is weighed out, and put into 300 ml of deionized water and 1.5 mol/L H4HCO3 solution; an N1SO4 solution is added
dropwise while stirring magnetically, wherein the total duration of the dropwise addition and reaction is 2 h, to give a solution with a pH of 7. After the reaction, centrifugation and water- washing are performed, then oven-drying and sieving are performed to obtain an AI2O3 powder coated with N1CO3 2Ni(OH)2 2H20. The powder obtained is loaded into a corundum crucible and sintered, causing the N1CO3 2Ni(OH)2 2H20 to decompose to give an NiO-coated Al203 powder; NiO then reacts with Al203 to obtain nickel-aluminum-spinel; the rate of temperature increase is 8°C/min, the sintering temperature is 1300°C, and the temperature is maintained for 2 h. The sintered powder is sieved, to obtain a nickel- aluminum-spinel-coated aluminum oxide composite material.
Example 3
[0034] 4.5 g of Al203 powder of average particle size 1 μιη is weighed out, and put into 300 ml of ethanol solution and 1.5 mol/L NH4HCO3 solution; an S04 solution is added dropwise while stirring magnetically, wherein the total duration of the dropwise addition and reaction is 2 h, to give a solution with a pH of 8. After the reaction, centrifugation and water- washing are performed, then oven-drying and sieving are performed to obtain an Al203 powder coated with N1CO3 2Ni(OH)2 2H20. The powder obtained is loaded into a corundum crucible and sintered, causing the N1CO3 2Ni(OH)2 2H20 to decompose to give an NiO-coated Al203 powder; NiO then reacts with Al203 to obtain nickel-aluminum-spinel; the rate of temperature increase is 5°C/min, the sintering temperature is 1200°C, and the temperature is maintained for 2 h. The sintered powder is sieved, to obtain a nickel- aluminum-spinel-coated aluminum oxide composite material.
Example 4
[0035] 4.5 g of Al203 powder of average particle size 100 μιη is weighed out, and put into 300 ml of ethanol solution and 1.5 mol/L NH4HCO3 solution; an S04 solution is added dropwise while stirring magnetically, wherein the total duration of the dropwise addition and reaction is 2 h, to give a solution with a pH of 8. After the reaction, centrifugation and water- washing are performed, then oven-drying and sieving are performed to obtain an Al203 powder coated with N1CO3 2Ni(OH)2 2H20. The powder obtained is loaded into a corundum crucible and sintered, causing the N1CO3 2Ni(OH)2 2H20 to decompose to give an NiO-coated Al203 powder; NiO then reacts with Al203 to obtain nickel-aluminum-spinel; the rate of temperature increase is 5°C/min, the sintering temperature is 1300°C, and the
temperature is maintained for 2 h. The sintered powder is sieved, to obtain a nickel- aluminum-spinel-coated aluminum oxide composite material.
Example 5
[0036] 4.5 g of AI2O3 powder of average particle size 100 μιη is weighed out, and put into 300 ml of deionized water solution and 1.5 mol/L H4HCO3 solution; an N1SO4 solution is added dropwise while stirring magnetically, wherein the total duration of the dropwise addition and reaction is 2 h, to give a solution with a pH of 7. After the reaction,
centrifugation and water-washing are performed, then oven-drying and sieving are performed to obtain an AI2O3 powder coated with N1CO3 2Ni(OH)2 2H2O. The powder obtained is loaded into a corundum crucible and sintered, causing the N1CO3 2Ni(OH)2 2H2O to decompose to give an NiO-coated AI2O3 powder; NiO then reacts with AI2O3 to obtain nickel-aluminum-spinel; the rate of temperature increase is 8°C/min, the sintering
temperature is 1250°C, and the temperature is maintained for 2 h. The sintered powder is sieved, to obtain a nickel-aluminum-spinel-coated aluminum oxide composite material.
[0037] The compositions and methods disclosed herein are further illustrated by the following aspects, which are non-limiting:
[0038] Aspect 1 : A method for preparing a NiAkC^-coated AI2O3 powder, the method comprising: contacting an uncoated AI2O3 powder with N1SO4 and H4HCO3 in an aqueous medium to provide an AI2O3 powder coated with a composition comprising nickel; and sintering the AI2O3 powder coated with a composition comprising nickel at a temperature and for a time effective to provide the NiAkC^-coated AI2O3 powder.
[0039] Aspect 2: The method according to aspect 1, further comprising isolating the AI2O3 powder coated with a composition comprising nickel before sintering.
[0040] Aspect 3 : The method according to aspect 2, further comprising sizing the the AI2O3 powder coated with a composition comprising nickel after isolation and before sintering.
[0041] Aspect 4: The method according to any one or more of aspects 1 to 3, further comprising sizing the NiAkC^-coated AI2O3 powder.
[0042] Aspect 5: The method according to aspect 1, comprising: dispersing the uncoated AI2O3 powder in deionized water; adding NH4HCO3 and N1SO4 to the uncoated AI2O3 powder to provide a coating on the surface of the AI2O3 powder, wherein the coating comprises nickel; separating the nickel-coated AI2O3 powder from the deionized water; oven- drying the separated AI2O3 powder; sieving the dried AI2O3 powder; sintering the sieved
AI2O3 powder to provide the NiAhC^-coated AI2O3 powder; and optionally, sieving the sintered Ni AhC^-coated AI2O3 powder.
[0043] Aspect 6: The method according to any one or more of aspects 1 to 5, wherein the coating comprises nickel comprises NiC03'2Ni(OH)2'2H20.
[0044] Aspect 7: The method according to any one or more of aspects 1 to 6, wherein the N1AI2O4 coating is nano structured.
[0045] Aspect 8: The method according to any one or more of aspects 1 to 7, wherein the uncoated AI2O3 powder has a particle size of 10 nanometers to 1 millimeter, preferably 1 to 100 μιη.
[0046] Aspect 9: The method according to any one or more of aspects 1 to 8, wherein the aqueous medium medium is deionized water or a water/ethanol solution.
[0047] Aspect 10: The method according to any one or more of aspects 1 to 9, comprising combining the uncoated AI2O3 powder and the NH4HCO3; then adding the N1SO4, preferably adding the H4HCO3 dropwise.
[0048] Aspect 11 : The method according to any one or more of aspects 1 to 10, wherein the pH of the aqueous medium is 7 to 8.
[0049] Aspect 12: The method according to any one or more of aspects 1 to 11, wherein a rate of temperature increase of sintering is 5 to 10°C/min, the sintering temperature is 1150 to 1350°C, and the temperature is maintained for 1 to 3 hours.
[0050] Aspect 13. A NiAhC^-coated AI2O3 powder prepared by any one or more of the methods of aspects 1 to 12.
[0051] While particular embodiments have been described, alternatives,
modifications, variations, improvements, and substantial equivalents that are or may be presently unforeseen may arise to applicants or others skilled in the art. Accordingly, the appended claims as filed and as they may be amended are intended to embrace all such alternatives, modifications variations, improvements, and substantial equivalents.
Claims
1. A method for preparing a NiAhC^-coated AI2O3 powder, the method comprising: contacting an uncoated AI2O3 powder with N1SO4 and H4HCO3 in an aqueous medium to provide an AI2O3 powder coated with a composition comprising nickel; and
sintering the AI2O3 powder coated with a composition comprising nickel at a temperature and for a time effective to provide the Ni AhC^-coated AI2O3 powder.
2. The method according to claim 1, further comprising isolating the AI2O3 powder coated with a composition comprising nickel before sintering.
3. The method according to claim 2, further comprising sizing the the AI2O3 powder coated with a composition comprising nickel after isolation and before sintering.
4. The method according to any one or more of claims 1 to 3, further comprising sizing the NiAhC^-coated AI2O3 powder.
5. The method according to claim 1, comprising:
dispersing the uncoated AI2O3 powder in deionized water;
adding NH4HCO3 and N1SO4 to the uncoated AI2O3 powder to provide a coating on the surface of the AI2O3 powder, wherein the coating comprises nickel;
separating the nickel-coated AI2O3 powder from the deionized water;
oven-drying the separated AI2O3 powder;
sieving the dried AI2O3 powder;
sintering the sieved AI2O3 powder to provide the NiAhC^-coated AI2O3 powder; and optionally, sieving the sintered NiAhC^-coated AI2O3 powder.
6. The method according to any one or more of claims 1 to 5, wherein the coating comprises nickel comprises NiC03'2Ni(OH)2'2H20.
7. The method according to any one or more of claims 1 to 6, wherein the NiAl204 coating is nano structured.
8. The method according to any one or more of claims 1 to 7, wherein the uncoated AI2O3 powder has a particle size of 10 nanometers to 1 millimeter, preferably 1 to 100 μιη.
9. The method according to any one or more of claims 1 to 8, wherein the aqueous medium medium is deionized water or a water/ethanol solution.
10. The method according to any one or more of claims 1 to 9, comprising combining the uncoated AI2O3 powder and the H4HCO3; then adding the N1SO4, preferably adding the H4HCO3 dropwise.
11. The method according to any one or more of claims 1 to 10, wherein the pH of the aqueous medium is 7 to 8.
12. The method according to any one or more of claims 1 to 11, wherein a rate of temperature increase of sintering is 5 to 10°C/min, the sintering temperature is 1150 to 1350°C, and the temperature is maintained for 1 to 3 hours.
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CN201710184701.9 | 2017-03-24 | ||
CN201710184701.9A CN108622919A (en) | 2017-03-24 | 2017-03-24 | A kind of preparation method of nickel aluminate coated aluminum oxide |
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CN115058129A (en) * | 2022-05-24 | 2022-09-16 | 武汉济能纳米流体技术有限公司 | Preparation method and application of functional micro powder for engine coolant |
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CN114452979A (en) * | 2021-12-31 | 2022-05-10 | 大连理工大学 | Preparation method of acid-resistant water-resistant hydrogenation catalyst with spinel framework and surface modification |
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GAYAN P ET AL: "NiO/Al"2O"3 oxygen carriers for chemical-looping combustion prepared by impregnation and deposition-precipitation methods", FUEL, IPC SCIENCE AND TECHNOLOGY PRESS, GUILDFORD, GB, vol. 88, no. 6, 1 June 2009 (2009-06-01), pages 1016 - 1023, XP025952804, ISSN: 0016-2361, [retrieved on 20090103], DOI: 10.1016/J.FUEL.2008.12.007 * |
JIANFEN LI ET AL: "Development of Nano-NiO/Al 2 O 3 Catalyst to be Used for Tar Removal in Biomass Gasification", ENVIRONMENTAL SCIENCE & TECHNOLOGY, vol. 42, no. 16, 1 August 2008 (2008-08-01), US, pages 6224 - 6229, XP055479381, ISSN: 0013-936X, DOI: 10.1021/es800138r * |
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Cited By (2)
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CN115058129A (en) * | 2022-05-24 | 2022-09-16 | 武汉济能纳米流体技术有限公司 | Preparation method and application of functional micro powder for engine coolant |
CN115058129B (en) * | 2022-05-24 | 2023-09-12 | 武汉济能纳米流体技术有限公司 | Preparation method and application of functional micro powder for engine coolant |
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