CN112707422B - Gamma-alumina octahedral self-assembly particle material and preparation method thereof - Google Patents
Gamma-alumina octahedral self-assembly particle material and preparation method thereof Download PDFInfo
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 239000000463 material Substances 0.000 title claims abstract description 31
- 239000002245 particle Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 238000001338 self-assembly Methods 0.000 title description 7
- 239000013078 crystal Substances 0.000 claims abstract description 53
- 239000000843 powder Substances 0.000 claims abstract description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000003756 stirring Methods 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 12
- 239000002243 precursor Substances 0.000 claims abstract description 9
- 238000010335 hydrothermal treatment Methods 0.000 claims abstract description 8
- 239000000725 suspension Substances 0.000 claims abstract description 8
- 150000001412 amines Chemical class 0.000 claims abstract description 7
- 150000007524 organic acids Chemical class 0.000 claims abstract description 7
- 238000010008 shearing Methods 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims abstract description 5
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 4
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 4
- 239000007788 liquid Substances 0.000 claims abstract description 4
- 150000003839 salts Chemical class 0.000 claims abstract description 4
- 238000000227 grinding Methods 0.000 claims abstract description 3
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 235000011164 potassium chloride Nutrition 0.000 claims abstract description 3
- 239000001103 potassium chloride Substances 0.000 claims abstract description 3
- 238000000926 separation method Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 28
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 18
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 239000004317 sodium nitrate Substances 0.000 claims description 9
- 235000010344 sodium nitrate Nutrition 0.000 claims description 9
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 8
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 8
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 8
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 7
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 7
- 235000002639 sodium chloride Nutrition 0.000 claims description 7
- 159000000000 sodium salts Chemical class 0.000 claims description 7
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- 239000011236 particulate material Substances 0.000 claims description 6
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 4
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 claims description 4
- 235000019253 formic acid Nutrition 0.000 claims description 4
- 239000004323 potassium nitrate Substances 0.000 claims description 4
- 235000010333 potassium nitrate Nutrition 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 239000011780 sodium chloride Substances 0.000 claims description 4
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- 238000000498 ball milling Methods 0.000 claims description 2
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000003921 oil Substances 0.000 claims description 2
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 2
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 2
- 235000011151 potassium sulphates Nutrition 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 235000011152 sodium sulphate Nutrition 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 abstract 1
- 229910052708 sodium Inorganic materials 0.000 abstract 1
- 239000011734 sodium Substances 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 4
- 239000007900 aqueous suspension Substances 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 238000002003 electron diffraction Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000003889 chemical engineering Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000693 micelle Substances 0.000 description 2
- 238000005504 petroleum refining Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000004323 axial length Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 238000005063 solubilization Methods 0.000 description 1
- 230000007928 solubilization Effects 0.000 description 1
Images
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- 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
- C01F7/44—Dehydration of aluminium oxide or hydroxide, i.e. all conversions of one form into another involving a loss of water
- C01F7/441—Dehydration of aluminium oxide or hydroxide, i.e. all conversions of one form into another involving a loss of water by calcination
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
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- C—CHEMISTRY; METALLURGY
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
- C01P2004/11—Particle morphology extending in one dimension, e.g. needle-like with a prismatic shape
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- 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
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
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Abstract
The invention discloses a gamma-alumina octahedral self-assembled particle material and a preparation method thereof. The material has a pseudo-single crystal structure and a prism shape, and the length of alumina particles along the [110] crystal axis direction is 200-10000nm. The preparation method comprises the following steps: (1) Roasting the alumina precursor powder, then doping inorganic sodium and/or inorganic sylvite, then grinding the powder by using a ball mill, washing with water to remove salt, drying, preparing a suspension with a certain concentration, adding a certain amount of organic acid, and uniformly mixing by using a shearing stirrer; (2) Adding a certain amount of organic amine and low-carbon alcohol into the material obtained in the step (1) and uniformly stirring; (3) And (3) carrying out closed hydrothermal treatment on the material obtained in the step (2), and after the treatment is finished, carrying out solid-liquid separation, drying and roasting to obtain a product. The material has good application prospect in the field of catalysis, in particular in the field of distillate oil hydrogenation catalysis.
Description
Technical Field
The invention belongs to the field of inorganic material preparation, and particularly relates to a gamma-alumina octahedral self-assembled particle material and a preparation method thereof.
Background
The gamma-alumina is used as a good catalytic carrier material, and the surface property of the gamma-alumina has stronger correlation with the exposed crystal face of the crystal. For gamma-alumina, the results of prior studies indicate that the (110) crystal plane is thermodynamically most stable and is usually preferentially exposed. And other crystal faces of the gamma-alumina, such as the (111) face and the (100) face, have different atomic arrangement and interface properties from the (110) crystal face, so that the crystal face of the alumina can be regulated and controlled by a series of measures to obtain special physicochemical properties. However, the predominance of the gamma-alumina (110) crystal plane is difficult to change, depending on the crystal growth habit.
[ fine petrochemical, 2014, 31 (5): 38-43. It was found that the γ -alumina crystal mainly exposed the (110) plane family and the (111) plane family, in which the (110) plane family surface proportion was about 70.4% and the (111) plane family surface proportion was about 29.6%.
[ contemporary chemical engineering, 2015, 44 (5): 951-954 ] nanometer gamma-alumina single crystal particles containing high-index crystal planes such as (110), (752) and (541) are prepared. However, the crystal face of the high-index alumina has higher activity and is difficult to exist stably in thermodynamics.
[ petroleum refining and chemical engineering, 2013, 44 (9): 47-50 the crystal face distribution proportion of the alumina single crystal particles can be properly regulated and controlled by adding sodium nitrate into a hydrothermal system, but the gamma-alumina still takes the (110) crystal face as the main crystal face.
The self-assembly method is another means to adjust the crystal face distribution ratio of alumina. CN200910011627.6, CN200910206229.X and CN200910011626.1 adopt a molten salt super solubilization micelle self-assembly method to obtain more regular rod-shaped alumina secondary particles. [ Chinese science, 2009, 39 (5): 420-431 and [ journal of inorganic chemistry, 2015, 31 (8): 1539-1547 ] illustrate the mechanism of alumina supersolubilization micelle self-assembly. The self-assembly method can have important influence on the physical and chemical properties of the alumina material such as the pore structure, the aggregation state and the like, but the effect of regulating and controlling the crystal plane distribution is still not obvious.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a gamma-alumina octahedron self-assembly particle material and a preparation method thereof.
The gamma-alumina octahedral self-assembled particle material has a pseudo single crystal structure and a prismatic appearance, the upper hexagonal bottom surface and the lower hexagonal bottom surface are (110) crystal planes, the rectangular side surfaces of the prism are (111) crystal planes and (100) crystal planes respectively, and based on the total exposed area of the crystal planes of the alumina material, the distribution proportion of the (110) crystal planes is 16-35%, the distribution proportion of the (111) crystal planes is 35-75%, and the distribution proportion of the (100) crystal planes is 5-30%. The alumina particles have a length of 200-10000nm, preferably 2000-6000nm, along the [110] crystal axis.
The pseudo single crystal structure of the gamma-alumina octahedral self-assembled particle material is a self-assembled body which has the appearance characteristic of single crystal and is actually formed by orderly arranging superfine nanometer crystal grains.
The preparation method of the gamma-alumina octahedral self-assembled particle material comprises the following steps:
(1) Roasting the alumina precursor powder, adding a certain amount of inorganic sodium salt and/or inorganic potassium salt, grinding the powder by using a ball mill, washing the ground powder with water to remove salt, drying, preparing a suspension with a certain concentration, adding a certain amount of organic acid, and uniformly mixing by using a shearing stirrer;
(2) Adding a certain amount of organic amine and low-carbon alcohol into the material obtained in the step (1) and uniformly stirring;
(3) And (3) carrying out closed hydrothermal treatment on the material obtained in the step (2), and after the treatment is finished, carrying out solid-liquid separation, drying and roasting to obtain a product.
In the method of the present invention, the alumina precursor in step (1) refers to pseudo-boehmite and pseudo-boehmite powder modified by various elements such as silicon, boron, titanium, magnesium, lanthanum, etc.
In the method of the invention, the roasting temperature in the step (1) is 350-650 ℃, preferably 450-550 ℃, and the roasting time is 1-48 hours, preferably 2-24 hours.
In the method, the material in the step (1) is subjected to ball milling treatment to obtain powder with the granularity of more than 2000 meshes, and the powder granularity is preferably 5000-20000 meshes.
In the method, the inorganic sodium salt in the step (1) is one or more of sodium nitrate, sodium chloride or sodium sulfate, and the inorganic potassium salt in the step (1) is one or more of potassium nitrate, potassium chloride or potassium sulfate. The dosage of the inorganic sodium salt and/or the inorganic potassium salt accounts for 0.1 to 10 percent of the mass of the alumina precursor powder. The inorganic sodium salt and the inorganic potassium salt may be mixed in an arbitrary ratio.
In the method of the present invention, the concentration of the suspension in the step (1) is 1 to 200g/L, preferably 20 to 150g/L.
In the method of the present invention, the organic acid in step (1) is one or more of formic acid, acetic acid or citric acid, and the amount of the organic acid is 0.1% to 8% of the mass of the alumina precursor powder, preferably 0.5% to 5%.
In the method, the shearing and stirring conditions in the step (1) are as follows: the stirring speed is 1000-20000rpm, the stirring time is 1-60 minutes, preferably 2000-10000rpm, the stirring time is 3-10 minutes.
In the method, the organic amine in the step (2) is one or more of ethanolamine, diethanolamine, triethanolamine, aniline, diphenylamine, benzidine or o-phenylenediamine. The concentration of the organic amine in the material system is 1-200g/L, preferably 5-50g/L.
In the method of the present invention, the lower alcohol in step (2) is one or more of methanol, ethanol, propanol and propylene glycol, preferably methanol and/or ethanol. The concentration of the lower alcohol in the material system is 5-200g/L, preferably 10-100g/L.
In the method, the closed hydrothermal conditions in the step (3) are as follows: hydrothermal treatment at 80-300 deg.C for 0.5-48 hr, preferably 100-200 deg.C for 5-24 hr.
In the method of the present invention, the drying temperature in the step (3) is not more than 200 ℃, preferably not more than 120 ℃, and the drying degree is that the material reaches a constant weight at the drying temperature.
In the method, the roasting conditions in the step (3) are as follows: roasting at 450-750 deg.c for 1-24 hr, preferably at 500-650 deg.c for 3-12 hr.
The gamma-alumina octahedron self-assembled particle has unique crystal face distribution characteristic, simple preparation method and good application prospect in the field of distillate oil hydrogenation catalysis.
Drawings
FIG. 1 is a scanning electron micrograph of the gamma-alumina octahedral self-assembled particulate material prepared in example 1.
FIG. 2 is an electron diffraction spectrum in the [110] direction of the gamma-alumina octahedral self-assembled particulate material prepared in example 1.
Fig. 3 is an XRD spectrum of the gamma-alumina octahedral self-assembled particulate material prepared in example 1.
Detailed Description
The process of the present invention is described in detail by examples below. The particle size of the gamma-alumina material was measured according to scanning electron microscope images. Randomly measuring 20 particles, and taking the average axial length value as the height value of the particles; the crystal form is characterized by X-ray diffraction; collecting an electron diffraction spectrum through a transmission electron microscope, and processing a sample through a slicing means before carrying out electron diffraction analysis on a large-particle sample.
Example 1
15g of pseudo-boehmite powder is roasted for 10 hours at 500 ℃, 1 g of sodium chloride is added and mixed evenly, the mixture is ground into micro powder by a ball mill, particles with about 5000 meshes are sieved, the sodium chloride is removed by washing with distilled water, and then 30g/L of aqueous suspension is prepared. Adding acetic acid into the suspension, wherein the dosage of the acetic acid is 0.8 percent of the mass of the calcined powder, and shearing and stirring the mixture for 10 minutes at 5000 rpm. Adding aniline and ethanol into the system, wherein the final mass percent concentration of the aniline and the ethanol is 15g/L and 30g/L respectively, uniformly stirring, sealing the system, and heating to 200 ℃ for hydrothermal treatment for 3 hours. And roasting the product dried at the temperature of 120 ℃ at the temperature of 550 ℃ for 5 hours to obtain the product. The observation of a scanning electron microscope shows that the appearance of the product is approximately regular hexagonal prism. The XRD result of the product shows that the phase state is gamma phase. According to the shape and the included angle relationship, the orientation along the height direction of the column is [110], the bottom surface is a (110) crystal plane (in a hexagon shape), and the side surfaces of the hexagonal prism are respectively a (100) plane and a (111) plane. Wherein, 2 (110) surfaces, 2 (100) and 4 (111) surfaces are provided. The length along [110] direction was 4190nm, the average size of (100) crystal planes was 720nm. Multidot.4190nm, and the average size of (111) crystal planes was 850. Multidot.4190nm. It is found by calculation that the proportion of (110) plane is 17%, the proportion of (111) plane is 61%, and the proportion of (100) plane is 22%.
Example 2
15g of pseudo-boehmite powder is roasted for 10 hours at 550 ℃, then 0.5 g of sodium nitrate is added and mixed evenly, the mixture is ground into micro powder by a ball mill, particles about 8000 meshes are sieved, distilled water is used for washing to remove the sodium nitrate, and then 35g/L of water suspension is prepared. And adding formic acid into the suspension, wherein the amount of the formic acid is 2.5% of the mass of the calcined powder. The material was shear stirred at 5000rpm for 30 minutes. Adding ethanolamine and propanol into the system, wherein the mass percentage concentration of the ethanolamine and the propanol is 15g/L and 30g/L respectively, uniformly stirring, sealing the system, and heating to 200 ℃ for hydrothermal treatment for 12 hours. And roasting the product dried at the temperature of 120 ℃ for 4 hours at the temperature of 550 ℃ to obtain the product. The observation of a scanning electron microscope shows that the appearance of the product is approximately regular hexagonal prism. The XRD result of the product shows that the phase state is gamma phase. According to the relationship of the shape and the included angle, the orientation is [110] along the height direction of the column, the bottom surface is a (110) crystal face (in a hexagon shape), and the side surfaces of the hexagonal prism are respectively a (100) plane and a (111) plane. Wherein, 2 (110) surfaces, 2 (100) surfaces and 4 (111) surfaces are provided. The length along the (110) direction was 1580nm, the (100) plane average size was 255nm + 1580nm, and the (111) plane average size was 360 + 1580nm. The ratio of (110) planes was found to be 20%, the ratio of (111) planes was found to be 66%, and the ratio of (100) planes was found to be 14%.
Example 3
15g of pseudo-boehmite powder is roasted for 7 hours at 650 ℃, 1 g of potassium nitrate is added and mixed evenly, the mixture is ground into micro powder by a ball mill, particles with about 20000 meshes are sieved, the potassium nitrate is removed by washing with distilled water, and then 30g/L of aqueous suspension is prepared. And adding part of citric acid into the suspension, wherein the dosage of the citric acid is 3.5 percent of the mass of the calcined powder. The material was shear stirred at 10000rpm for 15 minutes. Adding aniline and ethanol into the system, wherein the mass percentage concentration of the aniline and the ethanol is 60g/L and 80g/L respectively, uniformly stirring, sealing the system, and heating to 180 ℃ for hydrothermal treatment for 12 hours. And roasting the product dried at the temperature of 120 ℃ for 4 hours at the temperature of 650 ℃ to obtain the product. The observation of a scanning electron microscope shows that the appearance of the product is approximately regular hexagonal prism. The XRD result of the product shows that the phase state is gamma phase. According to the relation of the shape and the included angle, the orientation is [110] along the column height direction, the bottom surface is a (110) crystal plane (in a hexagon), and according to the relation of the included angle, the side surfaces of the hexagonal prism are respectively a (100) plane and a (111) plane. Wherein, 2 (110) surfaces, 2 (100) surfaces and 4 (111) surfaces are provided. The length along [110] direction is 1050nm, the average size of (100) surface is 300nm 1050nm, and the average size of (111) surface is 285 nm 1050nm. It is found by calculation that the proportion of (110) plane is 35%, the proportion of (111) plane is 55%, and the proportion of (100) plane is 10%.
Comparative example 1
Reference [ petroleum refining and chemical, 2013, 44 (9): 47-50 ] by adding sodium nitrate to adjust the crystal plane distribution of the alumina single crystal grains. The test conditions were divided into two groups, group 1 without sodium nitrate and group 2 with sodium nitrate. The product is tested to contain (110), (111) and (100) low index crystal faces. The first set of three crystal planes is distributed: (110) % is 72.3%, (111)% is 20.5%, (100)% is 7.2%; the second set of three crystal planes are: (110) The number of facets was 64.2%, 26.4% for (111) facet, and 9.4% for (100) facet, and the distribution of (110) facet was more than 50% regardless of the addition of sodium nitrate.
Claims (15)
1. A gamma-alumina octahedral self-assembled particle material is characterized in that: the structure has a pseudo single crystal structure and a prism shape, the upper hexagonal bottom surface and the lower hexagonal bottom surface are (110) crystal faces, and the rectangular side surfaces of the prism are (111) crystal faces and (100) crystal faces respectively; based on the total area of the exposed crystal faces of the particle material, the distribution ratio of (110) crystal faces is 16-35%, the distribution ratio of (111) crystal faces is 35-75%, and the distribution ratio of (100) crystal faces is 5-30%.
2. The particulate material of claim 1, wherein: the alumina particles have a length of 200-100000nm along the [110] crystal axis.
3. A method for preparing a gamma-alumina octahedral self-assembled particulate material according to claim 1 or 2, characterized by comprising the following steps: (1) Roasting the alumina precursor powder, adding a certain amount of inorganic sodium salt and/or inorganic potassium salt, grinding the powder by using a ball mill, washing the ground powder with water to remove salt, drying, preparing a suspension with a certain concentration, adding a certain amount of organic acid, and uniformly mixing by using a shearing stirrer; (2) Adding a certain amount of organic amine and low-carbon alcohol into the material obtained in the step (1) and uniformly stirring; (3) Carrying out closed hydrothermal treatment on the material obtained in the step (2), and after the treatment is finished, carrying out solid-liquid separation, drying and roasting to obtain a product; the use amount of the inorganic sodium salt and/or the inorganic potassium salt in the step (1) accounts for 0.1 to 10 percent of the mass of the precursor powder after the roasting of the alumina; the concentration of the suspension liquid in the step (1) is 1-200g/L; the dosage of the organic acid in the step (1) is 0.1-8% of the mass of the alumina precursor powder; the concentration of the organic amine in the step (2) in a material system is 1-200g/L; the concentration of the low-carbon alcohol in the step (2) in a material system is 5-200g/L.
4. The method of claim 3, wherein: the alumina precursor in the step (1) is pseudo-boehmite or a pseudo-boehmite powder modified by silicon, boron, titanium, magnesium or lanthanum.
5. The method of claim 3, wherein: the roasting temperature in the step (1) is 350-650 ℃, and the roasting time is 1-48 hours.
6. The method of claim 3, wherein: the material in the step (1) is subjected to ball milling treatment to obtain powder with the particle size of more than 2000 meshes.
7. The method of claim 3, wherein: the inorganic sodium salt in the step (1) is one or more of sodium nitrate, sodium chloride or sodium sulfate; the inorganic potassium salt is one or more of potassium nitrate, potassium chloride or potassium sulfate.
8. The method of claim 3, wherein: the organic acid in the step (1) is one or more of formic acid, acetic acid or citric acid.
9. The method of claim 3, wherein: the shearing and stirring conditions in the step (1) are as follows: the stirring speed is 1000-20000rpm, and the stirring time is 1-60 minutes.
10. The method of claim 3, wherein: the organic amine in the step (2) is one or more of ethanolamine, diethanolamine, triethanolamine, aniline, diphenylamine, benzidine or o-phenylenediamine.
11. The method of claim 3, wherein: the lower alcohol in the step (2) is one or more of methanol, ethanol, propanol and propylene glycol.
12. The method of claim 3, wherein: the closed hydrothermal condition of the step (3) is as follows: carrying out hydrothermal treatment at 80-300 ℃ for 0.5-48 hours.
13. The method of claim 3, wherein: the drying temperature in the step (3) is not more than 200 ℃, and the drying degree is that the material reaches constant weight at the drying temperature.
14. The method of claim 3, wherein: the roasting conditions in the step (3) are as follows: roasting at 450-750 deg.c for 1-24 hr.
15. Use of the gamma-alumina octahedral self-assembled particulate material according to claim 1 in the field of distillate oil hydrogenation catalysis.
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