CN105417560B - Method for producing pseudo-boehmite by adopting inorganic membrane reactor - Google Patents
Method for producing pseudo-boehmite by adopting inorganic membrane reactor Download PDFInfo
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- CN105417560B CN105417560B CN201510808675.3A CN201510808675A CN105417560B CN 105417560 B CN105417560 B CN 105417560B CN 201510808675 A CN201510808675 A CN 201510808675A CN 105417560 B CN105417560 B CN 105417560B
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- boehmite
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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
- C01F7/04—Preparation of alkali metal aluminates; Aluminium oxide or hydroxide therefrom
- C01F7/14—Aluminium oxide or hydroxide from alkali metal aluminates
- C01F7/141—Aluminium oxide or hydroxide from alkali metal aluminates from aqueous aluminate solutions by neutralisation with an acidic agent
- C01F7/142—Aluminium oxide or hydroxide from alkali metal aluminates from aqueous aluminate solutions by neutralisation with an acidic agent with carbon dioxide
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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
-
- 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
Abstract
The invention discloses a method for producing pseudo-boehmite by adopting an inorganic membrane reactor. The method comprises a gel forming step, an aging step, a separating and washing step and a drying step. According to the method, the gel forming step comprises the step that a meta-aluminate solution makes contact with mixed gas in the inorganic membrane reactor to generate a reaction product, wherein the mixed gas comprises carbon dioxide gas and one or two of air and nitrogen; the pseudo-boehmite with the stable quality can be produced.
Description
Technical field
The present invention relates to a kind of method of boehmite, a kind of method that especially alkaline process produces boehmite.
Background technology
Alumina powder is often used in as drier, adsorbent, catalyst and catalyst carrier in chemical field.But
It is that naturally or manually a water aluminum oxide of production and the specific surface area of gibbsite are low, pore volume is small, activity is low, thus can not
For doing drier, adsorbent, catalyst and catalyst carrier.Boehmite has high-specific surface area, big pore volume, macropore
The features such as footpath, high activity, it is suitable for making the catalyst in field such as drier, adsorbent and petrochemical industry, chemical fertilizer and tail gas and urges
Agent carrier etc..Accordingly, it would be desirable to a water aluminum oxide or gibbsite are converted into boehmite.
Crystallization degree of pseudo-boehmite is low, and water content is higher than boehmite, is often existed with colloidal state.At present, boehmite
Method mainly includes aluminium alcoholates Hydrolyze method, acid system and alkaline process (carbonizatin method).
Having main steps that for aluminium alcoholates Hydrolyze method production boehmite is anti-with higher alcohol in the presence of a catalyst by metallic aluminium
Aluminium alcoholates should be generated.The product purity of aluminium alcoholates Hydrolyze method is high, but a large amount of waste water, Organic Alcohol recovery cost can be formed in production process
Greatly, boehmite selling at exorbitant prices is caused.
Acid system be with aluminium salts such as aluminum sulfate, aluminum nitrate, aluminium chloride as raw material, it is solvable with NaOH, sodium carbonate, ammoniacal liquor etc.
Property alkali carry out neutralization reaction and prepare boehmite, preparation process includes that plastic, aging, washing are dried etc..The main of acid system lacks
Point is the relatively costly of production boehmite.
China mainly produces boehmite using carbonizatin method.Department of chemistry of Tongji University, Shanghai Petroleum Chemical Engineering Institute, temperature
The units such as Zhou Jing crystal aluminas Co., Ltd have carried out deep development to alkaline process boehmite.The basic process steps of alkaline process
Including gel, aging, separation and washing, dry etc..During carbonizatin method plastic, there is NaOH and CO2Quick neutralization reaction,
NaAlO2With CO2Neutralization reaction, NaAlO2Spontaneous hydrolysis reaction, CO2With the aluminium hydroxide (hydrated alumina) and Na of generation2CO3
Recombination reaction, specific reaction equation is as follows：
2NaOH+CO2=Na2CO3+H2O (1)
2NaAlO2+CO2+3H2O=2Al (OH)3+Na2CO3 (2)
NaAlO2+2H2O=Al (OH)3+NaOH (3)
Na2CO3+CO2+2Al(OH)3=2NaAl (CO3)(OH)2+H2O (4)
The aluminium hydroxide of reaction (2) generation is converted into boehmite under optimum conditions, and reacts the hydrogen-oxygen of (3) generation
Change aluminium and be then converted into gibbsite, and reaction (2) and reaction (3) they are parallel reaction.Therefore, thin water aluminium is intended in the product of carbonizatin method
Stone or gibbsite content depend on the speed and the extent of reaction of reaction (2) and reaction (3).
Carbonizatin method prepares boehmite can rely on sintering process to produce alumina technology, using intermediate product NaAlO2It is molten
Liquid and CO2Used as reaction raw materials, process is simple is the minimum process route of cost.Formation waste liquid in production can return to oxidation
Aluminium production procedure is recycled, and basic no waste mine discharge, environmental pollution is small, is a kind of compared with competitive superiority and the method for future.
Chinese patent literature CN1091428C discloses a kind of preparation method of boehmite：By sodium metaaluminate or aluminic acid
Sodium solution and carbonated gas are contacted, and the plastic in the way of intermittently or serially, the aging aluminium hydroxide for obtaining is isolated
Solid product, washs and dries；The endpoint pH or process pH value of the plastic are controlled in the range of 6~9.5, plastic reaction
Time or the residence time be less than 40 minutes, plastic reaction 10~100 DEG C of temperature, plastic reaction terminate after be rapidly added alkalescence
Material, makes the pH value of slurries rise to more than 9.5 or carry out separation of solid and liquid and wash rapidly.
Chinese patent literature CN103449484A discloses a kind of method of continuous production boehmite：By sodium metaaluminate
Solution is continuously added in reaction unit, while being passed through the mixed gas of air and carbon dioxide, makes sodium aluminate solution shape
It is sufficiently mixed with gaseous mixture into powerful liquid stream；The flow of control mixed gas and sodium aluminate solution, generates reaction
Slurry temperature be 25~55 DEG C, pH value be 9.5~11；Slurry carries out aging, mistake after with the curved pipeline of multiple u-shapeds
Filter, washing and dried process, obtain boehmite.
The above method is used to being passed directly into CO in reaction unit2Decomposition plastic is carried out, thus is had the disadvantage that：Technique
Equipment falls behind, and automatization level is low, and efficiency is low；Conventional decomposition groove is to CO2Absorptivity is low, and production capacity is small；Reaction time
Long, product quality fluctuation is big；Production equipment easily scabs, and the cycle of operation is short；Continuous prodution relatively difficult to achieve.
Therefore, in the urgent need to a kind of method of boehmite, its product quality stabilization, it is possible to achieve continuous prodution.
The content of the invention
It is an object of the invention to provide a kind of method that use inorganic film reactor produces boehmite, it can give birth to
The boehmite of output quality stabilization.Further aim of the present invention is to provide a kind of production using inorganic film reactor to intend
The method of boehmite, it can realize continuous prodution.
Present inventor is studied with keen determination, it is found that following technical scheme can realize above-mentioned purpose.
A kind of method that use inorganic film reactor produces boehmite, described method includes plastic step：Will be inclined
Aluminate solution is contacted to form product with gaseous mixture in inorganic film reactor；Described gaseous mixture includes dioxy
Change carbon gas, also including one or two in air or nitrogen.
Method in accordance with the invention it is preferred that described inorganic film reactor includes housing and inorganic membrane assembly, it is described
Inorganic membrane assembly is arranged on enclosure interior；Described inorganic membrane assembly includes inoranic membrane；Described inoranic membrane be shaped as tubulose,
Hollow fiber, web-like or helical form；Described inoranic membrane includes matrix and the functional layer being carried on matrix, described function
The material of layer includes metal, alloy, glass or ceramics, and the material of described matrix includes cellular glass, sintering metal or ceramics.
Method in accordance with the invention it is preferred that the reaction temperature of described plastic step is 20~100 DEG C, product
PH value be 9~10.5.
Method in accordance with the invention it is preferred that in described plastic step, the average discharge of meta-aluminate solution is
150~200 ml/mins；The average discharge of gaseous mixture is 10~100 liters/min, and the pressure of gaseous mixture is more than 0.1MPa, mixes
Carbon dioxide accounts for 20~60vt% in closing gas.
Method in accordance with the invention it is preferred that described meta-aluminate is soluble alkali metal meta-aluminate；In inclined aluminium
It it is 20~50 g/l with the meta-aluminate concentration that aluminum oxide is counted in acid salt solution.
Method in accordance with the invention it is preferred that described method also includes：
Aging Step：Described product heat ageing is obtained into ageing products；
Separating, washing step：The ageing products are carried out into separation of solid and liquid to obtain solid matter, then using water to institute
The solid matter stated wash obtaining washed product；With
Drying steps：The washed product is dried to obtain boehmite.
Method in accordance with the invention it is preferred that in described Aging Step, aging temperature is 40~60 DEG C, when aging
Between be 50~200 minutes.
Method in accordance with the invention it is preferred that in described separating, washing step, wash temperature is 20~100 DEG C, is washed
Number of times is washed for 5~15 times；The pH value of final washes is 6.8~7.
Method in accordance with the invention it is preferred that in described drying steps, drying temperature is 105~130 DEG C, is dried
Time is 2~24 hours.
Method in accordance with the invention it is preferred that the pore volume of described boehmite is 0.35~0.45 ml/g, than
Surface area is 280~500m2/g。
The present invention is reacted meta-aluminate solution with the gaseous mixture containing carbon dioxide in inorganic film reactor,
Gas concentration lwevel can be effectively controlled in inorganic film reactor, so as to promote meta-aluminate anti-with the neutralization of carbon dioxide
The reaction of meta-aluminate spontaneous hydrolysis is answered and suppresses, so as to obtain the boehmite of steady quality.According to currently preferred skill
Art scheme, using tubular type inorganic film reactor, hollow fiber form inorganic film reactor can realize continuous prodution.
Brief description of the drawings
Fig. 1 is of the invention into adhesive dispenser.
Fig. 2 is the XRD of boehmite prepared by the embodiment of the present invention 1.
Description of reference numerals is as follows：
1- meta-aluminate feed units；2- gaseous mixture feed units；3- inorganic film reactors；The storage of 4- product is single
Unit；5- measures supply unit；6- flow controlling units.
Specific embodiment
With reference to specific embodiment, the present invention is further illustrated, but protection scope of the present invention is not limited to
This.
" boehmite " chemical formula of the invention is (A12O3·xH2O, 2>x>1), also referred to as " false boehmite ",
With boehmite ((A1 in its structure2O3·H2O) it is similar to, but its crystallinity is very low, and close to gelinite, its crystallization water is high
In boehmite (referring to " chemical encyclopedia, Beijing：Chemical Industry Press, 1998, volume 10, page 938 ").
" vt% " of the invention represents percentage by volume, and " wt% " represents percetage by weight.
The method of boehmite of the invention includes plastic step.Optionally, the method for boehmite of the invention
Aging Step, separating, washing step and drying steps can also be included.
<Plastic step>
Plastic step of the invention is to be contacted with shape meta-aluminate solution in inorganic film reactor with gaseous mixture
Into product.Gaseous mixture of the invention includes carbon dioxide.
In the present invention, described inorganic film reactor can be inorganic selected from tubular type inorganic film reactor or hollow fiber form
Membrane reactor.Tubular type described here, hollow fiber form each mean the shape of inoranic membrane.Preferably, inoranic membrane of the invention
Reactor is tubular type inorganic film reactor or hollow fiber form inorganic film reactor.
In the present invention, described inorganic film reactor includes housing and inorganic membrane assembly, and described inorganic membrane assembly sets
Put in enclosure interior.In the present invention, the housing is tightly connected with inorganic membrane assembly, can be using the conventional method in this area
Sealed, repeated no more here.The structure of inorganic film reactor of the invention can be known in the art those, here not
Repeat again.
Inorganic membrane assembly of the invention includes inoranic membrane.Inoranic membrane of the invention include metal film, alloy film, ceramic membrane or
Glass-film；Preferably ceramic membrane or glass-film；More preferably ceramic membrane.The shape of inoranic membrane of the invention can for tubulose, in
Hollow fiber shape, web-like or helical form.Inoranic membrane of the invention can be the ceramic membrane of tubulose or hollow fiber, tubulose or hollow
Fibrous glass-film, web-like or spiral helicine metal film, or be web-like or spiral helicine alloy film.Preferably, this hair
Bright inoranic membrane can be the ceramic membrane of tubulose or hollow fiber.Generally, it is considered that tubulose, hollow fiber, web-like or spiral
The inoranic membrane of shape is not suitable for the continuous production of boehmite；Inoranic membrane that is of the invention then finding above-mentioned shape, especially
The ceramic membrane of tubulose or hollow fiber, can be used for the continuous production of boehmite.
Inoranic membrane of the invention includes matrix and the functional layer being carried on matrix, and the material of described functional layer includes gold
Category, alloy, glass or ceramics, the material of described matrix include cellular glass, sintering metal or ceramics.Function of the invention
Layer is preferably glass material or ceramic material, more preferably ceramic material；Matrix of the invention is preferably glass material or ceramics
Material, more preferably ceramic material.
In the present invention, the reaction temperature of described plastic step can be 20~100 DEG C, preferably 20~70 DEG C, more
Preferably 20~50 DEG C.In the present invention, the pH value of the product of described plastic step can be 9~10.5, preferably
9.1~10, more preferably 9.2~9.5.
In the present invention, the pH value of described meta-aluminate solution is 10~14, preferably 12~14.Inclined aluminium of the invention
Acid salt solution includes meta-aluminate, water and pH adjusting agent.Meta-aluminate of the invention can be soluble alkali metal meta-aluminic acid
Salt, such as sodium metaaluminate or potassium metaaluminate etc., preferably sodium metaaluminate.PH adjusting agent of the invention can be NaOH, hydrogen
Potassium oxide or ammoniacal liquor etc., preferably NaOH.In meta-aluminate solution of the invention, the meta-aluminate in terms of aluminum oxide is dense
It is 20~50 g/l to spend, preferably 25~40 g/l, more preferably 30~35 g/l.In the present invention, in described plastic
The average discharge of the meta-aluminate solution in step be 150~200 ml/mins, preferably 160~180 ml/mins, more
Preferably 165~175 ml/mins.
Meta-aluminate of the present invention can be prepared using industrial aluminium hydroxide with highly basic or alkali carbonate reaction,
Can also be prepared with highly basic or alkali carbonate using Industry Waste aluminium hydroxide.
In the present invention, the average discharge of the gaseous mixture in described plastic step can be 10~100 liters/min,
Preferably 30~80 liters/min, more preferably 70~76 liters/min.The pressure of the gaseous mixture in described plastic step can
With more than 0.1MPa, more preferably preferably 0.10~1.0MPa, preferably 0.11~0.5MPa, 0.12~0.26MPa.At this
In the gaseous mixture of invention, including carbon dioxide, air and/or nitrogen can be included, other inert gases can also be included, for example
Helium, argon gas.Preferably, gaseous mixture of the invention is made up of carbon dioxide and nitrogen；Or by carbon dioxide
Constituted with air；Or be made up of carbon dioxide, air and nitrogen.In gaseous mixture of the invention, carbon dioxide
Account for 20~60vt%, more preferably preferably 25~40vt%, 30~35vt%.
<Aging Step>
Aging Step of the invention is that above-mentioned product heat ageing is obtained into ageing products.In the present invention, it is aging
Temperature can be 40~60 DEG C, more preferably preferably 45~55 DEG C, 50~55 DEG C；Ageing time can be 50~200 minutes,
Preferably 55~150 minutes, more preferably 60~120 minutes.
<Separating, washing step>
Separating, washing step of the invention is that the ageing products are carried out into separation of solid and liquid to obtain solid matter, is then adopted
Described solid matter wash with water to obtain washed product.In the present invention, the method for separation of solid and liquid can include
Filter, centrifugation etc., preferably filter.The operating condition of separation of solid and liquid of the invention can using it is known in the art those, here
Repeat no more.In the present invention, wash temperature can be 20~100 DEG C, more preferably preferably 30~60 DEG C, 40~50 DEG C；
Washing times can be 5~15 times, preferably 8~10 times.In the present invention, the total amount of slurry is 10~30 liters, preferably
It is 13~20 liters；Each water consumption can be the same or different, preferably identical water consumption.In the present invention, it is final
The pH value of washes is 6.8~7, preferably 7.
<Drying steps>
Drying steps of the invention are that the washed product is dried to obtain into boehmite.In the present invention, temperature is dried
Degree can be 105~130 DEG C, more preferably preferably 110~120 DEG C, 115~118 DEG C；Drying time can be 2~24 small
When, preferably 3~10 hours, more preferably 3~5 hours.
<Boehmite>
The pore volume V of boehmite of the invention is 0.35~0.45 ml/g, preferably 0.38~0.44 ml/g；
Specific surface area S is 280~500m2/ g, preferably 285~420m2/g。
Boehmite of the invention can be used for producing activated alumina, and then as drier, adsorbent, catalyst
And catalyst carrier.
<Method of testing>
Specific surface area, pore volume using nitrogen absorption under low temperature BET method determine (- 196 DEG C, Kang Ta instrument companies of the U.S.
NOVA4000e types specific surface and lacunarity analysis instrument).
(CuK α, λ=0.154nm, sweep the X'pert-MPD types X-ray diffractometer of the Dutch PHILIPS Co. of XRD spectrum use
Retouch 5-80 ° of scope, 4 °/min of sweep speed) determine.
The ceramic membrane used in following examples is：Ceramic membrane materials α-Al2O3, membrane aperture is 0.3 μm, Nanjing Ai Yu fine jades
Film Science and Technology Ltd. product.
The gaseous mixture used in following examples is 30vt% carbon dioxide+70vt% air.
Embodiment
Below with reference to accompanying drawing, the present invention will be described in more detail.Fig. 1 includes inclined aluminium for of the invention into adhesive dispenser
Hydrochlorate feed unit 1, gaseous mixture feed unit 2, inorganic film reactor 3, product memory cell 4 measure the He of supply unit 5
Flow controlling unit 6.Meta-aluminate feed unit 1 (liquid phase feed unit) is by metering supply unit 5 and inorganic film reactor 3
Connection, for quantitatively supplying meta-aluminate solution to inorganic film reactor 3；Gaseous mixture feed unit 2 is controlled single by flow
Unit 6 is connected with inorganic film reactor 3, for quantitatively supplying gaseous mixture (carbonated) to inorganic film reactor 3.Reaction is produced
Thing memory cell 4 is connected by pipeline with inorganic film reactor 3, for accommodating product.
In meta-aluminate feed unit 1, by sodium metaaluminate stoste (alumina content：200 g/l) it is diluted with water to be formed
Sodium aluminate solution.The sodium aluminate solution (liquid phase) of meta-aluminate feed unit 1 is delivered to through metering supply unit 5 inorganic
Membrane reactor 3.Gaseous mixture (gas phase) in gaseous mixture feed unit 2 is delivered to inorganic film reactor through flow controlling unit 6
3.In inorganic film reactor 3, gaseous mixture diffuses to sodium aluminate solution through inorganic membrane assembly (ceramic film component), in gaseous mixture
Carbon dioxide contacted with sodium aluminate solution and plastic of decomposing reacts to form product, wherein comprising aluminium hydroxide.
The product is delivered to product memory cell 4.Intended through aging, filtering and washing, dry (device is not shown)
Boehmite.
, referring to table 1, the performance parameter of gained boehmite is referring to table 2 for other process conditions of embodiment 1~3.Implement
The XRD of boehmite prepared by example 1 is referring to Fig. 2.
Table 1
Table 2
| Performance parameter | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| Pore volume V (ml/g) | 0.38 | 0.42 | 0.44 |
| Specific surface area (m2/g) | 420.23 | 360.75 | 289.59 |
The performance parameter variations very little of the gained boehmite of embodiment 1~3, this shows that the method for the present invention can be obtained
The boehmite product of steady quality.
Additionally, embodiment 1~3 is repeated 5 times respectively, the performance parameter variations scope of gained boehmite is less than 1%,
This shows that the method for the present invention is reproducible.
The present invention is not limited to above-mentioned implementation method, in the case of without departing substantially from substance of the invention, this area skill
Any deformation that art personnel are contemplated that, improvement, replacement each fall within the scope of the present invention.
Claims (9)
1. a kind of method that use inorganic film reactor produces boehmite, it is characterised in that described method includes plastic
Step：Meta-aluminate solution is contacted to form product with gaseous mixture in inorganic film reactor；Described mixing
Gas bag includes carbon dioxide, also including one or two in air or nitrogen；
Wherein, described inorganic film reactor is tubular type inorganic film reactor；Described inorganic film reactor includes housing and nothing
Machine membrane module, described inorganic membrane assembly is arranged on enclosure interior；Described inorganic membrane assembly includes inoranic membrane；Described is inorganic
Film is the ceramic membrane of tubulose；
In described plastic step, the average discharge of meta-aluminate solution is 150~200 ml/mins；Gaseous mixture it is average
Flow is 10~100 liters/min.
2. method according to claim 1, it is characterised in that：The reaction temperature of described plastic step is 20~100 DEG C,
The pH value of product is 9~10.5.
3. method according to claim 1, it is characterised in that：In described plastic step, the pressure of gaseous mixture is more than
0.1MPa, carbon dioxide accounts for 20~60vt% in gaseous mixture.
4. method according to claim 1, it is characterised in that：Described meta-aluminate is soluble alkali metal meta-aluminic acid
Salt；It it is 20~50 g/l with the meta-aluminate concentration that aluminum oxide is counted in meta-aluminate solution.
5. method according to claim 1, it is characterised in that described method also includes：
Aging Step：Described product heat ageing is obtained into ageing products；
Separating, washing step：The ageing products are carried out into separation of solid and liquid to obtain solid matter, then using water to described
Solid matter wash obtaining washed product；With
Drying steps：The washed product is dried to obtain boehmite.
6. method according to claim 5, it is characterised in that：In described Aging Step, aging temperature is 40~60
DEG C, ageing time is 50~200 minutes.
7. method according to claim 5, it is characterised in that：In described separating, washing step, wash temperature is 20
~100 DEG C, washing times are 5~15 times；The pH value of final washes is 6.8~7.
8. method according to claim 6, it is characterised in that：In described drying steps, drying temperature be 105~
130 DEG C, drying time is 2~24 hours.
9. method according to claim 5, it is characterised in that：The pore volume of described boehmite is 0.35~0.45 milli
Rise/gram, specific surface area is 280~500m2/g。
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102642828A (en) * | 2012-04-19 | 2012-08-22 | 南京工业大学 | Method for preparing graphene by inorganic membrane reactor |
| CN102838148A (en) * | 2011-06-23 | 2012-12-26 | 中国石油化工股份有限公司 | Reactor and method used for preparing aluminum hydroxide |
| CN103100431A (en) * | 2011-11-09 | 2013-05-15 | 中国石油化工股份有限公司 | Aluminum hydroxide and preparation method thereof |
-
2015
- 2015-11-20 CN CN201510808675.3A patent/CN105417560B/en active Active
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102838148A (en) * | 2011-06-23 | 2012-12-26 | 中国石油化工股份有限公司 | Reactor and method used for preparing aluminum hydroxide |
| CN103100431A (en) * | 2011-11-09 | 2013-05-15 | 中国石油化工股份有限公司 | Aluminum hydroxide and preparation method thereof |
| CN102642828A (en) * | 2012-04-19 | 2012-08-22 | 南京工业大学 | Method for preparing graphene by inorganic membrane reactor |
Non-Patent Citations (1)
| Title |
|---|
| "Preparation of Pseudoboehmite with a Large Pore Volume and a Large Pore Size by Using a Membrane-Dispersion Microstructured Reactor through the Reaction of CO2 and a NaAlO2 Solution";Yujun Wang et al.;《Ind. Eng. Chem. Res.》;20110224;第50卷;第3890页图1、第3891页第3段、第3894页表格4 * |
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