CN110217812A - A method of aluminium oxide is prepared by crystal aluminum chloride - Google Patents
A method of aluminium oxide is prepared by crystal aluminum chloride Download PDFInfo
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- CN110217812A CN110217812A CN201910631208.6A CN201910631208A CN110217812A CN 110217812 A CN110217812 A CN 110217812A CN 201910631208 A CN201910631208 A CN 201910631208A CN 110217812 A CN110217812 A CN 110217812A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0248—Compounds of B, Al, Ga, In, Tl
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0274—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04 characterised by the type of anion
- B01J20/0288—Halides of compounds other than those provided for in B01J20/046
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/20—Halogens or halogen compounds
- B01D2257/204—Inorganic halogen compounds
- B01D2257/2047—Hydrofluoric acid
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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
- 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
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
Abstract
The present invention provides a kind of methods for preparing aluminium oxide by crystal aluminum chloride, the calcined crystalline aluminium chloride first at 200~350 DEG C, until forming the intermediate product of unformed shape, then calcine intermediate product at 1000~1300 DEG C and the aluminium oxide is made.The present invention also provides a kind of hydrogen fluoride adsorbents prepared by the method for the present invention.Resulting aluminium oxide significantly improves the adsorption capacity of hydrogen fluoride by the method for the invention, is highly suitable as the hydrogen fluoride adsorbent of commercial fluorided hydrogen absorbent, especially aluminium electrolytic industry, the method for the present invention simple process and low cost, environmental-friendly and convenient for operation.
Description
Technical field
The present invention relates to chemical materials preparation fields, and in particular to a method of aluminium oxide is prepared by crystal aluminum chloride.
Background technique
Hydrogen fluoride is a kind of poisonous gas pollutant, is listed in one of the gaseous pollutant of state key monitoring.If
People lives for a long time, work the contaminated area excessively high in hydrogen fluoride concentration, the fluorine-containing material of excess intake, will cause osteosclerosis,
Osteoproliferation and tracheitis etc. cause the diseases such as fluorosis of bone, seriously endanger human health.The excessive fluorine of plant absorption, it will shadow
The growth for arriving crops is rung, the plant underproduction, even withered etc. serious consequences are caused.Hydrogen fluoride gas in atmosphere is dissolved in rainwater
In after drop on workshop, equipment or other metal components with rainwater, it will cause irreclaimable heavy corrosion, influence
The service life of building reduces the normal use time limit of equipment.
Certain chemical industry smelting processes, as that can generate the harmful smoke containing hydrogen fluoride during aluminum electrolysis, disperse is in sky
In gas, working condition can be deteriorated, seriously affect the health of producers.China's aluminium electroloysis professional standard regulation, electrolytic aluminium
Total fluorine content is no more than 3mg/m in the exhaust gas that factory outwardly discharges3。
Aluminium oxide is easy to that chemical reaction occurs with hydrogen fluoride to form firm Al-F chemical bond, is a kind of preferable hydrogen fluoride
Adsorbent.Especially in aluminium electrolysis process, aluminium oxide, will not be to production process also simultaneously as the primary raw material for producing primary aluminum
In additionally introduce other impurities, therefore aluminium oxide is used to handle and adsorb the cigarette containing hydrogen fluoride generated in aluminium electrolysis process
Gas.
The aluminous fly-ash generated using coal fired power generation is known as " acid system oxygen as raw material, by aluminium oxide prepared by acid technological process
Change aluminium ", this acid oxidation aluminium can solve the resource recycling of flyash to a certain extent, and can alleviate the country
The status of bauxite resource anxiety.But since there are bigger differences in production technology with traditional Bayer process aluminium oxide, at present this
The surface topography of kind of acid oxidation aluminium, particle diameter distribution, specific surface area, surface active groups distribution etc. all with Bayer process aluminium oxide
With notable difference.Therefore, as can preparation has the acid oxidation aluminium of high adsorption to hydrogen fluoride, it not only can solve flyash
Recycling problem, moreover it is possible to promote the development of aluminium electroloysis industry, have important economy and society meaning.
Summary of the invention
The present inventor is provided one kind and is prepared by crystal aluminum chloride by the further investigation to crystal aluminum chloride hydrolytic process
The method of aluminium oxide, obtained aluminium oxide have very excellent absorption property to hydrogen fluoride.
The present invention also provides a kind of hydrogen fluoride adsorbents.
It is provided by the invention by crystal aluminum chloride prepare aluminium oxide method the following steps are included:
S1: the calcined crystalline chlorination at 200~350 DEG C in the inert atmosphere that vapor relative humidity is 0~100%
Aluminium, until forming the intermediate product of unformed shape, by the Cl content of intermediate product described in quality be 5~15%, H and O total content is
40~55%；And
S2: the intermediate product made from step S1 is calcined at 1000~1300 DEG C, the aluminium oxide is made.
Aluminium oxide is mainly chemisorption for the absorption of hydrogen fluoride, and in adsorption process, fluorination hydrogen molecule is directly connected in
The hydroxyl group of Membranes On Alumina Particles Surface.Adsorption process can be divided into two stages, the first stage be hydrogen fluoride by with aluminium oxide table
The hydroxyl group in face reacts, and hydroxyl is replaced by fluorine ion；Second stage is to form hydrogen fluoride polymolecular under the action of hydrone
Layer, makes more to be fluorinated hydrogen molecule and is attached to oxidation aluminium surface.Aluminium oxide is improved to the absorption property of hydrogen fluoride, it is important to improve
Adsorption reaction rate in unit time, the specific surface area that one side alumina particle needs to have sufficiently large, and constitute this
The microscopic void of a little specific surface areas will have sufficiently large aperture, to guarantee that gas molecule can diffuse into these in a short time
Internal gutter is contacted with oxidation aluminium surface；On the other hand oxidation aluminium surface needs to have enough hydroxyl groups, with arrival table
The fluorination hydrogen molecule in face combines rapidly, completes adsorption reaction.
Method of the invention uses crystal aluminum chloride preparing alumina by hydrolysis, uses " low temperature+high temperature " in hydrolytic process
Two-part calcining manners.By low temperature calcination, formed unformed shape intermediate product (be schematically represented as Al-OH-Cl, wherein
Hydroxyl, chlorine, a small amount of hydrogen etc. can be contained), and Cl, H, O element composition therein is controlled, it can be reduced during sequential hydrolysis
AlCl3Phase or AlCl3·xH2The formation of O (0 < x < 6) phase so that final resulting alumina product be provided simultaneously with it is good microcosmic
Form (such as porosity, specific surface area) and more surface-active hydroxyl quantity, thus improve the adsorption energy to hydrogen fluoride
Power.
In some embodiments, the intermediate product is 60~80% relative to the weight-loss ratio of the crystal aluminum chloride.
In some embodiments, the constituent content in the intermediate product of the unformed shape can be normal by elemental analysis etc.
Test method is advised to obtain.
In some embodiments, the step S1 in vapor relative humidity be 20~100% inert atmosphere in into
Row.
In some embodiments, the step S2 is carried out in dry inert atmosphere.
In some embodiments, the inert atmosphere includes but is not limited to argon gas, nitrogen, dry air, carbon dioxide
Etc. atmosphere.
In some preferred embodiments, the calcination temperature in the step S1 is 260~300 DEG C.
In method provided by the invention, the step S1, step S2 calcination time can according to calciner it is different by
Those skilled in the art select or adjust.
In some embodiments, the calcination time in the step S1 is 0.5~3h；In some preferred embodiments
In, the calcination time in the step S1 is 2~3h, for example, 2h, 2.5h or 3h.
In some embodiments, the calcination time in the step S2 is 0.5~3h；In some preferred embodiments
In, the calcination time in the step S2 is 0.5~2h, for example, 0.5h, 1.0h, 1.5h or 2h.
In method provided by the invention, the step S1, step S2 calcination process in should ensure that the equal of material calcining
Even property and accuracy.For example, the deviation between actual calcination temperature and the calcination temperature of setting should be less than 10 DEG C；In another example
Material conversion between two different calcination temperatures need to undergo the temperature rise period, and the rate of heating is greater than 7 DEG C/min.
In some embodiments, calcining of the intermediate product from the calcination temperature of the step S1 to the step S2
The heating rate of temperature is 7~12 DEG C.
Aluminium oxide made from method provided by the invention is the mixture of a variety of crystal types, in some embodiments,
By quality include 2~10% alpha-phase aluminum oxide, 50~80% γ phase alumina and 15~40% θ phase alumina.
In some embodiments, aluminium oxide produced by the present invention also has one or more of following microscopic feature,
It is preferred that being provided simultaneously with whole features: total hole volume is 0.2~0.5mL/g, BET specific surface area is 60~120m2/ g, igloss (knot
Brilliant water content) it is 0.1~1.5% (preferably igloss is 0.1~0.7%).
The present invention also provides a kind of hydrogen fluoride adsorbents, are oxygen made from any one of above-mentioned technical proposal the method
Change aluminium.
Aluminium oxide made from method provided by the invention not only has high hydrogen fluoride adsorption capacity, but also also complies with
Requirement of the aluminum electrolysis process to alumina raw material, therefore particularly suitable for aluminum electrolysis process.
In some preferred embodiments, the hydrogen fluoride adsorbent is the adsorbent for aluminum electrolysis process.
Preparation method provided by the invention has the advantage that
(1) present invention makes aluminium oxide obtained have good microcosmic hole by the hydrolytic process of control crystal aluminum chloride
Gap, maintaining more surface-active hydroxyl quantity due to the synergistic effect of micromorphology and surface hydroxyl quantity makes oxygen
Change aluminium to be significantly improved to the adsorption capacity of hydrogen fluoride.
(2) alumina product of the method for the present invention preparation is high-quality, hydrogen fluoride adsorption rate is high, is highly suitable as industrial fluorine
Change the hydrogen fluoride adsorbent of hydrogen absorbent, especially aluminium electrolytic industry.
(3) depth that the chlorination aluminum feedstock that the present invention uses from flyash, can realize waste resource recycles.
(4) the method for the present invention simple process and low cost, it is environmental-friendly and convenient for operation.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of fused salt physicochemical properties comprehensive tester used in embodiment；
Fig. 2 is the structural schematic diagram of hydrogen fluoride adsorbent equipment used in embodiment；
Fig. 3 is the structural schematic diagram of the adsorption column of Fig. 2；
Fig. 4 is the XRD spectra of intermediate product obtained in embodiment 1,2,5,6；
Wherein, appended drawing reference is as follows:
101, nickel filament；102, electronic balance；103, corundum crucible；104, resistance furnace；105, thermocouple；106, gas is sent out
Raw device；107, lifting arm；
201, gas instrument is mixed；202, adsorption column；203, aluminium ingot is heated；204, insulating layer；205, temperature controller；206, it surround
Pipe；207, tail gas buffer；208, hydrogen fluoride concentration detector；209, solution bottle；210, porous sieve plate；
A, hydrogen fluoride-argon gas gaseous mixture；B, high-purity argon gas；C, gas to be adsorbed；D, alumina sample；E, absorption tail gas；
F, anhydrous calcium chloride.
Specific embodiment
Below in conjunction with specific embodiment, further details of the technical solution of the present invention.
In an embodiment of the present invention, used crystal aluminum chloride is commercially available Aluminum Chloride Hexahydrate, and solid, purity is greater than
99.0%, exist with crystal habit, unformed shape ingredient≤10%.
In an embodiment of the present invention, using device shown in FIG. 1 (fused salt physicochemical properties comprehensive tester, northeast
Device numbering: 20116967) metallurgy institute, university carries out calcination processing.As shown in Figure 1, by material crystal aluminium chloride be put into
Nickel filament 101 is lifted in the corundum crucible 103 of 102 lower section of electronic balance, and electronic balance 102 is used for while weighing corundum crucible
103 and it is contained in the weight of internal raw material.Corundum crucible 103 is placed in closed resistance furnace 104 in calcination process, is passed through
Thermocouple 105 controls the heating temperature of resistance furnace 104, and the gas generator 106 by being placed in 104 bottom of resistance furnace is surveyed in real time
Gas phase composition inside examination and adjustment 104 burner hearth of resistance furnace.Resistance furnace 104 is whole to be moved by lifting arm 107, to match
Close the pick-and-place of sample in resistance furnace 104.
In an embodiment of the present invention, using device shown in Fig. 2 (hydrogen fluoride adsorbent equipment, metallurgy institute, Northeastern University,
Device numbering: 20170574) it carries out aluminium oxide and the absorption property of hydrogen fluoride is tested.As shown in Fig. 2, use hydrogen fluoride concentration for
The hydrogen fluoride of 1000ppm-argon gas gaseous mixture A and high-purity argon gas B is original gas, is configured to hydrogen fluoride concentration through mixed gas instrument 201
For 500ppm hydrogen fluoride-argon gas gaseous mixture as gas C to be adsorbed, the flow of gas C to be adsorbed is 1L/min, gas to be adsorbed
Body C is preheated reach adsorption temp after, into warmed-up adsorption column 202 (Fig. 2 is not indicated, sees Fig. 3).Around adsorption column 202
Heating aluminium ingot 203 and insulating layer 204 are surrounded by guarantee the temperature of adsorption process, heating aluminium ingot 203 is connected with temperature control
Device 205, heating aluminium ingot 203 are also set up by circular tube 206 outside, and gas C to be adsorbed enters adsorption column by bottom by circular tube 206
In 202, it is discharged after absorption by top.Alumina sample D (Fig. 2 is not indicated, sees Fig. 3), adsorption temp are loaded in adsorption column 202
It is 10-180 DEG C, adsorption time 10-60min.Gas C to be adsorbed becomes absorption tail gas E after the absorption of adsorption column 202, inhales
Attached tail gas E is passed through in tail gas buffer 207 after the dry removal of impurities of anhydrous calcium chloride F, fluorination is equipped on tail gas buffer 207
Hydrogen concentration detector 208 can know remaining hydrogen fluoride concentration in absorption tail gas E in real time, and absorption tail gas E is through tail gas buffer
It is passed through after 207 in the solution bottle 209 of 0.1mol/L sodium hydroxide and carries out vent gas treatment.
The inside specific structure of adsorption column 202 (EZ series 10mL chromatographic column, Wuxi Tianyan Biological Technology Co., Ltd.) is such as
Shown in Fig. 3, alumina sample D to be tested is set in adsorption column with second level fixed bed form, and two layers of alumina sample is with 20-
The porous sieve plate 210 in 50 μm of apertures is spaced apart, and alumina sample is compacted fix by upper and lower sieve plate.The oxidation placed on every layer of sieve plate
Aluminium sample is 0.5g.
In an embodiment of the present invention, used Bayer process aluminium oxide is domestic commercially available sandy alumina, chemical purity
Meet trade mark AO-1 as defined in GB/T 24487-2009；Physical behavior meets " sand shape " classification (" pre-baking tank aluminium metallurgy " (third edition)
Qiu Zhuxian, 2008, metallurgical industry publishing house).
Other reagents involved in the embodiment of the present invention, device or operating method are that this field is normal unless otherwise instructed
See technology.
Embodiment 1
Crystal aluminum chloride is placed in device shown in FIG. 1, in the argon atmosphere of flowing after 200 DEG C keep the temperature 3 hours,
Sampling and testing intermediate product ingredient is unformed shape (see Fig. 4), and chlorinity 14.6%, H and O total content is 50.4%, weightless
Rate 68%.0.5 hour is kept the temperature then at 1300 DEG C, heating rate is 10 DEG C/min in temperature range, obtains alumina product, total hole
Volume is 0.21mL/g, BET specific surface area 60m2/ g, igloss 0.1%, object phase composition are (mass content): γ phase content
52%, θ phase content 38%, α phase content 10%.
The product aluminium oxide of acquisition is placed in adsorbent equipment shown in Fig. 2, adsorption time 20min, adsorption temp is
25 DEG C, (the load fluorine amount under the conditions of is 1.176gHF/100gAl with sand shape Bayer process aluminium oxide2O3) compare, the oxygen of the present embodiment
Changing aluminium product, (load fluorine amount is 1.627gHF/100gAl2O3) fluorination hydrogen adsorptive capacity can be improved 38%.
Embodiment 2
Crystal aluminum chloride is placed in device shown in FIG. 1, in the argon atmosphere of flowing after 350 DEG C keep the temperature 3 hours,
Sampling and testing intermediate product ingredient is unformed shape (see Fig. 4), and chlorinity 8.3%, H and O total content is 45.7%, weight-loss ratio
It is 76.8%.2 hours are kept the temperature then at 1000 DEG C, heating rate is 10 DEG C/min in temperature range, obtains alumina product, total hole
Volume 0.45mL/g, BET specific surface area 118m2/ g, igloss 0.7%, object phase composition are (mass content): γ phase content 78%, θ
Phase content 20%, α phase content 2%.
The product aluminium oxide of acquisition is placed in adsorbent equipment shown in Fig. 2, adsorption time 20min, adsorption temp is
25 DEG C, (the load fluorine amount under the conditions of is 1.176gHF/100gAl with sand shape Bayer process aluminium oxide2O3) compare, the present embodiment obtains
Alumina product (load fluorine amount be 1.635gHF/100gAl2O3) fluorination hydrogen adsorptive capacity can be improved 39%.
Embodiment 3
Crystal aluminum chloride is placed in device shown in FIG. 1, in the argon atmosphere of flowing after 250 DEG C keep the temperature 2 hours,
Sampling and testing intermediate product ingredient is unformed shape, and chlorinity 10.2%, H and O total content is 44.8%, and weight-loss ratio is
75%.1 hour is kept the temperature then at 1100 DEG C, heating rate is 10 DEG C/min in temperature range, obtains alumina product, total hole volume
For 0.3mL/g, BET specific surface area 75m2/ g, igloss 0.7%, object phase composition are (mass content): γ phase content 66%, θ phase
Content 29%, α phase content 5%.
The product aluminium oxide of acquisition is placed in adsorbent equipment shown in Fig. 2, adsorption time 20min, adsorption temp is
25 DEG C, (the load fluorine amount under the conditions of is 1.176gHF/100gAl with sand shape Bayer process aluminium oxide2O3) compare, the present embodiment obtains
Alumina product (load fluorine amount be 1.545gHF/100gAl2O3) fluorination hydrogen adsorptive capacity can be improved 31%.
Embodiment 4
Crystal aluminum chloride is placed in device shown in FIG. 1, in the argon atmosphere of flowing after 300 DEG C keep the temperature 2 hours,
Sampling and testing intermediate product ingredient is unformed shape, and chlorinity 9.2%, H and O total content is 45.3%, and weight-loss ratio is
76.5%.1 hour is kept the temperature then at 1200 DEG C, heating rate is 10 DEG C/min in temperature range, obtains alumina product, total pore volume
Product is 0.26mL/g, BET specific surface area 72m2/ g, igloss 0.6%, object phase composition are (mass content): γ phase content 60%,
θ phase content 35%, α phase content 5%.
The product aluminium oxide of acquisition is placed in adsorbent equipment shown in Fig. 2, adsorption time 60min, adsorption temp is
80 DEG C, (the load fluorine amount under the conditions of is 3.139gHF/100gAl with sand shape Bayer process aluminium oxide2O3) compare, the present embodiment obtains
Alumina product (load fluorine amount be 3.323gHF/100gAl2O3) fluorination hydrogen adsorptive capacity can be improved 6%.
Embodiment 5
Crystal aluminum chloride is placed in device shown in FIG. 1, in constant atmosphere, (vapor relative humidity 100%, remaining is
Argon atmosphere) in after 200 DEG C keep the temperature 3 hours, sampling and testing intermediate product ingredient is unformed shape (see Fig. 4), and chlorinity is
13.0%, H and O total content are 52%, weight-loss ratio 67%.0.5 hour is kept the temperature then at 1300 DEG C, heating rate in temperature range
For 10 DEG C/min, alumina product, total hole volume 0.35mL/g, BET specific surface area 90m are obtained2/ g, igloss 0.5%, object
Phase composition is (mass content): γ phase content 52%, θ phase content 39%, α phase content 9%.
The product aluminium oxide of acquisition is placed in adsorbent equipment shown in Fig. 2, adsorption time 20min, adsorption temp is
25 DEG C, (the load fluorine amount under the conditions of is 1.176gHF/100gAl with sand shape Bayer process aluminium oxide2O3) compare, the present embodiment obtains
Alumina product (load fluorine amount be 1.687gHF/100gAl2O3) fluorination hydrogen adsorptive capacity can be improved 43%.
Embodiment 6
Crystal aluminum chloride is placed in device shown in FIG. 1, in constant atmosphere, (vapor relative humidity 100%, remaining is
Argon atmosphere) in after 350 DEG C keep the temperature 3 hours, sampling and testing intermediate product ingredient is unformed shape (see Fig. 4), and chlorinity is
7.0%, H and O total content are 46.5%, weight-loss ratio 78%.2 hours are kept the temperature then at 1000 DEG C, heating rate in temperature range
For 10 DEG C/min, alumina product, total hole volume 0.49mL/g, BET specific surface area 112m are obtained2/ g, igloss 1.0%,
Object phase composition is (mass content): γ phase content 75%, θ phase content 23%, α phase content 2%.
The product aluminium oxide of acquisition is placed in adsorbent equipment shown in Fig. 2, adsorption time 20min, adsorption temp is
25 DEG C, (the load fluorine amount under the conditions of is 1.176gHF/100gAl with sand shape Bayer process aluminium oxide2O3) compare, the present embodiment obtains
Alumina product (load fluorine amount be 1.694gHF/100gAl2O3) fluorination hydrogen adsorptive capacity can be improved 44%.
Embodiment 7
Crystal aluminum chloride is placed in device shown in FIG. 1, in constant atmosphere, (vapor relative humidity 20%, remaining is
Argon atmosphere) in 200 DEG C keep the temperature 3 hours after, sampling and testing intermediate product ingredient be unformed shape, chlorinity 13.2%, H
It is 51% with O total content, weight-loss ratio 67%.Then at 1300 DEG C keep the temperature 0.5 hour, in temperature range heating rate be 10 DEG C/
Min obtains alumina product, total hole volume 0.24mL/g, BET specific surface area 65m2/ g, igloss 0.3%, object phase composition
For (mass content): γ phase content 53%, θ phase content 37%, α phase content 10%.
The product aluminium oxide of acquisition is placed in adsorbent equipment shown in Fig. 2, adsorption time 20min, adsorption temp is
25 DEG C, (the load fluorine amount under the conditions of is 1.176gHF/100gAl with sand shape Bayer process aluminium oxide2O3) compare, the present embodiment obtains
Alumina product (load fluorine amount be 1.7gHF/100gAl2O3) fluorination hydrogen adsorptive capacity can be improved 45%.
Embodiment 8
Crystal aluminum chloride is placed in device shown in FIG. 1, in constant atmosphere, (vapor relative humidity 20%, remaining is
Argon atmosphere) in 350 DEG C keep the temperature 3 hours after, sampling and testing intermediate product ingredient be unformed shape, chlorinity 8.2%, H
It is 46% with O total content, weight-loss ratio 78%.Then at 1000 DEG C keep the temperature 2 hours, in temperature range heating rate be 10 DEG C/
Min obtains alumina product, total hole volume 0.41mL/g, BET specific surface area 93m2/ g, igloss 0.7%, object phase composition
For (mass content): γ phase content 74%, θ phase content 24%, α phase content 2%.
The product aluminium oxide of acquisition is placed in adsorbent equipment shown in Fig. 2, adsorption time 20min, adsorption temp is
25 DEG C, (the load fluorine amount under the conditions of is 1.176gHF/100gAl with sand shape Bayer process aluminium oxide2O3) compare, the present embodiment obtains
Alumina product (load fluorine amount be 1.696gHF/100gAl2O3) fluorination hydrogen adsorptive capacity can be improved 44%.
Industrial applicibility
As embodiment 1-8 as it can be seen that relative to alumina product made from Bayer process, aluminium oxide made from the method for the present invention
The adsorbance of hydrogen fluoride is significantly increased, can be used as a kind of hydrogen fluoride adsorbent of inexpensive, high adsorption efficiency, it is especially suitable
Industrial application is closed, aluminium electrolytic industry is particularly suitable for.
Unless limited otherwise, term used herein is the normally understood meaning of those skilled in the art.
Embodiment described in the invention is merely for exemplary purpose, the protection scope being not intended to limit the invention,
Those skilled in the art can be made within the scope of the invention various other replacements, changes and improvements, thus, the present invention is not limited to
Above embodiment, and be only defined by the claims.
Claims (10)
1. a kind of method for preparing aluminium oxide by crystal aluminum chloride, which comprises the following steps:
S1: in vapor relative humidity be 0~100% inert atmosphere at 200~350 DEG C calcined crystalline aluminium chloride, until
The intermediate product for forming unformed shape by the Cl content of intermediate product described in quality is 5~15%, H and O total content be 40~
55%；And
S2: the intermediate product made from step S1 is calcined at 1000~1300 DEG C, the aluminium oxide is made.
2. the method according to claim 1, wherein the step S1 in vapor relative humidity be 20~
It is carried out in 100% inert atmosphere.
3. according to the method described in claim 2, it is characterized in that, the inert atmosphere is argon gas, nitrogen, dry air or two
Carbonoxide atmosphere.
4. method according to claim 1-3, which is characterized in that the calcination temperature in the step S1 is 260
~300 DEG C.
5. method according to claim 1-4, which is characterized in that the calcination time in the step S1 is 0.5
~3h；Preferably 2~3h.
6. method according to claim 1-5, which is characterized in that the intermediate product is forged by the step S1's
Burn calcination temperature from temperature to the step S2 heating rate be 7~12 DEG C.
7. method according to claim 1-6, which is characterized in that the calcination time in the step S2 is 0.5
~3h；Preferably 0.5~2h.
8. method according to claim 1-7, which is characterized in that the aluminium oxide includes 2~10% by quality
Alpha-phase aluminum oxide, 50~80% γ phase alumina and 15~40% θ phase alumina.
9. method according to claim 1-8, which is characterized in that the total hole volume of the aluminium oxide be 0.2~
0.5mL/g, and/or BET specific surface area are 60~120m2/ g, and/or igloss (crystal water content) are 0.1~1.5%.
10. a kind of hydrogen fluoride adsorbent, which is characterized in that for aluminium oxide made from any one of claim 1-9 the method；It is excellent
Selection of land, the hydrogen fluoride adsorbent are the adsorbent for aluminum electrolysis process.
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| CN111204784A (en) * | 2020-01-20 | 2020-05-29 | 东北大学 | Method and device for deep hydrolysis and dechlorination of crystalline aluminum chloride |
| CN111517343A (en) * | 2020-05-15 | 2020-08-11 | 江西鹏腾实业有限公司 | Preparation method of high-purity nano aluminum oxide |
| CN114272743A (en) * | 2021-11-25 | 2022-04-05 | 浙江工业大学 | Gas-phase fluorine removal device and application thereof in fluorine removal |
| CN115504493A (en) * | 2022-11-07 | 2022-12-23 | 神华准能资源综合开发有限公司 | Method for preparing alumina aerogel from crystalline aluminum chloride |
| CN115501866A (en) * | 2022-10-29 | 2022-12-23 | 中船(邯郸)派瑞特种气体股份有限公司 | Hydrogen fluoride adsorbent and preparation and application method thereof |
| CN115805001A (en) * | 2023-02-10 | 2023-03-17 | 湖南五创循环科技股份有限公司 | Method for treating organic waste gas in waste power battery black powder roasting process |
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| CN115805001A (en) * | 2023-02-10 | 2023-03-17 | 湖南五创循环科技股份有限公司 | Method for treating organic waste gas in waste power battery black powder roasting process |
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