CN108383144A - A kind of sponge structure γ-Al2O3Material and preparation method thereof - Google Patents
A kind of sponge structure γ-Al2O3Material and preparation method thereof Download PDFInfo
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- CN108383144A CN108383144A CN201810231982.3A CN201810231982A CN108383144A CN 108383144 A CN108383144 A CN 108383144A CN 201810231982 A CN201810231982 A CN 201810231982A CN 108383144 A CN108383144 A CN 108383144A
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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
- C01F7/30—Preparation of aluminium oxide or hydroxide by thermal decomposition or by hydrolysis or oxidation of aluminium compounds
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2004/60—Particles characterised by their size
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- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/14—Pore volume
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- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
- C01P2006/17—Pore diameter distribution
Abstract
The present invention relates to a kind of sponge structure γ Al2O3Material and preparation method thereof, this method include obtaining alumina precursor after silicon source solution a is mixed thermal response with organic ligand solution b, and alumina precursor is calcined obtain aluminium oxide intermediate under inert gas protection；Aluminium oxide intermediate is heat-treated in air atmosphere, the γ Al with spongy nano-porous structure are made2O3Material.The method of the present invention without tedious steps such as pH adjustings, neutralization, agings, and does not need outer doping, dispersant, has the features such as simple for process, reaction step is few.It obtains that there is uniform spongelike structure and there are large specific surface area (300 350m2/ g) gamma-alumina powder, be of great significance to the expansion of improvement and its application of gamma-alumina pore passage structure and surface nature.
Description
Technical field
The present invention relates to a kind of sponge structure γ-Al2O3Material and preparation method thereof belongs to new material technology field.
Background technology
Alumina material is most commonly seen one of the catalyst carrier in Industrial Catalysis field, is a kind of widely used and very
Important porous material.Compared with traditional porous material, alumina material is in addition to abundant duct, there is also have surface
Acid and a variety of crystalline phases, can be used as adsorbent, catalyst and catalyst carrier.In the alumina crystalline phase being had found at existing 8 kinds,
γ-Al2O3It is most important, most widely used transition alumina in industry.γ type aluminium oxide is not soluble in water, can be dissolved in strong acid
Or strong base solution, it, which is heated to 1200 DEG C, can be completely converted into alpha-type aluminum oxide.γ type aluminium oxide has following property：First,
With multi-pore channel structure, there is higher specific surface area；Second, have good thermal stability and chemical stability；Third, can
It is resistant to high pressure, resistant to breakage is functional.
Related γ-Al at present2O3In terms of the research of material is concentrated mainly on catalyst carrier.The γ-in catalytic process
Al2O3Pattern, pore structure and surface nature, all to diffusion of the dispersion of catalyst activity component, reactant and product etc.
With large effect.Currently, γ-Al2O3Pattern with rodlike, sheet, it is spherical, fibrous based on, existing preparation method is past
It is past complex, it needs to carry out accuracy controlling to pH value.Although in addition, with mesoporous hole inside the aluminium oxide with the above pattern
Road, but hole link is poor, some internal gutters are not connected to outside, and inner surface is not fully utilized.And it is situated between
The formation in hole is mainly derived from subgrain and accumulates the unordered accumulation hole to be formed, this is to the preparation of catalyst and the diffusion of reactant
It is unfavorable.
Chinese patent literature CN103359765A discloses a kind of mesoporous gamma-alumina preparation method of morphology controllable, the party
Silicon source, dispersant, precipitating reagent are dissolved in deionized water by method, then by above-mentioned mixed solution temperature be 80~180 DEG C of conditions
Under, the different morphologies of zero dimension, peacekeeping three-dimensional are made by suction filtration, washing, drying and roasting in crystallization 6~48 hours
Mesoporous gamma-alumina material, in the preparation method modulation of pattern depend on dispersant (polyethylene glycol, ammonium citrate,
CTAB or polypyrrole alkanone), it is harsh to the proportion requirement of silicon source and dispersant, if subsequent process is dealt with improperly, easily introduce
Impurity, and hole link is poor.
Chinese patent literature CN106276994B discloses a kind of preparation method of sheet gamma-alumina, and this method is by aluminium
The clear solution formed behind source and urea dissolving is transferred in autoclave, is mixed with hydrogen in carbon monoxide or carbon monoxide
Under gas atmosphere, certain temperature and pressure is maintained to be reacted.Although this method can prepare a sheet of bigger serface γ oxygen
Change aluminium, but this method needs high pressure, and the flammable explosive gas such as carbon monoxide, hydrogen is needed to do protection gas, safety is poor.
Chinese patent literature CN103663524 discloses a kind of 3D bar-shaped nanostructures γ phase aluminas material and preparation side
Method, this method use sodium phosphate or sodium metasilicate for precipitating reagent under hydrothermal conditions, and potassium sulfate or sodium sulphate and combinations thereof are addition
Aluminium chloride is placed at 150-160 DEG C with urea after reacting 8-15h by agent, after cooling, being filtered, washed, drying, roast, is prepared
The gamma-alumina of Rod-like shape is gone out, this method precipitating reagent, the subsequent processing of additive and purification process are complicated, especially alkaline
Ion, if being unable to Economical Purification, impurity can generate strong influence to the surface nature of final aluminium oxide.
The shortcomings that the above preparation or processing method and deficiency limit the preparation of gamma-alumina material, modification and answer
With.
Invention content
In view of the deficiencies of the prior art, the present invention provides a kind of sponge structure γ-Al2O3Material and preparation method thereof, this hair
There is bright gamma-alumina spongelike structure and abundant opening duct, large specific surface area can be provided more for activated centre
More anchored sites, and the diffusion for reactants and products molecule provides facility.
The preparation method is simple for process, and reaction step is few, without tedious steps such as pH adjustings, neutralization, agings, and does not need
Outer doping, dispersant.
Technical scheme is as follows：
A kind of sponge structure γ-Al2O3Material, for the gamma-alumina material in threadiness or bulk, fibre length is 1-3 μm,
Fiber rib width is 400-500nm, and blocky length is 1-5 μm, and blocky width is 0.8-3 μm；With spongy nano-porous structure,
Surface has hole, internal gutter to be connected to outside, specific surface area 300-350m2/ g, hole hold 0.5-0.8cm3/ g, aperture point
Cloth concentrates on 2-20nm, most probable pore size 6-10nm.
The present invention also provides a kind of sponge structure γ-Al2O3The preparation method of material.
The preparation method of sponge structure gamma-alumina, including steps are as follows：
(1) silicon source is dissolved in solvent a, organic ligand is dissolved in solvent b by obtained solution a, obtained solution b；By solution
A is sufficiently stirred after being mixed with solution b, and thermal response postcooling is filtered, washed, dries, and obtains faint yellow alumina precursor；
(2) alumina precursor is warming up to 300-1000 DEG C under inert gas protection to calcine 0.5-12 hours, it is cooling,
Obtain aluminium oxide intermediate；
(3) aluminium oxide intermediate is warming up to 400-900 DEG C of heat treatment 2-12h in air atmosphere, being made has sponge
γ-the Al of shape nano-porous structure2O3Material.
According to currently preferred, the silicon source described in step (1) is aluminum perchlorate, aluminium acetate, aluminum sulfate, aluminium chloride, nitre
Sour aluminium, aluminium bromide, silver iodide, aluminum fluoride, aluminum potassium sulfate 12 hydrate, aluctyl, aluminium secondary butylate, aluminium isopropoxide or levulinic
One or more of ketone aluminium mixes.
According to currently preferred, the organic ligand described in step (1) is Isosorbide-5-Nitrae-terephthalic acid (TPA), M-phthalic acid, 1,
One in 4- naphthalene dicarboxylic acids, 2,3- naphthalene dicarboxylic acids, 2,6 naphthalene dicarboxylic acid, 4 4'- biphenyl dicarboxylic acids or azobenzene -4,4- dicarboxylic acids
Kind or two or more mixing.
According to currently preferred, the solvent a described in step (1) is methanol, ethyl alcohol, deionized water or N, N- dimethyl methyls
One kind in amide, the solvent b are one kind in methanol, ethyl alcohol, deionized water or n,N-Dimethylformamide.
According to currently preferred, the molar ratio of aluminium element and organic ligand is (0.1- in the silicon source described in step (1)
4)：1.
According to currently preferred, the molar ratio of aluminium element and solvent a are 0.5 in the silicon source described in step (1)：(20-
50)。
According to currently preferred, the molar ratio of ligand and solvent b described in step (1) is 0.5：(20-50).
According to currently preferred, in step (1), the thermal response is that system reacts 10-75h at 150-220 DEG C.
According to currently preferred, in step (2), calcination temperature is 600-900 DEG C, and calcination time is 2-5 hours.
According to currently preferred, in step (2), heating rate is 1-10 DEG C/min.
According to currently preferred, in step (2), the inert atmosphere is one kind in nitrogen, helium or argon gas.
According to currently preferred, in step (2), inert gas flow velocity 1-500mL/min；It is further preferred that institute
It is 20-100mL/min to state inert gas flow velocity；
According to currently preferred, in step (3), heat treatment temperature is 400-600 DEG C, and heat treatment time is 2-7 hours.
According to currently preferred, in step (3), heating rate is 1-20 DEG C/min, it is preferred that heating rate 5-10
℃/min。
Sponge structure γ-Al of the present invention2O3The principle that material is formed：
The present invention is using aluminium salt and the metal-organic framework material of organic ligand formation as template, in inert atmosphere protection
Under, hard template is served as using organic ligand in-situ carburization, while avoiding the dehydration aggregation of alumina cluster, removes generated in-situ carbon
After template, the spongelike structure gamma-alumina that internal gutter penetrates through and structure is special is prepared.The shape of sponge structure aluminium oxide
At the structure for depending primarily on presoma-aluminium based metal organic framework materials.There is machine frame in the aluminium based metal of various topological structure
In frame material, only alumina cluster exists in the form of one-dimensional chain and arranges in stratiform, connects to form one-dimensional perforation through organic ligand
The metal-organic framework material in duct after heat treatment, easily forms spongiform porous structure.Due to its internal aluminium cluster with it is organic
Ligand is in interval layered distribution, and when being heat-treated under an inert atmosphere, organic ligand in-situ carburization forms hard template intercalation,
Avoid the aggregation between the aluminium cluster of layered distribution.It is then heat-treated in air, carbon template is removed, to aoxidize
The duct that stratiform is mutually communicated is formd inside aluminium, finally obtains the alumina material with spongelike structure.The method of the present invention
The gamma-alumina of preparation inherits the original pattern of MOFs presomas, and it is spongiform porous structure to form internal.
The beneficial effects of the present invention are：
1, method of the invention without tedious steps such as pH adjustings, neutralization, agings, and does not need outer doping, dispersion
Agent has the features such as simple for process, reaction step is few.It obtains that there is uniform spongelike structure and there is large specific surface area
(300-350m2/ g) gamma-alumina powder, the expansion to improvement and its application of gamma-alumina pore passage structure and surface nature
It is of great significance.
2, gamma-alumina of the invention has the porous structure of special sponge and abundant opening duct, larger ratio
Surface area can provide more anchored sites for activated centre, and the diffusion for reactants and products molecule provides facility.It should
Gamma-alumina is suitable as the carrier of load type metal catalyst, is particularly suitable for application as the load of hydrodesulfurization reaction catalyst
Body.
Description of the drawings
Fig. 1 is the X-ray powder diffraction pattern (PXRD) of gamma-alumina made from embodiment 1；
Fig. 2 is scanning electron microscope (SEM) figure of gamma-alumina made from embodiment 1；
Fig. 3 is transmission electron microscope (TEM) figure of gamma-alumina made from embodiment 1；
Fig. 4 is the low temperature nitrogen adsorption desorption curve graph of gamma-alumina made from embodiment 1；
Fig. 5 is the graph of pore diameter distribution of gamma-alumina made from embodiment 1；
Fig. 6 is scanning electron microscope (SEM) figure of gamma-alumina made from embodiment 2；
Fig. 7 is transmission electron microscope (TEM) figure of gamma-alumina made from comparative example 1.
Specific implementation mode
Explanation is further explained to the present invention with reference to specific embodiments and the drawings, but the invention is not limited in
This.Test method described in following example is unless otherwise specified conventional method；The instrument and material, such as without special theory
It is bright, commercially obtain.
Embodiment 1：
A kind of sponge structure γ-Al2O3The preparation method of material, steps are as follows：
(1) 0.75g is taken, 2mmol aluminum nitrates, which are dissolved in as silicon source in 10mL water, obtains solution a, takes 0.216g, 1mmol1,
4- naphthalenedicarboxylic acids, which are dissolved in as organic ligand in 10mL ethyl alcohol, is used as solution b；Al in aluminum nitrate: the molar ratio of organic ligand is 2:
1；
It is 1 by volume by solution a and solution b：1 ratio mixing, stirs evenly, is placed in ptfe autoclave
In, 180 DEG C are warming up to, thermal response 24 hours.After reaction, temperature is cooled to room temperature taking-up, by sediment deionized water
It is washed respectively with ethyl alcohol, finally obtains pale yellow powder, as alumina precursor.
(2) alumina precursor prepared in 0.4g steps (1) is weighed to be placed in tube furnace, in a nitrogen atmosphere with 5 DEG C/
Min from room temperature rise to 800 DEG C heat preservation 2h after natural cooling, obtain aluminium oxide intermediate；
(3) the aluminium oxide intermediate in step (2) is placed in Muffle furnace, after rising to 500 DEG C of heat preservation 5h with 10 DEG C/min
Natural cooling obtains the γ-Al with spongy nano-porous structure2O3Material.
The X-ray powder diffraction figure of gained aluminium oxide is as shown in Figure 1, as shown in Figure 1, obtained material is the γ oxygen of pure phase
Change aluminium, undoped with other impurity.Fig. 2 is the SEM pictures of gained gamma-alumina, it can be seen from the figure that gamma-alumina is in fiber
Shape form exists, and length is 2 μm, and rib width is 450nm, and there is apparent hole on surface.Fig. 3 schemes for its TEM, as seen from the figure, in
Portion is spongelike structure, and duct is connected to outside, has abundant inner surface.Fig. 4 is that the cryogenic nitrogen aspiration of gamma-alumina is de-
Attached curve, the thermoisopleth are typical Type IV types, show that the gamma-alumina has mesopore orbit feature, while its BET method ratio
Surface area has reached 350m2/ g, Kong Rong have reached 0.63cm3/g.Fig. 5 is the graph of pore diameter distribution of spongy gamma-alumina, display production
Product pore-size distribution is concentrated mainly between 2-20nm, and most probable pore size is 8nm or so.
Embodiment 2
A kind of sponge structure γ-Al2O3The preparation method of material, steps are as follows：
It is silicon source to take 1.3g, 3.46mmol aluminum nitrates, and Isosorbide-5-Nitrae-terephthalic acid (TPA) of 0.287g, 1.73mmol are ligand, nitre
Al in sour aluminium: the molar ratio of organic ligand is 2: 1；The drug weighed up is mixed with 5mL water respectively, stirs evenly, is added together
In ptfe autoclave.With the heating rate of 3 DEG C/min, 210 DEG C are warming up to, thermal response 72h.After reaction, temperature
It is cooled to room temperature taking-up, sediment is washed with deionized, and 60 DEG C of dryings finally obtain alumina precursor.Before aluminium oxide
Drive body be placed in tube furnace, in a nitrogen atmosphere with 10 DEG C/min from room temperature rise to 700 DEG C heat preservation 2h after natural cooling.Then again
Be placed in Muffle furnace, with 10 DEG C/min rise to 600 DEG C heat preservation 6h after natural cooling, obtain that there is spongy nano-porous structure
Gamma-alumina.
The SEM of gamma-alumina made from the embodiment is as shown in fig. 6, from fig. 6, it can be seen that gamma-alumina is in bulk form
In the presence of length is 3 μm, and rib width is 1.85 μm, and there is apparent hole similar to Example 1 on surface.
Embodiment 3
A kind of sponge structure γ-Al2O3The preparation method of material, steps are as follows：
It is silicon source to take 0.467g, 3.46mmol aluminium chloride, and the 2,6-naphthalenedicarboxylic acid of 0.378g, 1.73mmol are ligand, chlorine
Change Al in aluminium: the molar ratio of organic ligand is 2: 1, and the drug weighed up is mixed with 5mL water respectively, stirs evenly, sequentially adds
In ptfe autoclave, with the heating rate of 3 DEG C/min, 200 DEG C are warming up to, thermal response 12h.After reaction, temperature
It is cooled to room temperature taking-up, sediment is washed with deionized, and 60 DEG C of dryings finally obtain alumina precursor.Before aluminium oxide
Drive body be placed in tube furnace, in a nitrogen atmosphere with 10 DEG C/min from room temperature rise to 800 DEG C heat preservation 3h after natural cooling, then again
Be placed in Muffle furnace, with 5 DEG C/min rise to 600 DEG C heat preservation 4h after natural cooling, obtain that there is spongy nano-porous structure
Gamma-alumina.
Embodiment 4
A kind of sponge structure γ-Al2O3The preparation method of material, steps are as follows：
It is silicon source to take 0.96g, 2.8mmol aluminum sulfate, and the 4 4'- biphenyl dicarboxylic acids of 0.52g, 2.14mmol are ligand, sulphur
Al in sour aluminium: the molar ratio of organic ligand is 1.3: 1, and the drug weighed up is dissolved in 30mL n,N-Dimethylformamide respectively
(DMF), it mixes, stirs evenly in equal volume after dissolving, be placed in ptfe autoclave, with the heating rate of 3 DEG C/min, rise
Temperature is to 120 DEG C, and thermal response is for 24 hours.After reaction, temperature is cooled to room temperature taking-up, and sediment is washed with DMF, and 60 DEG C of dryings obtain
To alumina precursor.Presoma is placed in tube furnace, 700 DEG C of heat preservations are risen to from room temperature with 10 DEG C/min in a nitrogen atmosphere
Natural cooling after 2h, is then placed in Muffle furnace again, with 10 DEG C/min rise to 500 DEG C heat preservation 5h after natural cooling, had
The gamma-alumina of spongy nano-porous structure.
Embodiment 5
A kind of sponge structure γ-Al2O3The preparation method of material, steps are as follows：
Take 0.053g, 3.46mmol aluminium chloride is silicon source, azobenzene -4,4- dicarboxylic acids of 0.107g, 1.73mmol be with
Body, Al in aluminium chloride: the molar ratio of organic ligand is 2: 1, and the drug weighed up is mixed with 5mL DMF respectively, is stirred evenly, according to
In secondary addition ptfe autoclave, with the heating rate of 3 DEG C/min, 180 DEG C are warming up to, thermal response 15h.Reaction terminates
Afterwards, temperature is cooled to room temperature taking-up, and sediment is washed with DMF, and 60 DEG C of dryings obtain alumina precursor.Presoma is placed in
In tube furnace, in a nitrogen atmosphere with 3 DEG C/min from room temperature rise to 700 DEG C heat preservation 2h after natural cooling, be then placed in Muffle again
In stove, natural cooling after 600 DEG C of heat preservation 6h is risen to 10 DEG C/min, obtains having the γ of spongy nano-porous structure to aoxidize
Aluminium.
Comparative example 1
A kind of γ-Al2O3The preparation method of material is carried out by method described in embodiment 1, the difference is that, 1 is selected,
3,5- trimesic acids prepare alumina precursor as organic ligand, remaining method and step obtain corresponding with embodiment 1
Gamma-alumina, internal structure are as shown in Figure 7.
Fig. 7 and Fig. 2 is compared, it can be clearly seen that, Fig. 7 material internals are solid construction, do not form spongelike structure, because
The selection of this organic ligand is most important to the formation of spongelike structure.
Experimental example
Using spongy aluminium oxide made from embodiment 1 and comparative example 1 as carrier, it is (Co) MoS to be prepared for active component2's
Hydrobon catalyst, specific preparation method are as follows：
(1) 0.5g alumina powders are weighed, its water absorption rate is surveyed.
(2) by the water absorption rate measured in step 1, the water of corrresponding quality is weighed, by 0.655g cobalt nitrate hexahydrates and 0.1326g
Ammonium heptamolybdate is dissolved, and clear maceration extract is configured to.
(3) maceration extract is added dropwise in alumina support, and is stirred continuously to maceration extract and fully absorbs, is uniformly mixed.
A night is stood at room temperature.
(4) the above catalyst precursor is placed in drying in 120 DEG C of baking ovens, is subsequently placed at 500 DEG C and roasts 3h, must aoxidizes
State catalyst.
(5) the above oxidized catalyst is placed in tube furnace, is passed through H2S/H2Gaseous mixture (volume ratio 10:90, gas
Flow velocity is 100mLmin-1), tube furnace is warming up to 400 DEG C of reaction 4h, room temperature is then down to, obtains that there is catalytic activity
Sulphided state catalyst.
Using dibenzothiophenes as raw material, the reactivity of sulphided state catalyst is investigated, as shown in table 1.
1 embodiment 1 of table, the Hydrobon catalyst desulfurization results table that comparative example 1 is carrier
It can reflect from the comparison of above-mentioned desulfurization effect, be aoxidized with the γ with spongy nano-porous structure of the present invention
Aluminium, which is the catalyst of carrier, has very strong reactivity, significantly larger than the catalyst reaction activity of comparative example 1, therefore, has
The gamma-alumina of spongy nano-porous structure increases specific surface area, is conducive to the high degree of dispersion of active component；Internal gutter
It is connected to outside, is conducive to the diffusion of reactant and product molecule, to make catalyst reaction activity get a promotion.
Above-described embodiment 1-5 is not limitation of the invention, and in the actual production process, technological parameter and proportioning can
Meet needed for production by multiple amplification.Under the guide of above-described embodiment 1-5, other combination this field skills not enumerated
Art personnel can obviously realize.
It should be noted that any equivalent way that those skilled in the art are made under the introduction of this specification, or
Obvious variant should all be within the scope of the present invention.
Claims (10)
1. a kind of sponge structure γ-Al2O3Material, for the gamma-alumina material in threadiness or bulk, fibre length is 1-3 μm, fine
Dimension rib width is 400-500nm, and blocky length is 1-5 μm, and blocky width is 0.8-3 μm；With spongy nano-porous structure, table
Face has hole, internal gutter to be connected to outside, specific surface area 300-350m2/ g, hole hold 0.5-0.8cm3/ g, pore-size distribution
Concentrate on 2-20nm, most probable pore size 6-10nm.
2. a kind of preparation method of sponge structure gamma-alumina, including steps are as follows：
(1) silicon source is dissolved in solvent a, organic ligand is dissolved in solvent b by obtained solution a, obtained solution b；By solution a with
It is sufficiently stirred after solution b mixing, thermal response postcooling is filtered, washed, dries, and obtains faint yellow alumina precursor；
(2) alumina precursor is warming up to 300-1000 DEG C under inert gas protection to calcine 0.5-12 hours, it is cooling, it obtains
Aluminium oxide intermediate；
(3) aluminium oxide intermediate is warming up to 400-900 DEG C of heat treatment 2-12h in air atmosphere, being made has spongy receive
γ-the Al of rice porous structure2O3Material.
3. the preparation method of sponge structure gamma-alumina according to claim 2, which is characterized in that described in step (1)
Silicon source is aluminum perchlorate, aluminium acetate, aluminum sulfate, aluminium chloride, aluminum nitrate, aluminium bromide, silver iodide, aluminum fluoride, alum 12
One or more of hydrate, aluctyl, aluminium secondary butylate, aluminium isopropoxide or aluminium acetylacetonate mix.
4. the preparation method of sponge structure gamma-alumina according to claim 2, which is characterized in that described in step (1)
Organic ligand is Isosorbide-5-Nitrae-terephthalic acid (TPA), M-phthalic acid, Isosorbide-5-Nitrae-naphthalene dicarboxylic acids, 2,3- naphthalene dicarboxylic acids, 2,6- naphthalene dicarboxylic acids, 4
One or more of 4'- biphenyl dicarboxylic acids or azobenzene -4,4- dicarboxylic acids mix.
5. the preparation method of sponge structure gamma-alumina according to claim 2, which is characterized in that described in step (1)
Solvent a is one kind in methanol, ethyl alcohol, deionized water or n,N-Dimethylformamide, and the solvent b is methanol, ethyl alcohol, goes
One kind in ionized water or N,N-dimethylformamide.
6. the preparation method of sponge structure gamma-alumina according to claim 2, which is characterized in that described in step (1)
The molar ratio of aluminium element and organic ligand is (0.1-4) in silicon source：1, the molar ratio of aluminium element and solvent a is in the silicon source
0.5：The molar ratio of (20-50), the ligand and solvent b are 0.5：(20-50).
7. the preparation method of sponge structure gamma-alumina according to claim 2, which is characterized in that described in step (1)
Thermal response be system react 10-75h at 150-220 DEG C.
8. the preparation method of sponge structure gamma-alumina according to claim 2, which is characterized in that in step (2), calcining
Temperature is 600-900 DEG C, and calcination time is 2-5 hours.
9. the preparation method of sponge structure gamma-alumina according to claim 2, which is characterized in that in step (2), heating
Rate is 1-10 DEG C/min, and the inert atmosphere is one kind in nitrogen, helium or argon gas, inert gas flow velocity 1-500mL/
min；It is further preferred that the inert gas flow velocity is 20-100mL/min.
10. the preparation method of sponge structure gamma-alumina according to claim 2, which is characterized in that in step (3), heat
Treatment temperature is 400-600 DEG C, and heat treatment time is 2-7 hours, and heating rate is 1-20 DEG C/min, it is preferred that heating rate
For 5-10 DEG C/min.
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| CN109894088A (en) * | 2019-04-23 | 2019-06-18 | 巢湖学院 | A kind of synthetic method of porous, crystallization the metal covalent organic frame material of two dimension containing aluminium and material obtained |
| CN111318294A (en) * | 2018-12-13 | 2020-06-23 | 中国石油化工股份有限公司 | Hydrotreating catalyst and preparation method and application thereof |
| CN111943242A (en) * | 2019-05-17 | 2020-11-17 | 国家能源投资集团有限责任公司 | Mesoporous gamma-Al2O3Preparation method of carrier and mesoporous gamma-Al2O3Carrier |
| CN112501605A (en) * | 2020-12-01 | 2021-03-16 | 湖北超卓航空科技股份有限公司 | Preparation method of functional composite cold spray coating |
| CN112717984A (en) * | 2019-10-28 | 2021-04-30 | 中国石油化工股份有限公司 | Hydrocracking catalyst, and preparation method and application thereof |
| CN112850764A (en) * | 2021-01-26 | 2021-05-28 | 大连理工大学 | Method for preparing shape-controllable aluminum oxide hollow microspheres without template agent |
| CN113248200A (en) * | 2021-05-10 | 2021-08-13 | 北京固斯特国际化工有限公司 | Permeable cross-linked reinforcing anticorrosive material for concrete cooling tower and application thereof |
| CN114057505A (en) * | 2021-12-13 | 2022-02-18 | 西安邮电大学 | Preparation method of porous flaky alumina framework |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111318294A (en) * | 2018-12-13 | 2020-06-23 | 中国石油化工股份有限公司 | Hydrotreating catalyst and preparation method and application thereof |
| CN109894088A (en) * | 2019-04-23 | 2019-06-18 | 巢湖学院 | A kind of synthetic method of porous, crystallization the metal covalent organic frame material of two dimension containing aluminium and material obtained |
| CN109894088B (en) * | 2019-04-23 | 2021-07-30 | 巢湖学院 | Synthetic method of aluminum-containing two-dimensional porous and crystalline metal covalent organic framework material and prepared material |
| CN111943242A (en) * | 2019-05-17 | 2020-11-17 | 国家能源投资集团有限责任公司 | Mesoporous gamma-Al2O3Preparation method of carrier and mesoporous gamma-Al2O3Carrier |
| CN111943242B (en) * | 2019-05-17 | 2022-12-23 | 国家能源投资集团有限责任公司 | Mesoporous gamma-Al 2 O 3 Preparation method of carrier and mesoporous gamma-Al 2 O 3 Carrier |
| CN112717984A (en) * | 2019-10-28 | 2021-04-30 | 中国石油化工股份有限公司 | Hydrocracking catalyst, and preparation method and application thereof |
| CN112501605A (en) * | 2020-12-01 | 2021-03-16 | 湖北超卓航空科技股份有限公司 | Preparation method of functional composite cold spray coating |
| CN112850764A (en) * | 2021-01-26 | 2021-05-28 | 大连理工大学 | Method for preparing shape-controllable aluminum oxide hollow microspheres without template agent |
| CN113248200A (en) * | 2021-05-10 | 2021-08-13 | 北京固斯特国际化工有限公司 | Permeable cross-linked reinforcing anticorrosive material for concrete cooling tower and application thereof |
| CN114057505A (en) * | 2021-12-13 | 2022-02-18 | 西安邮电大学 | Preparation method of porous flaky alumina framework |
| CN114057505B (en) * | 2021-12-13 | 2023-02-28 | 西安邮电大学 | Preparation method of porous flaky alumina framework |
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Effective date of registration: 20221207 Address after: 251800 Gongye 9th Road, Economic Development Zone, Yangxin County, Binzhou City, Shandong Province Patentee after: Shandong Yangxin Longtai Chemical Technology Co.,Ltd. Address before: 266580 No. 66 Changjiang West Road, Huangdao District, Qingdao, Shandong. Patentee before: CHINA University OF PETROLEUM (EAST CHINA) |