CN108101081A - A kind of preparation method of modified aluminas - Google Patents
A kind of preparation method of modified aluminas Download PDFInfo
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- CN108101081A CN108101081A CN201611052882.1A CN201611052882A CN108101081A CN 108101081 A CN108101081 A CN 108101081A CN 201611052882 A CN201611052882 A CN 201611052882A CN 108101081 A CN108101081 A CN 108101081A
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- aluminium oxide
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- deionized water
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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
- C01F7/021—After-treatment of oxides or hydroxides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- 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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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- 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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Abstract
The present invention provides a kind of preparation method of modified aluminas, and the aluminium oxide is gamma-alumina, and the surface area of aluminium oxide is 100~500m2/ g, pore volume are 0.1~0.6cm3/g.Aluminium oxide with deionized water is mixed, stirred, is dry by the preparation method；It mixes, stir with ethyl alcohol again, is dry, then handling at a certain temperature；It mixes, stir with auxiliary agent, deionized water again, be then directly separated dry and high-temperature process；Then mix, stir with auxiliary agent, deionized water again, be then directly separated dry and high-temperature process and obtain modified aluminas product.Aluminium oxide provided by the invention have alkalescence can modulation feature, meet adsorbent and carrier to aluminium oxide Bu Tong alkalescence matter the needs of.
Description
Technical field
The present invention relates to a kind of alumina preparation method, particularly a kind of alkaline matter can modulation alumina preparation method.
Background technology
Aluminium oxide is a kind of industrial important porous material, is widely used as catalyst carrier and adsorbent etc..It is existing
In technology, prepared on aluminium oxide and modified technology is primarily directed to the acidity for improving aluminium oxide, adjust pore structure, Yi Jigai
Kind structural stability etc..Patent CN104588011A alkane dehydrogenating catalysts and preparation method thereof, using alcohols modification side
Method handles aluminium oxide.Detailed process is：Sn alumina supports heating vacuumize process will be contained, then add in alcohol under vacuum conditions
Class solvent recovers normal pressure, is heated to reflux handling.The patent describes, and alcohols solvent carries out surface to the alumina support for loading Sn
Modified, alcohol solvent molecules can preferentially occupy the adsorption potential of alumina carrier surface containing Sn, the anchor that active metal Pt can be oriented
Surely exposed Sn surfaces are arrived, Pt-Sn is made to generate synergistic effect, improves the selectivity of propylene and the activity stability of catalyst.Together
When modification can save dechlorination process, avoid the agglomeration of Pt particles；Catalyst surface acidity can be also reduced, inhibits carbon distribution,
Improve catalyst stability.
The drinking water adsorption-defluorination device and method of patent CN103693771A plural serial stages, discloses a kind of aluminium oxide
Method of modifying.Its method of modifying is by activated alumina filling device, with clear water filtration and washing filtrate, then uses bodied ferric sulfate
And/or ferric sulfate aqueous solution circulating filtration, then exhaust iron salt solutions；Then filtrate is rinsed with clear water, obtains modification with Fe suction
Attached dose.This method can improve the efficiency of fluorine removal.The inventor is " long run test of modified activated aluminum oxide adsorption-defluorination is ground
Study carefully "（Beijing University of Chemical Technology's journal (natural science edition), the third phases of volume 39 in 2012）, the modification theory of ferric sulfate is done and is understood
It releases, it is believed that Fe only forms unformed deposition on the surface of activated alumina, and modified activated alumina adsorbents surface particles become
Small, surface free energy increases, absorption property enhancing, promotes the surface precipitation of fluorine ion.
Patent CN102847541A Coal tar hydrodemetalization catalysts and preparation method thereof, disclose a kind of aluminium oxide
Method of modifying.Whole operation step is first to take or prepare alumina support；Aluminium oxide is handled with organic acid soln again, then uses nitre
The aluminium oxide of sour aluminum solutions dipping, finally dry, roasting obtain modified aluminium oxide supports；Then hydrogenation active component is loaded, is obtained
To Hydrodemetalation catalyst.The activity and activity stability of catalyst can be improved by modified method, delays catalysis
The service cycle of agent.
A kind of alumina modified method is disclosed in the method for purification of patent CN102850175B coking benzenes, method is to use
The ethanol solution that concentration is 50%~70% rinses activated alumina, and concentration is put into after dry at 110~150 DEG C as 0.5~1.0
It is handled in the aluminum sulfate solution of mol/L；It is multiple with pure water rinsing again；Finally drying roasting obtains the acidic oxidation of aluminum sulfate modification
Aluminium.When modified aluminium oxide purifies for coking benzene, it can preferably remove the sulphur compound in raw material coking benzene, nitrogenize
The impurity such as object, moisture, micro tar heavy constituent, solid residue improve the quality of coking benzene.
Patent CN1953806A prepares method and the use of active chromium/aluminium oxide catalyst by using sulfuric acid salt treatment
The polymer of the chromium/aluminium oxide catalyst production is directed to the modification technology of aluminium oxide.These patents are all with sulfuric acid salt treatment
Alumina support, the method are that sulfate with aluminium oxide effect is roasted or aoxidized with sulfuric acid salt treatment simultaneously with chromium again
Acted on again with chromium after aluminium roasting etc..And think that sulfate provides acidity for chromium, and cause aluminium oxide a small amount of or be not sintered.
A kind of alumina in high hydrothermal stability of patent CN100431964C and preparation method thereof, is related to aluminium oxide
Method of modifying.Its method is that phosphorous species such as ammonium phosphate, ammonium hydrogen phosphate or phosphoric acid are dissolved in deionized water, and aluminium oxide is impregnated
Modified ball-aluminium oxide is obtained in solution, then through drying and roasting.The invention introduces phosphate anion, makes itself and aluminium oxide
The hydroxyl reaction of hole wall reduces the quantity of hydroxyl, prevents the sintering and phase transformation in aluminium oxide duct, and it is steady to reach raising aluminium oxide hydro-thermal
Qualitatively purpose.
The catalyst that patent CN1063099C is used to prepare propylene glycol discloses a kind of method of modifying of aluminium oxide.It is described
Aluminium oxide is first carried out reaming modification by method with acid or alkali, then impregnates alkali metal fluoride.Wherein specific soda acid processing side
Method is acid or soda-dip processing aluminium oxide, is after cooling 7 with deionised water to pH value, then dries.Soda acid processing
Purpose expands the duct of aluminium oxide.
A kind of alumina supports of siliceous and titanium of patent CN1331605C and preparation method thereof, in the patent auxiliary agents of silicon be
It is introduced during aluminium hydroxide plastic, specific surface area, aperture and the pore volume that can be improved；Auxiliary agent titanium is after plastic, aging
Preceding addition, can greatly improve carrier surface acid amount and B acid amounts.This external application titanium modifies oxidation aluminium surface, weakens activity gold
Belong to the interaction with carrier, improve the dispersiveness of active metal.
A kind of production methods of modified aluminas of patent CN101069832.Its main method of modifying is with acetic acid and chlorination
Palladium handles aluminium hydroxide, and aluminium oxide is then made, and improves large specific surface area with this, increases the rate of filtration.
" modification of aluminium oxide and its application in directed preparing dimethyl ether by synthetic gas reaction "（Catalysis journal, 2006）With
Anion-modified γ-the Al of oxygen-containing acid group of boron, p and s2O3, for Dehydration of methanol, it is found that modified by sulfate radicle can be notable
Improve γ-Al2O3Methanol dehydration activity, boron modification then reduces methanol dehydration activity, and although P Modification improves dehydration anti-
The activity answered, but the amplitude very little improved.
In chemical engineering industry, aluminium oxide is used mainly as acid carrier or adsorbent.But actually aluminium oxide is a kind of
Soda acid amphoteric compound, compared to Acidity, alkalescence is weaker.So aluminium oxide is carried generally by some alkaline matters are loaded
Its high alkaline matter.Such as by KOH and K2CO3Alkaline matters is waited to load to Al2O3Surface, so that it may generate preferable basic sites；By alkali
The carbonate or acetate of the Cs of property loads to Al2O3Surface, pyrolytic can generate super base position.Patent CN103508864A
A kind of preparation method of 2- isopropyls -5- methyl -2- hexenoic aldehydes, the modified method for improving aluminium oxide alkalescence being related to.It is modified
Method is carrying alkali metal hydroxide or alkali carbonate using aluminium oxide as carrier.
A kind of Supported palladium catalysts of patent CN103691437A and preparation method thereof, the modified raising oxygen being related to
Change the method for aluminium alkalescence.Method of modifying is to add in aluminium oxide in lanthanum salt solution to impregnate, and is adsorbed and is done under vacuum
Dry, high-temperature calcination obtains modified catalyst carrier.Modification can inhibit Al during high-temperature process2O3The growth of crystal grain, enhancing
Carrier surface alkalescence, increases surface area, improves the Pd concentration of catalyst surface, reduces Pd layer thickness, so as to improve catalyst
Hydrogenation activity and selectivity.
In present chemical industry, aluminium oxide is a kind of very important industrial carrier and sorbing material.Although aluminium oxide
It prepares and is modified the significant progress having been achieved with, but increasingly harsh Green Chemistry and environmentally friendly chemistry urge aluminium oxide etc.
That changes material proposes higher requirement, this just needs to develop new aluminium oxide preparation and modification technology, to meet different answer
With demand and environmental requirement.
The content of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of modified aluminas preparation method, prepared by the method for the present invention
Obtained modified aluminas be a kind of alkaline matter can modulation aluminium oxide, preparation method is simple and practicable, low production cost.
The present invention provides a kind of preparation method of modified aluminas, and the crystal structure of the modified aluminas is gamma oxidation
Aluminium, the surface area of modified aluminas is 100~500m2/ g, pore volume are 0.1~0.6cm3/ g, the alkali number ratio of the modified aluminas
The alkali number of native oxide aluminum feedstock reduces by 0.1~99%, and the preparation method comprises the following steps：
（1）Aluminium oxide and deionized water are mixed and stirred for uniformly, then dry 10~20 h at 100~180 DEG C；
（2）By step（1）Obtained aluminium oxide is mixed and stirred for uniformly with ethyl alcohol, dry 10~20 h at 100~180 DEG C,
Then processing is 1~7 h at 200~320 DEG C；
（3）By step（2）Aluminium oxide, auxiliary agent, deionized water is obtained to be mixed and stirred for uniformly, being then directly separated by filtration drying；
（4）By step（3）Obtained substance 1~12 h of calcination process at 400~650 DEG C in a nitrogen atmosphere；
（5）By step（4）Obtained aluminium oxide, auxiliary agent, deionized water are mixed and stirred for uniformly, are then directly separated by filtration dry
It is dry；
（6））By step（5）Obtained substance 1~12 h of calcination process at 400~650 DEG C in a nitrogen atmosphere, is modified
Alumina product.
In the method for the present invention, step（1）Described in aluminium oxide for gama-alumina, the gama-alumina can be commercially available
Commodity or self-control.
In the method for the present invention, step（1）Described in aluminium oxide and deionized water mass ratio be 0.5~5：10, preferably
For 1~4：10.
In the method for the present invention, step（1）Described in drying temperature for 110~170 DEG C, drying time is 12~18h.
In the method for the present invention, step（2）Described in ethyl alcohol be absolute ethyl alcohol.
In the method for the present invention, step（2）Described in aluminium oxide and ethyl alcohol mass ratio be 0.5~5：10, it is preferably 1~4：
10。
In the method for the present invention, step（2）The drying temperature is 110~170 DEG C；Drying time is 12~18h.
In the method for the present invention, step（3）Described in auxiliary agent be copper nitrate or aluminium chloride.
In the method for the present invention, step（3）Described in aluminium oxide, auxiliary agent, deionized water mass ratio be 1~30：0.05
~60：100, it is preferably 1.5~28：0.1~55：100.
In the method for the present invention, step（3）It is described to be directly separated as without washing or other solvent washing operations, directly
It is filtered separation.
In the method for the present invention, step（3）The drying temperature is 100~180 DEG C, preferably 110~170 DEG C；When dry
Between for 10~20 h, be preferably 12~18h.
In the method for the present invention, step（4）Described in treatment temperature be 450~600 DEG C, processing time be 2~10h.
In the method for the present invention, step（5）Described in aluminium oxide, auxiliary agent, deionized water mass ratio be 1~30：0.05
~30：100, it is preferably 1.5~28：0.1~28：100.
In the method for the present invention, step（5）Described in auxiliary agent be copper nitrate or aluminium chloride.
In the method for the present invention, step（5）It is described to be directly separated as without washing or other solvent washing operations, directly
It is filtered separation.
In the method for the present invention, step（5）The drying temperature is 100~180 DEG C, preferably 110~170 DEG C；When dry
Between for 10~20 h, be preferably 12~18h.
In the method for the present invention, step（6）Described in treatment temperature be 450~600 DEG C, processing time be 2~10h.
Aluminium oxide alkalescence provided by the invention uses carbon dioxide temperature programmed desorption (CO2- TPD) method characterization, it is used
Instrument is the 2920 type chemical adsorption instruments of AutoChem of Merck ＆ Co., Inc of U.S. production.Embodiments process is：Sample is existed
300 DEG C of processing 1h in 30mL/min helium atmospheres；Then 70 DEG C are cooled to, in 30mL/min CO2-He（CO25%, He is accounted for account for
95%）2h is handled in atmosphere；Then in 30mL/min He atmosphere, 70 DEG C of processing 1h；Finally in the He atmosphere of 10mL/min,
The CO of sample is carried out with 10 DEG C/min rates2- TPD is characterized.The calculating of alkali number uses integrating peak areas method, with native aluminum oxide
Alkali number is 100%, passes through the alkali number of peak area comparing calculation aluminium oxide of the present invention.
Other physico-chemical properties of modified aluminas provided by the invention are using other conventional characterizing method characterizations.
Aluminium oxide provided by the invention is alkaline adjustable alumina oxide, and the alkali of aluminium oxide can be adjusted according to actual demand
Property.Adsorbent and catalyst carrier are may be used as, meets the needs of adsorbent and carrier to the different alkaline matter of aluminium oxide.
Compared with existing alumina material, modified aluminas prepared by the method for the present invention have alkaline matter can modulation spy
Point especially reduces the characteristics of alkaline on demand.Preparation method of the present invention mainly utilizes additive modification aluminium oxide, in of the invention
The auxiliary agent of use can accurately and with high selectivity the basic sites with aluminium oxide be had an effect, and aluminium oxide alkalescence is reduced so as to play
Effect；It is physically or chemically acted on without active sites other with aluminium oxide generation, because of the crystal structure without changing aluminium oxide, hole
The physico-chemical properties such as structure, therefore alkaline matter can be only adjusted, do not change the other feature of aluminium oxide substantially.This point and other oxidations
The modification technology of aluminium is different, and other technologies are that other other elements are introduced in aluminium oxide, and the shape characteristic hole of aluminium oxide is tied
Structure thermal property etc. has change.And the method for the present invention also adds in the operation of auxiliary agent using substep, can so greatly promote oxygen
Change the modified effect of aluminium.Because for copper nitrate and aluminium chloride both auxiliary agents, the compounding agent solution of high concentration is not strengthened
With the effect of the basic sites of aluminium oxide, and it auxiliary agent is come to modified aluminas in two steps can obtain instead to help better than single high concentration
The effect of agent processing.The preparation method of aluminium oxide provided by the invention, operating procedure is simple and practicable, raw materials used cheap and easy to get,
Low production cost is easy to industrialized production.
Description of the drawings
Fig. 1 is the CO of sample and native oxide aluminum feedstock that embodiment 1 is prepared2- TPD spectrograms.
The CO of the sample that Fig. 2 positions embodiment 6 is prepared and native oxide aluminum feedstock2- TPD spectrograms.
Specific embodiment
The preparation method of aluminium oxide of the present invention is described in detail below by specific embodiment, but is not limited to
Embodiment.
Embodiment 1
（1）10g aluminium oxide with 100mL deionized waters is mixed, stirs 30 min, then 150 DEG C of dry 15h；
（2）By step（1）It obtains aluminium oxide to mix with 100mL ethyl alcohol, stirs 30 min, then 150 DEG C of dry 15h, then exist
260 DEG C of processing 4h；
（3）By step（2）It obtains aluminium oxide to mix with 12g aluminium chloride, 100mL deionized waters, stirs 5h, then directly filtering point
From then 150 DEG C of dry 15h；
（4）By step（3）Obtained substance 500 DEG C of processing 6h in nitrogen atmosphere；
（5）By step（4）It obtains aluminium oxide to mix with 12g aluminium chloride, 100mL deionized waters, stirs 5h, then directly filtering point
From then 150 DEG C of dry 15h；
（6）By step（5）Obtained substance 500 DEG C of processing 6h in nitrogen atmosphere, finally obtain modified aluminas.Gained sample
Number CL1, the alkaline matter of gained sample are shown in Fig. 1, and other properties are shown in Table 1.It was found from Fig. 1 and table 1, the alkali of modified aluminium oxide
It measures as the 28.8% of native aluminum oxide, surface area 207m2/ g illustrates that the method for the present invention can effectively reduce the alkalescence of aluminium oxide,
And other properties of aluminium oxide are not changed substantially.
Embodiment 2
（1）10g aluminium oxide with 90mL deionized waters is mixed, stirs 30 min, then 140 DEG C of dry 15h；
（2）By step（1）It obtains aluminium oxide to mix with 90mL ethyl alcohol, stirs 30 min, then 140 DEG C of dry 15h, then exist
265 DEG C of processing 4h；
（3）By step（2）It obtains aluminium oxide to mix with 10g aluminium chloride, 90mL deionized waters, stirs 4h, then directly filtering point
From then 150 DEG C of dry 15h；
（4）By step（3）Obtained substance 500 DEG C of processing 5h in nitrogen atmosphere；
（5）By step（4）It obtains aluminium oxide to mix with 10g aluminium chloride, 100mL deionized waters, stirs 5h, then directly filtering point
From then 150 DEG C of dry 15h；
（6）By step（5）Obtained substance 500 DEG C of processing 5h in nitrogen atmosphere, finally obtain modified aluminas.Gained sample
Number CL2, the physico-chemical property of gained sample are shown in Table 1.
Embodiment 3
（1）10g aluminium oxide with 90mL deionized waters is mixed, stirs 30 min, then 140 DEG C of dry 15h；
（2）By step（1）It obtains aluminium oxide to mix with 90mL ethyl alcohol, stirs 30 min, then 140 DEG C of dry 15h, then exist
260 DEG C of processing 4h；
（3）By step（2）It obtains aluminium oxide to mix with 8g aluminium chloride, 100mL deionized waters, stirs 6h, then directly filtering point
From then 150 DEG C of dry 15h；
（4）By step（3）Obtained substance 450 DEG C of processing 6h in nitrogen atmosphere；
（5）By step（4）It obtains aluminium oxide to mix with 8g aluminium chloride, 100mL deionized waters, stirs 5h, then directly filtering point
From then 150 DEG C of dry 15h；
（6）By step（5）Obtained substance 450 DEG C of processing 6h in nitrogen atmosphere, finally obtain modified aluminas.Gained sample
Number CL3, the physico-chemical property of gained sample are shown in Table 1.
Embodiment 4
（1）18g aluminium oxide with 100mL deionized waters is mixed, stirs 30 min, then 140 DEG C of dry 15h；
（2）By step（1）It obtains aluminium oxide to mix with 100mL ethyl alcohol, stirs 30 min, then 140 DEG C of dry 15h, then exist
235 DEG C of processing 4h；
（3）By step（2）It obtains aluminium oxide to mix with 3.8g aluminium chloride, 100mL deionized waters, stirs 8h, then directly filter
It separates, then 150 DEG C of dry 15h；
（4）By step（3）Obtained substance 600 DEG C of processing 6h in nitrogen atmosphere；
（5）By step（4）It obtains aluminium oxide to mix with 3g aluminium chloride, 100mL deionized waters, stirs 8h, then directly filtering point
From then 150 DEG C of dry 15h；
（6）By step（5）Obtained substance 600 DEG C of processing 6h in nitrogen atmosphere, finally obtain modified aluminas.Gained sample
Number CL4, the physico-chemical property of gained sample are shown in Table 1.
Embodiment 5
（1）12g aluminium oxide with 100mL deionized waters is mixed, stirs 30 min, then 140 DEG C of dry 15h；
（2）By step（1）It obtains aluminium oxide to mix with 100mL ethyl alcohol, stirs 30 min, then 140 DEG C of dry 15h, then exist
260 DEG C of processing 4h；
（3）By step（2）It obtains aluminium oxide to mix with 4g aluminium chloride, 100mL deionized waters, stirs 7h, then directly filtering point
From then 150 DEG C of dry 15h；
（4）By step（3）Obtained substance 550 DEG C of processing 6h in nitrogen atmosphere；
（5）By step（4）It obtains aluminium oxide to mix with 2g aluminium chloride, 100mL deionized waters, stirs 5h, then directly filtering point
From then 150 DEG C of dry 15h；
（6）By step（5）Obtained substance 550 DEG C of processing 6h in nitrogen atmosphere, finally obtain modified aluminas.Gained sample
Number CL5, the physico-chemical property of gained sample are shown in Table 1.
Embodiment 6
（1）10g aluminium oxide with 100mL deionized waters is mixed, stirs 30 min, then 150 DEG C of dry 15h.
（2）By step（1）It obtains aluminium oxide to mix with 100mL ethyl alcohol, stirs 30 min, then 150 DEG C of dry 15h, connect
It and handles 4h at 260 DEG C.
（3）By step（2）It obtains aluminium oxide to mix with 10g copper nitrates, 100mL deionized waters, stirs 5h, then direct mistake
Filter separates, then 150 DEG C of dry 15h.
（4）By step（3）Obtained substance 500 DEG C of processing 6h in nitrogen atmosphere.
（5）By step（4）It obtains aluminium oxide to mix with 10g copper nitrates, 100mL deionized waters, stirs 5h, then direct mistake
Filter separates, then 150 DEG C of dry 15h；
（6）By step（5）Obtained substance 550 DEG C of processing 6h in nitrogen atmosphere, finally obtain modified aluminas.Gained sample
Number CL6, the alkaline matter of gained sample are shown in Fig. 2, and other properties are shown in Table 1.It was found from Fig. 2 and table 1, the alkali of modified aluminium oxide
It measures as the 54.5% of native aluminum oxide, surface area 206m2/ g illustrates that the method for the present invention can effectively reduce the alkalescence of aluminium oxide,
And other properties of aluminium oxide are not changed substantially.
Embodiment 7
（1）10g aluminium oxide with 90mL deionized waters is mixed, stirs 30 min, then 140 DEG C of dry 15h；
（2）By step（1）It obtains aluminium oxide to mix with 90mL ethyl alcohol, stirs 30 min, then 140 DEG C of dry 15h, then exist
265 DEG C of processing 4h；
（3）By step（2）It obtains aluminium oxide to mix with 8.5g copper nitrates, 90mL deionized waters, stirs 4h, then directly filtering point
From then 150 DEG C of dry 15h；
（4）By step（3）Obtained substance 500 DEG C of processing 5h in nitrogen atmosphere；
（5）By step（4）It obtains aluminium oxide to mix with 8.5g copper nitrates, 100mL deionized waters, stirs 5h, then directly filter
It separates, then 150 DEG C of dry 15h；
（6）By step（5）Obtained substance 550 DEG C of processing 6h in nitrogen atmosphere, finally obtain modified aluminas.Gained sample
Number CL7, the physico-chemical property of gained sample are shown in Table 1.
Embodiment 8
（1）10g aluminium oxide with 90mL deionized waters is mixed, stirs 30 min, then 140 DEG C of dry 15h；
（2）By step（1）It obtains aluminium oxide to mix with 90mL ethyl alcohol, stirs 30 min, then 140 DEG C of dry 15h, then exist
260 DEG C of processing 4h；
（3）By step（2）It obtains aluminium oxide to mix with 8g copper nitrates, 100mL deionized waters, stirs 6h, then directly filtering point
From then 150 DEG C of dry 15h；
（4）By step（3）Obtained substance 450 DEG C of processing 6h in nitrogen atmosphere；
（5）By step（4）It obtains aluminium oxide to mix with 10g copper nitrates, 100mL deionized waters, stirs 5h, then directly filtering point
From then 150 DEG C of dry 15h；
（6）By step（5）Obtained substance 550 DEG C of processing 6h in nitrogen atmosphere, finally obtain modified aluminas.It finally obtains
Alkaline adjustable alumina oxide.Gained sample number into spectrum CL8, the physico-chemical property of gained sample are shown in Table 1.
Embodiment 9
（1）18g aluminium oxide with 100mL deionized waters is mixed, stirs 30 min, then 140 DEG C of dry 15h；
（2）By step（1）It obtains aluminium oxide to mix with 100mL ethyl alcohol, stirs 30 min, then 140 DEG C of dry 15h, then exist
235 DEG C of processing 4h；
（3）By step（2）It obtains aluminium oxide to mix with 2.6g copper nitrates, 100mL deionized waters, stirs 8h, then directly filter
It separates, then 150 DEG C of dry 15h；
（4）By step（3）Obtained substance 600 DEG C of processing 6h in nitrogen atmosphere；
（5）By step（4）It obtains aluminium oxide to mix with 3g copper nitrates, 100mL deionized waters, stirs 8h, then directly filtering point
From then 150 DEG C of dry 15h；
（6）By step（5）Obtained substance 600 DEG C of processing 6h in nitrogen atmosphere, finally obtain alkaline adjustable alumina oxide.Institute
Sample number into spectrum CL9 is obtained, the physico-chemical property of gained sample is shown in Table 1.
Embodiment 10
（1）12g aluminium oxide with 100mL deionized waters is mixed, stirs 30 min, then 140 DEG C of dry 15h；
（2）By step（1）It obtains aluminium oxide to mix with 100mL ethyl alcohol, stirs 30 min, then 140 DEG C of dry 15h, then exist
260 DEG C of processing 4h；
（3）By step（2）It obtains aluminium oxide to mix with 1g copper nitrates, 100mL deionized waters, stirs 7h, then directly filtering point
From then 150 DEG C of dry 15h；
（4）By step（3）Obtained substance 550 DEG C of processing 6h in nitrogen atmosphere；
（5）By step（4）It obtains aluminium oxide to mix with 1g copper nitrates, 100mL deionized waters, stirs 5h, then directly filtering point
From then 150 DEG C of dry 15h；
（6）By step（5）Obtained substance 550 DEG C of processing 6h in nitrogen atmosphere, finally obtain modified aluminas.Gained sample
Number CL10, the physico-chemical property of gained sample are shown in Table 1.
Comparative example 1
Contrast experiment is carried out using condition substantially the same manner as Example 1.
（1）10g aluminium oxide with 100mL deionized waters is mixed, stirs 30 min, then 150 DEG C of dry 15h；
（2）By step（1）It obtains aluminium oxide to mix with 100mL ethyl alcohol, stirs 30 min, then 150 DEG C of dry 15h, then exist
260 DEG C of processing 4h；
（3）By step（2）It obtains aluminium oxide to mix with 24g aluminium chloride, 100mL deionized waters, stirs 5h, then directly filtering point
From then 150 DEG C of dry 15h；
（4）By step（3）Obtained substance 500 DEG C of processing 6h in nitrogen atmosphere, finally obtain modified aluminas.Gained sample
Number CL11, the property of gained sample are shown in Table 1.As known from Table 1, the alkali number of modified aluminium oxide is native aluminum oxide
72.5%, the alkali number of embodiment 1 is the 28.8% of native aluminum oxide, although illustrating that this method can reduce the alkalescence of aluminium oxide,
Be no 1 step-by-step processing of embodiment effect it is good.
Comparative example 2
Contrast experiment is carried out using condition substantially the same manner as Example 6.
（1）10g aluminium oxide with 100mL deionized waters is mixed, stirs 30 min, then 150 DEG C of dry 15h.
（2）By step（1）It obtains aluminium oxide to mix with 100mL ethyl alcohol, stirs 30 min, then 150 DEG C of dry 15h, connect
It and handles 4h at 260 DEG C.
（3）By step（2）It obtains aluminium oxide to mix with 20g copper nitrates, 100mL deionized waters, stirs 5h, then direct mistake
Filter separates, then 150 DEG C of dry 15h.
（4）By step（3）Obtained substance 500 DEG C of processing 6h in nitrogen atmosphere, finally obtain modified aluminas.Gained
Sample number into spectrum CL12, as known from Table 1, the alkali number of modified aluminium oxide are the 90.2% of native aluminum oxide, the alkali number of embodiment 1
For the 54.5% of native aluminum oxide, although illustrating that this method can reduce the alkalescence of aluminium oxide, there is no embodiment 6 to locate step by step
The effect of reason is good.
The property of the sample obtained by embodiment of table 1
Note：CL0 is native aluminum oxide before modified in table 1, and the alkali number of sample is using the alkali number of CL0 as reference.
Claims (14)
1. a kind of preparation method of modified aluminas, the crystal structure of the modified aluminas is gama-alumina, modified aluminas
Surface area be 100~500m2/ g, pore volume are 0.1~0.6cm3/ g, the alkali number of the modified aluminas are more former than native aluminum oxide
The alkali number of material reduces by 0.1~99%, and the preparation method comprises the following steps：（1）Aluminium oxide and deionized water are mixed and stirred for
Uniformly, then dry 10~20 h at 100~180 DEG C；
（2）By step（1）Obtained aluminium oxide is mixed and stirred for uniformly with ethyl alcohol, dry 10~20 h at 100~180 DEG C,
Then processing is 1~7 h at 200~320 DEG C；
（3）By step（2）Aluminium oxide, auxiliary agent, deionized water is obtained to be mixed and stirred for uniformly, being then directly separated by filtration drying；
（4）By step（3）Obtained substance 1~12 h of calcination process at 400~650 DEG C in a nitrogen atmosphere；
（5）By step（4）Obtained aluminium oxide, auxiliary agent, deionized water are mixed and stirred for uniformly, are then directly separated by filtration dry
It is dry；
（6）By step（5）Obtained substance 1~12 h of calcination process at 400~650 DEG C in a nitrogen atmosphere, is modified
Alumina product.
2. according to the method for claim 1, it is characterised in that：Step（1）Described in aluminium oxide be gama-alumina.
3. according to the method for claim 1, it is characterised in that：Step（1）Described in aluminium oxide and deionized water matter
Amount is than being 0.5~5：10, it is preferably 1~4：10.
4. according to the method for claim 1, it is characterised in that：Step（1）Described in drying temperature for 110~170 DEG C,
Drying time is 12~18h.
5. according to the method for claim 1, it is characterised in that：Step（2）Described in ethyl alcohol be absolute ethyl alcohol.
6. according to the method for claim 1, it is characterised in that：Step（2）Described in aluminium oxide and ethyl alcohol mass ratio be
0.5~5：10, it is preferably 1~4：10.
7. according to the method for claim 1, it is characterised in that：Step（2）The drying temperature is 110~170 DEG C；It is dry
The dry time is 12~18h.
8. according to the method for claim 1, it is characterised in that：Step（3）Described in auxiliary agent be copper nitrate or aluminium chloride.
9. according to the method for claim 1, it is characterised in that：Step（3）Described in aluminium oxide, auxiliary agent, deionized water
Mass ratio be 1~30：0.05~60：100, it is preferably 1.5~28：0.1~55：100.
10. according to the method for claim 1, it is characterised in that：Step（3）And step（5）Described in be directly separated for
Without washing or other solvent washing operations, separation is directly filtered.
11. according to the method for claim 1, it is characterised in that：Step（3）And step（5）Described in drying temperature be
100~180 DEG C, preferably 110~170 DEG C；Drying time is 10~20 h, is preferably 12~18h.
12. according to the method for claim 1, it is characterised in that：Step（4）It is 450 with treatment temperature described in step (6)
~600 DEG C, processing time is 2~10h.
13. according to the method for claim 1, it is characterised in that：Step（5）Described in aluminium oxide, auxiliary agent, deionized water
Mass ratio be 1~30：0.05~30：100, it is preferably 1.5~28：0.1~28：100.
14. according to the method for claim 1, it is characterised in that：Step（5）Described in auxiliary agent be copper nitrate or chlorination
Aluminium.
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| CN102728396A (en) * | 2012-06-04 | 2012-10-17 | 华东理工大学 | Preparation method and application of gamma-alumina supported aluminum trichloride catalyst |
| CN102921436A (en) * | 2012-11-02 | 2013-02-13 | 华东理工大学 | Clean preparation method and application of modified AlCl3/gamma-Al2O3 catalyst |
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| CN114524444B (en) * | 2020-10-31 | 2024-02-09 | 中国石油化工股份有限公司 | Modification method of alumina |
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