CN110272057A - A method of ordered mesoporous material Al-MCM-41 is prepared using rectorite - Google Patents
A method of ordered mesoporous material Al-MCM-41 is prepared using rectorite Download PDFInfo
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Abstract
The invention belongs to field of material preparation, specifically disclose a kind of method for preparing ordered mesoporous material Al-MCM-41 using rectorite, and rectorite obtains acidification rectorite through acid soak, separation of solid and liquid, washing, drying；Acidification rectorite is separated by solid-liquid separation through alkali leaching processing, after, obtains alkali leaching liquor；Alkali leaching liquor is mixed with strongly acidic cation-exchange, is then separated by solid-liquid separation mixed solution, obtains siliceous silicon source filtrate；Siliceous silicon source filtrate, cationic surfactant are mixed, hydro-thermal reaction is then carried out, obtains presoma；By presoma through calcination processing, ordered mesoporous material Al-MCM-41 is obtained.Silicon and aluminum source is added using cheap natural accumulation supporting stone mineral as raw material, without additional in the regulation present invention, prepares ordered mesoporous material Al-MCM-41；The ordered mesoporous material Al-MCM-41 mesopore orbit of preparation is parallel to each other, and cross section is in Hexagonal array, has regular two-dimentional hexagonal structure, specific surface area is up to 1105m2/ g, pore volume can reach 1.12cm3/ g, pore-size distribution are concentrated, and pore performance is good.
Description
Technical field
The invention belongs to field of inorganic nonmetallic material, and in particular to a kind of to prepare ordered mesoporous material using rectorite
The method of Al-MCM-41.
Background technique
Ordered mesoporous material is the new material to grow up at the end of the 20th century, the duct which has height rule orderly
Structure, pore size is adjustable, there is higher specific surface area and biggish adsorption capacity.1992, Mobil company was with surface-active
Agent is template, and the M41S series silicon-based mesoporous material of high-sequential is prepared using hydrothermal synthesis method, and pass includes: orientation row
The hexagonal phase cylindrical hole (MCM-41) of column, the cubic phase multi-panel body opening (MCM-48) of three-dimensional regular arrangement, stratiform arranged in parallel
Hole (MCM-50).Because of its unique structure and property, silicon base ordered mesopore material is widely used in that separation, catalysis, environment controls
Reason, drug release and other biological field, after especially being modified by organic reagent, it be provided with different biochemistry, physics,
Chemical property becomes a kind of nano material of great Development volue to show outstanding application prospect.
Currently, preparing silicon source used by silicon base ordered mesopore material is mostly chemical reagent, as ethyl orthosilicate (TEOS),
Environmental pollution is easily caused in methyl orthosilicate (TMOS) and sodium metasilicate etc., expensive starting materials and chemical reagent preparation process.And day
Right silicate mineral, it is resourceful, it is cheap, it is rich in silicon, aluminium element, is the reason for preparing silicon-based mesoporous material on a large scale
Think raw material.The Chinese patent application (CN106145132A) of Guan Ai etc., which discloses, a kind of prepares order mesoporous material using attapulgite
Expect the method for Al-MCM-41, the specific surface area of prepared ordered mesoporous material Al-MCM-41 is up to 998m2/ g, pore volume can
Reach 0.80cm3/ g or more, pore-size distribution are concentrated, and pore performance is good, has widened the application field of attapulgite.Fan Jianwei's etc.
Chinese patent application (CN103861556A) discloses a kind of method using coal ash for manufacturing for mesoporous material, prepared fine coal
Grey base SBA-15 has regular two-dimentional hexagonal structure, 0.6~0.9cm of Kong Rongwei3/ g, specific surface area are up to 800m2/ g, aperture
For 5~8nm, the application field of flyash has been widened.The Chinese patent application (CN101643217A) of Yang Huaming etc. discloses one
The method that kind prepares ordered mesoporous material using bentonite, the specific surface area of prepared ordered mesoporous material reach as high as
1000m2/ g or more, Kong Rong can reach 1.00cm3/ g or more, pore-size distribution are concentrated, and bentonitic application field has been widened.Zhou Chun
The Chinese patent application (CN102992348B) of space etc. discloses one kind and prepares orderly complex mesoporous material by raw material of galapectite
The method of Al-SBA-15 has widened the application field of galapectite.The Chinese patent applications such as Wu Qisheng (CN102060301A) are open
A kind of method preparing mesoporous material as raw material using Coaseries kaolin, gained mesoporous material specific surface area are 800~1200m2/
G has widened the application field of Coaseries kaolin.The Chinese patent application (CN104016369A) of Du Chunfang etc. discloses a kind of benefit
With kaolin synthesizing high-stability ordered mesoporous material Al-SBA-15, preparation process is simple, and raw material is easy to get, loose operation condition,
The ordered mesoporous material of synthesis has good hydrothermal stability and catalytic activity, has widened kaolinic application field.In addition,
Also it is reported about the research for preparing ordered mesoporous material as raw material using sepiolite, diatomite, talcum.But all kinds of natural
Silicate mineral in, there is no at present about exploitation rectorite prepare ordered mesoporous material Al-MCM-41 research report.
Rectorite crystal structure and attapulgite, bentonite, galapectite, kaolin, sepiolite, diatomite, talcum etc. are viscous
Native mineral are different, it is a kind of mineral with special aluminosilicate crystals structure, by dioctahedron mica layer and dioctahedron
Montmorillonite layer replaces stacking under special natural conditions by 1: 1 regularly and forms, and is not the simple combination of the two, thus
Form a kind of rule space layer clay mineral.Rectorite elementary layer is different from mica layer and is added with the simple mathematical of montmorillonite layer, it
Between have the difference of matter.In mica mineral structure sheaf, the tetrahedron on both sides is all high point lotus in elementary layer；And in montmorillonite
In mineral, the tetrahedron on both sides is all low spot lotus in elementary layer, and this unique structural unit layer is rather rare.The hair of rectorite
Now more than 100 years existing away from the present, researcher is concentrated mainly on high-quality deep drilling mud, catalysis to the development and utilization of rectorite at present
The fields such as agent carrier, lubricating ester, ceramics, rubber, environment-friendly materials, filtering material, coating deflocculant.However, in the prior art, also
It has no and overcomes the problems, such as to extract silicon and aluminum source by raw material of rectorite, so that the related report of ordered mesoporous material Al-MCM-41 be made
Road.
Summary of the invention
It is this object of the present invention is to provide a kind of method for preparing ordered mesoporous material Al-MCM-41 using rectorite
Method prepares Al-MCM-41 using rectorite as raw material.
A method of ordered mesoporous material Al-MCM-41 is prepared using rectorite, comprising the following steps:
Step (1): rectorite obtains acidification rectorite through acid soak, separation of solid and liquid, washing, drying；
Step (2): acidification rectorite is separated by solid-liquid separation through alkali leaching processing, after, obtains alkali leaching liquor；
Step (3): alkali leaching liquor is mixed with strongly acidic cation-exchange, is then separated by solid-liquid separation mixed solution, is obtained
To siliceous silicon source filtrate；
Step (4): siliceous silicon source filtrate that step (3) is obtained, cationic surfactant mixing then carry out hydro-thermal
Reaction, obtains presoma；
Step (5): by presoma through calcination processing, ordered mesoporous material Al-MCM-41 is obtained.
It has been disclosed in the prior art with attapulgite, bentonite, galapectite, kaolin, sepiolite, diatomite, talcum
Equal clay minerals are raw material, obtain silicon and aluminum source.Rectorite is because having the structural property different from these clay minerals, it has been disclosed that
Sial source technology, which is extracted, from clay mineral is not suitable for rectorite.The present invention was once attempted using rectorite as raw material, using soda acid
Leaching method and hydrothermal method are hampered by the unique crystal structure of rectorite, are difficult to that ordered mesoporous material Al- is successfully made always
MCM-41；The present inventor passes through numerous studies, and discovery is failed using the preparation that rectorite prepares ordered mesoporous material Al-MCM-41
The main reason for when being to extract silicon source using disclosed alkali leaching technology, because of the unique crystal structure of rectorite, during alkali soaks
However, residual base, however, the present invention works, early period neutralizes the alkali remained in alkali leaching liquor using inorganic acid, still can not successfully be prepared with
Sequence mesoporous material Al-MCM-41.By further studying, it is a discovery of the invention that carrying out strong-acid type sun to rectorite alkali infusion solution
Ordered mesoporous material Al-MCM-41 can be unexpectedly made in ion exchange resin treatment.
The present invention, by the acidic leaching with alkaline leaching-resin treatment technology, overcomes benefit innovatively using rectorite as raw material
With rectorite prepare mesoporous material Al-MCM-41 existing for can not succeed prepare technical difficulty, obtain be suitable for silicon and aluminum source, then
Using cationic surfactant as template, using hydrothermal crystallizing reaction method preparation cellular structure, regular, pore size can
It adjusts, the higher ordered mesoporous material Al-MCM-41 of specific surface area.Method proposed by the present invention does not have to add any pure silicon or pure
Aluminum chemistry reagent can expand the application field of rectorite, realize the recycling of rectorite.
Preferably, the acid solution is the aqueous solution of inorganic acid in step (1)；Preferably aqueous hydrochloric acid solution.
Preferably, in step (1), the acid solution H+Concentration is 2~8mol/L.
Preferably, the solid-to-liquid ratio of rectorite and acid solution is 1: 30~1: 100g/mL in step (1).
Preferably, the temperature of acid soak process is 60~140 DEG C in step (1)；Soaking time is 4~12 hours.
After acid soak processing, be separated by solid-liquid separation after being cooled to room temperature (such as filter), obtained solid product spend from
Sub- water washing to neutral (no chloride ion), drying, grinding obtains acidification rectorite powder.
Preferably, the lye that the dipped journey of alkali uses is the aqueous solution of alkali metal hydroxide；Preferred lye is hydrogen-oxygen
Change sodium solution.
Preferably, in lye, OH-Concentration be 2~6mol/L.
Preferably, the solid-to-liquid ratio of acidification rectorite and lye is 1: 5~1: 20g/mL.
Preferably, the temperature of the dipped journey of alkali is 10~50 DEG C；Time be 8~for 24 hours.
The pH value of alkali leaching liquor obtained by step (2) is 14.00~14.60；Remain alkali used in the dipped journey of alkali；This hair
It is bright to be innovatively added into alkali leaching liquor obtained by step (2) in strongly acidic cation-exchange and however, residual base, by mixed liquor
It is filtered, takes filtrate as silicon and aluminum source.
Preferably, the alkali remained in alkali leaching liquor is neutralized using strongly acidic cation-exchange in step (3),
It is 13.00~13.40 to alkali leaching liquor pH value.Innovative point is that strongly acidic cation-exchange discharges H during this+With alkali
OH in leachate-Reaction generates H2O, while adsorbing cation that alkali in alkali leaching liquor introduces (such as Na+), it obtains without hydrogen-oxygen
(sodium silicate solution pH value is 13.00~13.40 to the silicon and aluminum source solution of change sodium, so the present invention regulates and controls alkali leaching liquor pH value extremely
It 13.00~13.40), can using strongly acidic cation-exchange, compared to the existing conventional neutralization using the acid such as HCl
Ordered mesoporous material Al-MCM-41 is unexpectedly successfully made.
The strongly acidic cation-exchange can be known to those skilled in the art any classification strong acid
Type cation exchange resin.
The siliceous silicon source filtrate that cationic surfactant and step (3) are obtained mixes, and regulates and controls siliceous silicon source using acid
The pH value of filtrate, then keeps the temperature in a high pressure reaction kettle, carries out hydro-thermal reaction, and after reaction, processing obtains presoma.
Preferably, the cationic surfactant is cetyl trimethylammonium bromide.
Preferably, the concentration of the cationic surfactant of the starting soln of hydro-thermal reaction is 0.1~0.5mol/L.
Preferably, the pH value of the starting soln of hydro-thermal reaction is 8~12.
Preferably, the temperature of hydro-thermal reaction is 100~150 DEG C；The hydro-thermal reaction time is 24~72h.
After hydro-thermal reaction, after reaction vessel is cooled to room temperature, product alcohol, deionized water are washed to supernatant
Liquid is free of surfactant, and drying, grinding obtain presoma.
Presoma is subjected to calcination processing, surfactant is removed, obtains ordered mesoporous material Al-MCM-41.
Calcination process can carry out in existing conventional equipment, carry out preferably in Muffle furnace.
Preferably, the atmosphere of calcination processing is air atmosphere.
Preferably, the temperature of calcination processing is 500~600 DEG C.
Preferably, the heating rate of calcination process is 1~3 DEG C/min.
Preferably, calcination time is 4~10h.
The present invention provides a kind of method for more preferably preparing ordered mesoporous material Al-MCM-41 using rectorite, tool
Preparation step are as follows:
(1) using natural accumulation supporting stone as raw material, the aqueous hydrochloric acid solution of 2~8mol/L is leaching agent, is 1: 30 according to solid-to-liquid ratio
The ratio of~1: 100 (g: mL) takes rectorite and combined, in 60~140 DEG C of at a temperature of magnetic agitation 4~12
Hour after obtain dirty solution, filtered after being cooled to room temperature, to filter obtained solid product be washed with deionized to
Neutral (no chloride ion), drying, grinding at a temperature of 80 DEG C, obtains acidification rectorite powder；
(2) using acidification rectorite powder obtained by step (1) as raw material, the sodium hydrate aqueous solution of 2~6mol/L is to leach
Agent takes acidification rectorite powder and sodium hydrate aqueous solution to mix, 10 according to the ratio that solid-to-liquid ratio is 1: 5~1: 20 (g: mL)
Magnetic agitation obtained dirty solution after 8~24 hours at a temperature of~50 DEG C, was filtered after being cooled to room temperature, filtrate (pH
Value is 14.00~14.60) it is spare；
(3) it is added into filtrate obtained by step (2) in strongly acidic cation-exchange and remaining sodium hydroxide, until alkali soaks
Liquid pH value is 13.00~13.40 out, and mixed liquor is filtered, takes filtrate as silicon and aluminum source.
(4) cationic surfactant cetyl trimethylammonium bromide (CTAB) is added into filtrate obtained by step (3),
Use 0.5~6mol/L aqueous hydrochloric acid solution regulation mixed solution pH value for 8~12,60 DEG C at a temperature of magnetic agitation 2 hours
After be transferred to autoclave, at a temperature of 100~150 DEG C hydrothermal crystallizing react 24~72h, after reaction kettle is cooled to room temperature, will
Product alcohol, deionized water wash to supernatant and are free of CTAB, and drying, grinding, obtain presoma at a temperature of 80 DEG C.
(5) presoma obtained by step (4) is put into Muffle furnace, 500~600 DEG C of temperature lower calcination keeps the temperature 4~10h
(heating rate is 1~3 DEG C/min), removes surfactant, obtains ordered mesoporous material Al-MCM-41.
Compared with prior art, the features of the present invention and beneficial effect are:
(1) present invention is using rectorite as raw material, and by acidic leaching with alkaline leaching-resin treatment technology, it is special because of rectorite to overcome
Alkali has remaining technical problem and obtains silicon and aluminum source when structural property causes to extract silicon source using disclosed alkali leaching technology, this process
It is not necessary that silicon and aluminum source is additionally added, ordered mesoporous material Al-MCM-41 is prepared by chemical method, has widened the application neck of rectorite
Domain has the potentiality for producing the mineral-base composite material of high added value；
(2) silicon source extractive technique of the invention can be realized under normal temperature conditions, energy saving, reduce production cost；
(3) present invention neutralizes the alkali remained in alkali leaching liquor, i.e. strong-acid type sun using strongly acidic cation-exchange
Ion exchange resin discharges H+With OH in alkali leaching liquor-Reaction generates H2O, while adsorbing Na in alkali leaching liquor+, obtain not hydrogeneous
The silicon and aluminum source solution of sodium oxide molybdena.
(4) preparation process environmental pollution of the present invention is small, and preparation process is simple, and raw material reserves are big, cheap；
(5) duct of the ordered mesoporous material Al-MCM-41 prepared by the present invention is parallel to each other, and cross section is arranged in six sides
Column have regular two-dimentional hexagonal structure；
(6) specific surface area of the ordered mesoporous material Al-MCM-41 prepared by the present invention is up to 1105m2/ g, pore volume can
Reach 1.12cm3/ g or more, pore-size distribution are concentrated, and pore performance is good.
Detailed description of the invention:
Fig. 1 is the X-ray diffractogram of rectorite raw ore；
Fig. 2 is prepared by ordered mesoporous material Al-MCM-41 prepared by the embodiment of the present invention 1~2 and comparative example 1~4
The small angle X-ray diffraction figure of white powder；
Fig. 3 is the Wide angle X-ray diffraction figure of ordered mesoporous material Al-MCM-41 prepared by the embodiment of the present invention 1~2；
Fig. 4 is the N of ordered mesoporous material Al-MCM-41 prepared by the embodiment of the present invention 22Adsorption-desorption isothermal (a)
With BJH pore size distribution curve (b)；
Fig. 5 is the stereoscan photograph of ordered mesoporous material Al-MCM-41 prepared by the embodiment of the present invention 2；
Fig. 6 is the transmission electron microscope photo of ordered mesoporous material Al-MCM-41 prepared by the embodiment of the present invention 2.
Specific embodiment
The present invention provides a kind of method for preparing ordered mesoporous material Al-MCM-41 using rectorite, specific preparation step
Suddenly are as follows:
(1) using natural accumulation supporting stone as raw material, the aqueous hydrochloric acid solution of 2~8mol/L is leaching agent, is 1:30 according to solid-to-liquid ratio
The ratio of~1: 100 (g: mL) takes rectorite and combined, in 60~140 DEG C of at a temperature of magnetic agitation 4~12
Hour after obtain dirty solution, filtered after being cooled to room temperature, to filter obtained solid product be washed with deionized to
Neutral (no chloride ion), drying, grinding at a temperature of 80 DEG C, obtains acidification rectorite powder；
(2) using acidification rectorite powder obtained by step (1) as raw material, the sodium hydrate aqueous solution of 2~6mol/L is to leach
Agent takes acidification rectorite powder and sodium hydrate aqueous solution to mix, 10 according to the ratio that solid-to-liquid ratio is 1: 5~1: 20 (g: mL)
Magnetic agitation obtained dirty solution after 8~24 hours at a temperature of~50 DEG C, was filtered after being cooled to room temperature, filtrate (pH
Value is 14.00~14.60) it is spare；
(3) it is added into filtrate obtained by step (2) in strongly acidic cation-exchange and remaining sodium hydroxide, until alkali soaks
Liquid pH value is 13.00~13.40 out, and mixed liquor is filtered, takes filtrate as silicon and aluminum source.
(4) cationic surfactant cetyl trimethylammonium bromide (CTAB) is added into filtrate obtained by step (3),
Use 0.5~6mol/L aqueous hydrochloric acid solution regulation mixed solution pH value for 8~12,60 DEG C at a temperature of magnetic agitation 2 hours
After be transferred to autoclave, at a temperature of 100~150 DEG C hydrothermal crystallizing react 24~72h, after reaction kettle is cooled to room temperature, will
Product alcohol, deionized water wash to supernatant and are free of CTAB, and drying, grinding, obtain presoma at a temperature of 80 DEG C.
(5) presoma obtained by step (4) is put into Muffle furnace, 500~600 DEG C of temperature lower calcination keeps the temperature 4~10h
(heating rate is 1~3 DEG C/min), removes surfactant, obtains ordered mesoporous material Al-MCM-41.
The present invention will be further described with reference to embodiments.
In the present invention, the strongly acidic cation-exchange can be selected strong-acid type cation known in the art and hand over
Change resin, in following embodiment, unless specified or limited otherwise, be selected from model 001 × 7 (732) strongly acidic cation-exchange,
Producer is the resin of Shanghai Hua Mo Industrial Co., Ltd..
Embodiment 1
(1) natural accumulation supporting stone 5g is weighed, the aqueous hydrochloric acid solution 250ml of 6mol/L is measured, by rectorite and aqueous hydrochloric acid solution
Mixing, 110 DEG C at a temperature of magnetic agitation 12 hours after obtain dirty solution, filtered after being cooled to room temperature, to pumping
Filter obtained solid product is washed with deionized to neutral (no chloride ion), and it is tired to obtain acidification for drying, grinding at a temperature of 80 DEG C
Hold in the palm stone powder；
(2) it weighs and is acidified rectorite powder 3g obtained by step (1), measure the sodium hydrate aqueous solution 30ml of 4mol/L, it will
Be acidified rectorite powder and sodium hydrate aqueous solution mixing, 30 DEG C at a temperature of magnetic agitation 20 hours after obtain dirty solution,
It is filtered after being cooled to room temperature, filtrate (pH value is 14.00~14.60) is spare；
(3) strongly acidic cation-exchange is added into filtrate obtained by step (2) regulates and controls pH value and (neutralize residual to 13.30
Remaining sodium hydroxide), mixed liquor is filtered, deionized water is added into filtrate to 50ml as silicon and aluminum source.
(4) 0.5g cetyl trimethylammonium bromide (CTAB) is weighed in 100mL beaker, and 10mL deionized water is added,
Stirring and dissolving forms CTAB solution, is added in 50ml filtrate obtained by step (3), using 0.5~6mol/L aqueous hydrochloric acid solution tune
Mixed solution pH value is controlled to 9,60 DEG C at a temperature of magnetic agitation 2 hours after be transferred to autoclave, 110 DEG C of temperature is lauched
Thermal crystallisation reacts for 24 hours, after reaction kettle is cooled to room temperature, product alcohol, deionized water is washed to supernatant without CTAB, 80
It dries, grind at a temperature of DEG C, obtain presoma.
(5) presoma obtained by step (4) is put into Muffle furnace (air atmosphere), 550 DEG C of temperature lower calcination keeps the temperature 6h
(heating rate is 2 DEG C/min), removes surfactant, obtains ordered mesoporous material Al-MCM-41, specific surface area 968m2/
G, pore volume 0.83m3/ g, average pore size 3.4nm.
Embodiment 2
(1) natural accumulation supporting stone 5g is weighed, the aqueous hydrochloric acid solution 250ml of 6mol/L is measured, by rectorite and aqueous hydrochloric acid solution
Mixing, 110 DEG C at a temperature of magnetic agitation 12 hours after obtain dirty solution, filtered after being cooled to room temperature, to pumping
Filter obtained solid product is washed with deionized to neutral (no chloride ion), and it is tired to obtain acidification for drying, grinding at a temperature of 80 DEG C
Hold in the palm stone powder；
(2) it weighs and is acidified rectorite powder 3g obtained by step (1), measure the sodium hydrate aqueous solution 30ml of 4mol/L, it will
Be acidified rectorite powder and sodium hydrate aqueous solution mixing, 30 DEG C at a temperature of magnetic agitation 20 hours after obtain dirty solution,
It is filtered after being cooled to room temperature, filtrate (pH value is 14.00~14.60) is spare；
(3) strongly acidic cation-exchange is added into filtrate obtained by step (2) regulates and controls pH value and (neutralize residual to 13.30
Remaining sodium hydroxide), mixed liquor is filtered, deionized water is added into filtrate to 50ml as silicon and aluminum source.
(4) 1g cetyl trimethylammonium bromide (CTAB) is weighed in 100mL beaker, and 10mL deionized water is added, stirs
Dissolution is mixed, CTAB solution is formed, is added in 50ml filtrate obtained by step (3), is regulated and controled using 0.5~6mol/L aqueous hydrochloric acid solution
Mixed solution pH value to 9,60 DEG C at a temperature of magnetic agitation 2 hours after be transferred to autoclave, hydro-thermal at a temperature of 110 DEG C
Crystallization for 24 hours, after reaction kettle is cooled to room temperature, product alcohol, deionized water is washed to supernatant without CTAB, 80 DEG C
At a temperature of drying, grinding, obtain presoma.
(5) presoma obtained by step (4) is put into Muffle furnace (air atmosphere), 550 DEG C of temperature lower calcination keeps the temperature 6h
(heating rate is 2 DEG C/min), removes surfactant, obtains ordered mesoporous material Al-MCM-41, specific surface area is
1105m2/ g, pore volume 1.12m3/ g, average pore size 3.8nm.
Comparative example 1
It is compared with embodiment 2, difference is, in step (3), strongly acidic cation-exchange is not added in alkali leaching liquor, tool
Gymnastics is made as follows:
(1) natural accumulation supporting stone 5g is weighed, the aqueous hydrochloric acid solution 250ml of 6mol/L is measured, by rectorite and aqueous hydrochloric acid solution
Mixing, 110 DEG C at a temperature of magnetic agitation 12 hours after obtain dirty solution, filtered after being cooled to room temperature, to pumping
Filter obtained solid product is washed with deionized to neutral (no chloride ion), and it is tired to obtain acidification for drying, grinding at a temperature of 80 DEG C
Hold in the palm stone powder；
(2) it weighs and is acidified rectorite powder 3g obtained by step (1), measure the sodium hydrate aqueous solution 30ml of 4mol/L, it will
Be acidified rectorite powder and sodium hydrate aqueous solution mixing, 30 DEG C at a temperature of magnetic agitation 20 hours after obtain dirty solution,
It is filtered after being cooled to room temperature, filtrate is spare；
(3) deionized water is added to 50ml as silicon and aluminum source (pH value 14.20) into filtrate obtained by step (2).
(4) 1g cetyl trimethylammonium bromide (CTAB) is weighed in 100mL beaker, and 10mL deionized water is added, stirs
Dissolution is mixed, CTAB solution is formed, is added in 50ml filtrate obtained by step (3), is regulated and controled using 0.5~6mol/L aqueous hydrochloric acid solution
Mixed solution pH value to 9,60 DEG C at a temperature of magnetic agitation 2 hours after be transferred to autoclave, hydro-thermal at a temperature of 110 DEG C
Crystallization for 24 hours, after reaction kettle is cooled to room temperature, product alcohol, deionized water is washed to supernatant without CTAB, 80 DEG C
At a temperature of drying, grinding, obtain presoma.
(5) presoma obtained by step (4) is put into Muffle furnace (air atmosphere), 550 DEG C of temperature lower calcination keeps the temperature 6h
(heating rate is 2 DEG C/min), removes surfactant, obtains white powder, prepares ordered mesoporous material Al-MCM-41 mistake
It loses.
Comparative example 2
It is compared with embodiment 2, difference is, in step (3), exchanges tree using the HCl replacement strong-acid type cation
Rouge regulates and controls the pH value of solution to 13.30, and concrete operations are as follows:
(1) natural accumulation supporting stone 5g is weighed, the aqueous hydrochloric acid solution 250ml of 6mol/L is measured, by rectorite and aqueous hydrochloric acid solution
Mixing, 110 DEG C at a temperature of magnetic agitation 12 hours after obtain dirty solution, filtered after being cooled to room temperature, to pumping
Filter obtained solid product is washed with deionized to neutral (no chloride ion), and it is tired to obtain acidification for drying, grinding at a temperature of 80 DEG C
Hold in the palm stone powder；
(2) it weighs and is acidified rectorite powder 3g obtained by step (1), measure the sodium hydrate aqueous solution 30ml of 4mol/L, it will
Be acidified rectorite powder and sodium hydrate aqueous solution mixing, 30 DEG C at a temperature of magnetic agitation 20 hours after obtain dirty solution,
It is filtered after being cooled to room temperature, filtrate (pH value is 14.00~14.60) is spare；
(3) 3mol/L aqueous hydrochloric acid solution is added into filtrate obtained by step (2) and regulates and controls pH value to 13.30 (neutralization residual hydrogens
Sodium oxide molybdena), mixed liquor is filtered, deionized water is added into filtrate to 50ml as silicon and aluminum source.
(4) 1g cetyl trimethylammonium bromide (CTAB) is weighed in 100mL beaker, and 10mL deionized water is added, stirs
Dissolution is mixed, CTAB solution is formed, is added in 50ml filtrate obtained by step (3), is regulated and controled using 0.5~6mol/L aqueous hydrochloric acid solution
Mixed solution pH value to 9,60 DEG C at a temperature of magnetic agitation 2 hours after be transferred to autoclave, hydro-thermal at a temperature of 110 DEG C
Crystallization for 24 hours, after reaction kettle is cooled to room temperature, product alcohol, deionized water is washed to supernatant without CTAB, 80 DEG C
At a temperature of drying, grinding, obtain presoma.
(5) presoma obtained by step (4) is put into Muffle furnace (air atmosphere), 550 DEG C of temperature lower calcination keeps the temperature 6h
(heating rate is 2 DEG C/min), removes surfactant, obtains white powder, prepares ordered mesoporous material Al-MCM-41 mistake
It loses.
Comparative example 3
It is compared with embodiment 2, difference is, in step (3), using strongly acidic cation-exchange, regulates and controls solution
PH value is 9, and concrete operations are as follows:
(1) natural accumulation supporting stone 5g is weighed, the aqueous hydrochloric acid solution 250ml of 6mol/L is measured, by rectorite and aqueous hydrochloric acid solution
Mixing, 110 DEG C at a temperature of magnetic agitation 12 hours after obtain dirty solution, filtered after being cooled to room temperature, to pumping
Filter obtained solid product is washed with deionized to neutral (no chloride ion), and it is tired to obtain acidification for drying, grinding at a temperature of 80 DEG C
Hold in the palm stone powder；
(2) it weighs and is acidified rectorite powder 3g obtained by step (1), measure the sodium hydrate aqueous solution 30ml of 4mol/L, it will
Be acidified rectorite powder and sodium hydrate aqueous solution mixing, 30 DEG C at a temperature of magnetic agitation 20 hours after obtain dirty solution,
It is filtered after being cooled to room temperature, filtrate (pH value is 14.00~14.60) is spare；
(3) strongly acidic cation-exchange is added into filtrate obtained by step (2) and regulates and controls pH value to 9, by mixed liquor into
Row filters, and deionized water is added into filtrate to 50ml as silicon and aluminum source.
(4) 1g cetyl trimethylammonium bromide (CTAB) is weighed in 100mL beaker, and 10mL deionized water is added, stirs
Dissolution is mixed, CTAB solution is formed, is added in 50ml filtrate obtained by step (3), is regulated and controled using 0.5~6mol/L aqueous hydrochloric acid solution
Mixed solution pH value to 9,60 DEG C at a temperature of magnetic agitation 2 hours after be transferred to autoclave, hydro-thermal at a temperature of 110 DEG C
Crystallization for 24 hours, after reaction kettle is cooled to room temperature, product alcohol, deionized water is washed to supernatant without CTAB, 80 DEG C
At a temperature of drying, grinding, obtain presoma.
(5) presoma obtained by step (4) is put into Muffle furnace (air atmosphere), 550 DEG C of temperature lower calcination keeps the temperature 6h
(heating rate is 2 DEG C/min), removes surfactant, obtains white powder, prepares ordered mesoporous material Al-MCM-41 mistake
It loses.
Embodiment 3
(1) natural accumulation supporting stone 5g is weighed, the aqueous hydrochloric acid solution 250ml of 6mol/L is measured, by rectorite and aqueous hydrochloric acid solution
Mixing, 110 DEG C at a temperature of magnetic agitation 12 hours after obtain dirty solution, filtered after being cooled to room temperature, to pumping
Filter obtained solid product is washed with deionized to neutral (no chloride ion), and it is tired to obtain acidification for drying, grinding at a temperature of 80 DEG C
Hold in the palm stone powder；
(2) it weighs and is acidified rectorite powder 3g obtained by step (1), measure the sodium hydrate aqueous solution 30ml of 2mol/L, it will
Be acidified rectorite powder and sodium hydrate aqueous solution mixing, 30 DEG C at a temperature of magnetic agitation 20 hours after obtain dirty solution,
It is filtered after being cooled to room temperature, filtrate (pH value is 14.00~14.60) is spare；
(3) strongly acidic cation-exchange is added into filtrate obtained by step (2) regulates and controls pH value and (neutralize residual to 13.30
Remaining sodium hydroxide), mixed liquor is filtered, deionized water is added into filtrate to 50ml as silicon and aluminum source.
(4) 0.5g cetyl trimethylammonium bromide (CTAB) is weighed in 100mL beaker, and 10mL deionized water is added,
Stirring and dissolving forms CTAB solution, is added in 50ml filtrate obtained by step (3), using 0.5~6mol/L aqueous hydrochloric acid solution tune
Mixed solution pH value is controlled to 9,60 DEG C at a temperature of magnetic agitation 2 hours after be transferred to autoclave, 110 DEG C of temperature is lauched
Thermal crystallisation reacts for 24 hours, after reaction kettle is cooled to room temperature, product alcohol, deionized water is washed to supernatant without CTAB, 80
It dries, grind at a temperature of DEG C, obtain presoma.
(5) presoma obtained by step (4) is put into Muffle furnace (air atmosphere), 550 DEG C of temperature lower calcination keeps the temperature 6h
(heating rate is 2 DEG C/min), removes surfactant, obtains ordered mesoporous material Al-MCM-41, specific surface area 850m2/
G, pore volume 0.75m3/ g, average pore size 3.5nm.
Embodiment 4
(1) natural accumulation supporting stone 5g is weighed, the aqueous hydrochloric acid solution 150ml of 2mol/L is measured, by rectorite and aqueous hydrochloric acid solution
Mixing, 120 DEG C at a temperature of magnetic agitation 12 hours after obtain dirty solution, filtered after being cooled to room temperature, to pumping
Filter obtained solid product is washed with deionized to neutral (no chloride ion), and it is tired to obtain acidification for drying, grinding at a temperature of 80 DEG C
Hold in the palm stone powder；
(2) it weighs and is acidified rectorite powder 3g obtained by step (1), measure the sodium hydrate aqueous solution 30ml of 4mol/L, it will
Be acidified rectorite powder and sodium hydrate aqueous solution mixing, 30 DEG C at a temperature of magnetic agitation 20 hours after obtain dirty solution,
It is filtered after being cooled to room temperature, filtrate (pH value is 14.00~14.60) is spare；
(3) strongly acidic cation-exchange is added into filtrate obtained by step (2) regulates and controls pH value and (neutralize residual to 13.30
Remaining sodium hydroxide), mixed liquor is filtered, deionized water is added into filtrate to 50ml as silicon and aluminum source.
(4) 0.5g cetyl trimethylammonium bromide (CTAB) is weighed in 100mL beaker, and 10mL deionized water is added,
Stirring and dissolving forms CTAB solution, is added in 50ml filtrate obtained by step (3), using 0.5~6mol/L aqueous hydrochloric acid solution tune
Mixed solution pH value is controlled to 9,60 DEG C at a temperature of magnetic agitation 2 hours after be transferred to autoclave, 110 DEG C of temperature is lauched
Thermal crystallisation reacts for 24 hours, after reaction kettle is cooled to room temperature, product alcohol, deionized water is washed to supernatant without CTAB, 80
It dries, grind at a temperature of DEG C, obtain presoma.
(5) presoma obtained by step (4) is put into Muffle furnace (air atmosphere), 550 DEG C of temperature lower calcination keeps the temperature 6h
(heating rate is 2 DEG C/min), removes surfactant, obtains ordered mesoporous material Al-MCM-41, specific surface area 853m2/
G, pore volume 0.68m3/ g, average pore size 1.6nm.
Embodiment 5
(1) natural accumulation supporting stone 5g is weighed, the aqueous hydrochloric acid solution 250ml of 8mol/L is measured, by rectorite and aqueous hydrochloric acid solution
Mixing, 80 DEG C at a temperature of magnetic agitation 12 hours after obtain dirty solution, filtered after being cooled to room temperature, to suction filtration
Obtained solid product is washed with deionized to neutral (no chloride ion), and drying, grinding at a temperature of 80 DEG C obtain being acidified tired support
Stone powder；
(2) it weighs and is acidified rectorite powder 3g obtained by step (1), measure the sodium hydrate aqueous solution 15ml of 4mol/L, it will
Be acidified rectorite powder and sodium hydrate aqueous solution mixing, 30 DEG C at a temperature of magnetic agitation 20 hours after obtain dirty solution,
It is filtered after being cooled to room temperature, filtrate (pH value is 14.00~14.60) is spare；
(3) strongly acidic cation-exchange is added into filtrate obtained by step (2) regulates and controls pH value and (neutralize residual to 13.30
Remaining sodium hydroxide), mixed liquor is filtered, deionized water is added into filtrate to 50ml as silicon and aluminum source.
(4) 0.5g cetyl trimethylammonium bromide (CTAB) is weighed in 100mL beaker, and 10mL deionized water is added,
Stirring and dissolving forms CTAB solution, is added in 50ml filtrate obtained by step (3), using 0.5~6mol/L aqueous hydrochloric acid solution tune
Mixed solution pH value is controlled to 9,60 DEG C at a temperature of magnetic agitation 2 hours after be transferred to autoclave, 110 DEG C of temperature is lauched
Thermal crystallisation reacts for 24 hours, after reaction kettle is cooled to room temperature, product alcohol, deionized water is washed to supernatant without CTAB, 80
It dries, grind at a temperature of DEG C, obtain presoma.
(5) presoma obtained by step (4) is put into Muffle furnace (air atmosphere), 550 DEG C of temperature lower calcination keeps the temperature 6h
(heating rate is 2 DEG C/min), removes surfactant, obtains ordered mesoporous material Al-MCM-41, specific surface area 753m2/
G, pore volume 0.63m3/ g, average pore size 1.1nm.
Embodiment 6
(1) natural accumulation supporting stone 5g is weighed, the aqueous hydrochloric acid solution 500ml of 6mol/L is measured, by rectorite and aqueous hydrochloric acid solution
Mixing, 130 DEG C at a temperature of magnetic agitation 12 hours after obtain dirty solution, filtered after being cooled to room temperature, to pumping
Filter obtained solid product is washed with deionized to neutral (no chloride ion), and it is tired to obtain acidification for drying, grinding at a temperature of 80 DEG C
Hold in the palm stone powder；
(2) it weighs and is acidified rectorite powder 3g obtained by step (1), measure the sodium hydrate aqueous solution 45ml of 4mol/L, it will
Be acidified rectorite powder and sodium hydrate aqueous solution mixing, 30 DEG C at a temperature of magnetic agitation 20 hours after obtain dirty solution,
It is filtered after being cooled to room temperature, filtrate (pH value is 14.00~14.60) is spare；
(3) strongly acidic cation-exchange is added into filtrate obtained by step (2) regulates and controls pH value and (neutralize residual to 13.30
Remaining sodium hydroxide), mixed liquor is filtered, deionized water is added into filtrate to 50ml as silicon and aluminum source.
(4) 0.5g cetyl trimethylammonium bromide (CTAB) is weighed in 100mL beaker, and 10mL deionized water is added,
Stirring and dissolving forms CTAB solution, is added in 50ml filtrate obtained by step (3), using 0.5~6mol/L aqueous hydrochloric acid solution tune
Mixed solution pH value is controlled to 9,60 DEG C at a temperature of magnetic agitation 2 hours after be transferred to autoclave, 110 DEG C of temperature is lauched
Thermal crystallisation reacts for 24 hours, after reaction kettle is cooled to room temperature, product alcohol, deionized water is washed to supernatant without CTAB, 80
It dries, grind at a temperature of DEG C, obtain presoma.
(5) presoma obtained by step (4) is put into Muffle furnace (air atmosphere), 550 DEG C of temperature lower calcination keeps the temperature 6h
(heating rate is 2 DEG C/min), removes surfactant, obtains ordered mesoporous material Al-MCM-41, specific surface area 821m2/
G, pore volume 0.72m3/ g, average pore size 2.7nm.
Embodiment 7
(1) natural accumulation supporting stone 5g is weighed, the aqueous hydrochloric acid solution 250ml of 6mol/L is measured, by rectorite and aqueous hydrochloric acid solution
Mixing, 110 DEG C at a temperature of magnetic agitation 12 hours after obtain dirty solution, filtered after being cooled to room temperature, to pumping
Filter obtained solid product is washed with deionized to neutral (no chloride ion), and it is tired to obtain acidification for drying, grinding at a temperature of 80 DEG C
Hold in the palm stone powder；
(2) it weighs and is acidified rectorite powder 3g obtained by step (1), measure the sodium hydrate aqueous solution 30ml of 4mol/L, it will
Be acidified rectorite powder and sodium hydrate aqueous solution mixing, 10 DEG C at a temperature of magnetic agitation 20 hours after obtain dirty solution,
It is filtered after being cooled to room temperature, filtrate (pH value is 14.00~14.60) is spare；
(3) strongly acidic cation-exchange is added into filtrate obtained by step (2) regulates and controls pH value and (neutralize residual to 13.30
Remaining sodium hydroxide), mixed liquor is filtered, deionized water is added into filtrate to 50ml as silicon and aluminum source.
(4) 0.5g cetyl trimethylammonium bromide (CTAB) is weighed in 100mL beaker, and 10mL deionized water is added,
Stirring and dissolving forms CTAB solution, is added in 50ml filtrate obtained by step (3), using 0.5~6mol/L aqueous hydrochloric acid solution tune
Mixed solution pH value is controlled to 9,60 DEG C at a temperature of magnetic agitation 2 hours after be transferred to autoclave, 110 DEG C of temperature is lauched
Thermal crystallisation reacts for 24 hours, after reaction kettle is cooled to room temperature, product alcohol, deionized water is washed to supernatant without CTAB, 80
It dries, grind at a temperature of DEG C, obtain presoma.
(5) presoma obtained by step (4) is put into Muffle furnace (air atmosphere), 550 DEG C of temperature lower calcination keeps the temperature 6h
(heating rate is 2 DEG C/min), removes surfactant, obtains ordered mesoporous material Al-MCM-41, specific surface area 786m2/
G, pore volume 0.69m3/ g, average pore size 1.9nm.
Embodiment 8
(1) natural accumulation supporting stone 5g is weighed, the aqueous hydrochloric acid solution 250ml of 6mol/L is measured, by rectorite and aqueous hydrochloric acid solution
Mixing, 110 DEG C at a temperature of magnetic agitation 12 hours after obtain dirty solution, filtered after being cooled to room temperature, to pumping
Filter obtained solid product is washed with deionized to neutral (no chloride ion), and it is tired to obtain acidification for drying, grinding at a temperature of 80 DEG C
Hold in the palm stone powder；
(2) it weighs and is acidified rectorite powder 3g obtained by step (1), measure the sodium hydrate aqueous solution 30ml of 4mol/L, it will
Be acidified rectorite powder and sodium hydrate aqueous solution mixing, 50 DEG C at a temperature of magnetic agitation 20 hours after obtain dirty solution,
It is filtered after being cooled to room temperature, filtrate (pH value is 14.00~14.60) is spare；
(3) strongly acidic cation-exchange is added into filtrate obtained by step (2) regulates and controls pH value and (neutralize residual to 13.30
Remaining sodium hydroxide), mixed liquor is filtered, deionized water is added into filtrate to 50ml as silicon and aluminum source.
(4) 0.5g cetyl trimethylammonium bromide (CTAB) is weighed in 100mL beaker, and 10mL deionized water is added,
Stirring and dissolving forms CTAB solution, is added in 50ml filtrate obtained by step (3), using 0.5~6mol/L aqueous hydrochloric acid solution tune
Mixed solution pH value is controlled to 9,60 DEG C at a temperature of magnetic agitation 2 hours after be transferred to autoclave, 110 DEG C of temperature is lauched
Thermal crystallisation reacts for 24 hours, after reaction kettle is cooled to room temperature, product alcohol, deionized water is washed to supernatant without CTAB, 80
It dries, grind at a temperature of DEG C, obtain presoma.
(5) presoma obtained by step (4) is put into Muffle furnace (air atmosphere), 550 DEG C of temperature lower calcination keeps the temperature 6h
(heating rate is 2 DEG C/min), removes surfactant, obtains ordered mesoporous material Al-MCM-41, specific surface area 803m2/
G, pore volume 0.74m3/ g, average pore size 2.5nm.
Comparative example 4
This comparative example is inquired into, and does not carry out the resin treatment to alkali infusion solution, and concrete operations are as follows:
(1) natural accumulation supporting stone 5g is weighed, the aqueous hydrochloric acid solution 50ml of 1mol/L is measured, rectorite and aqueous hydrochloric acid solution is mixed
It closes, magnetic agitation obtained dirty solution after 12 hours at room temperature, was filtered after being cooled to room temperature, produced to obtained solid is filtered
Object is washed with deionized to neutral (no chloride ion), and drying, grinding at a temperature of 80 DEG C obtain acidification rectorite powder；
(2) it weighs and is acidified rectorite powder 3g obtained by step (1), measure the sodium hydrate aqueous solution 10ml of 1mol/L, it will
It is acidified rectorite powder and sodium hydrate aqueous solution mixing, magnetic agitation obtained dirty solution after 20 hours at room temperature, was cooled to
It is filtered after to room temperature, filtrate is spare；
(3) deionized water is added to 50ml as silicon and aluminum source into filtrate obtained by step (2).
(4) 0.5g cetyl trimethylammonium bromide (CTAB) is weighed in 100mL beaker, and 10mL deionized water is added,
Stirring and dissolving forms CTAB solution, is added in 50ml filtrate obtained by step (3), using 0.5~6mol/L aqueous hydrochloric acid solution tune
Mixed solution pH value is controlled to 9,60 DEG C at a temperature of magnetic agitation 2 hours after be transferred to autoclave, 110 DEG C of temperature is lauched
Thermal crystallisation reacts for 24 hours, after reaction kettle is cooled to room temperature, product alcohol, deionized water is washed to supernatant without CTAB, 80
It dries, grind at a temperature of DEG C, obtain presoma.
(5) presoma obtained by step (4) is put into Muffle furnace (air atmosphere), 550 DEG C of temperature lower calcination keeps the temperature 6h
(heating rate is 2 DEG C/min), removes surfactant, obtains white powder, prepares ordered mesoporous material Al-MCM-41 mistake
It loses.
Test experience:
1, white powder prepared by ordered mesoporous material Al-MCM-41 prepared by Example 1~2 and comparative example 1~4
Small angle X-ray diffraction analysis is carried out, as a result as shown in Fig. 2, ordered mesoporous material Al-MCM-41 prepared by Examples 1 to 2 goes out
Three characteristic diffraction peaks of typical MCM-41: (100), (110) and (200) diffraction maximum are showed, have shown prepared order mesoporous
Materials A l-MCM-41 has typical hexagonal structure, and the degree of order is higher；There is not allusion quotation in white powder prepared by comparative example 1~4
Three characteristic diffraction peaks of type MCM-41: (100), (110) and (200) diffraction maximum shows successfully prepare order mesoporous material
Expect Al-MCM-41.Embodiment 2 and embodiment 3 the result shows that alkali leaching solution carry out strongly acidic cation-exchange processing,
Alkali when extracting silicon source can be overcome to have remaining technical problem, success prepares ordered mesoporous material Al- by raw material of rectorite
MCM-41。
2, ordered mesoporous material Al-MCM-41 prepared by Example 1~2 carries out Wide angle X-ray diffraction analysis, as a result
As shown in figure 3, occurring diffraction maximum packet within the scope of 2 θ=22 °~24 °, show prepared ordered mesoporous material Al-MCM-
41 are made of amorphous silica.
3, ordered mesoporous material Al-MCM-41 prepared by Example 2 carries out nitrogen adsorption desorption analysis, as a result as schemed
Shown in 4, it is the feature of mesoporous material that prepared ordered mesoporous material Al-MCM-41 sample, which is typical IV type adsorption curve,
Sample specific surface area is 1105m2/ g, pore volume can reach 1.12cm3/ g, average pore size 3.8nm.
4, ordered mesoporous material Al-MCM-41 prepared by Example 2 is scanned electron microscope analysis, as a result such as Fig. 5 institute
Show, as can be seen from the figure prepared ordered mesoporous material Al-MCM-41 partial size is relatively uniform, and cellular structure needs transmission electron microscope
To characterize.
5, ordered mesoporous material Al-MCM-41 prepared by Example 2 carries out transmission electron microscope analysis, as a result such as Fig. 6 institute
Show, as can be seen from the figure prepared ordered mesoporous material Al-MCM-41 is perpendicular to mesopore orbit direction, in mesopore orbit
Portion's long-range order, along duct direction, duct in rule hexagonal structure, and duct is regular, size is uniform, the degree of order compared with
Height, this is consistent with SAXRD analysis result.
Claims (10)
1. a kind of method for preparing ordered mesoporous material Al-MCM-41 using rectorite, which comprises the following steps:
Step (1): rectorite obtains acidification rectorite through acid soak, separation of solid and liquid, washing, drying；
Step (2): acidification rectorite is separated by solid-liquid separation through alkali leaching processing, after, obtains alkali leaching liquor；
Step (3): alkali leaching liquor is mixed with strongly acidic cation-exchange, is then separated by solid-liquid separation mixed solution, is contained
Silicon and aluminum source filtrate；
Step (4): it is anti-then to carry out hydro-thermal for siliceous silicon source filtrate that step (3) is obtained, cationic surfactant mixing
It answers, obtains presoma；
Step (5): by presoma through calcination processing, ordered mesoporous material Al-MCM-41 is obtained.
2. the method for preparing ordered mesoporous material Al-MCM-41 using rectorite as described in claim 1, which is characterized in that
In step (1), the acid solution is the aqueous solution of inorganic acid, wherein H+Concentration is 2~8mol/L；
The solid-to-liquid ratio of rectorite and acid solution is 1: 30~1: 100g/mL.
3. the method for preparing ordered mesoporous material Al-MCM-41 using rectorite as claimed in claim 2, which is characterized in that
The temperature of acid soak process is 60~140 DEG C；Soaking time is 4~12 hours.
4. the method for preparing ordered mesoporous material Al-MCM-41 using rectorite as described in claim 1, which is characterized in that
The lye that the dipped journey of alkali uses is the aqueous solution of alkali metal hydroxide, in lye, OH-Concentration be 2~6mol/L；
The solid-to-liquid ratio for being acidified rectorite and lye is 1: 5~1: 20g/mL.
5. the method for preparing ordered mesoporous material Al-MCM-41 using rectorite as claimed in claim 4, which is characterized in that
The temperature of the dipped journey of alkali is 10~50 DEG C；Time be 8~for 24 hours.
6. the method for preparing ordered mesoporous material Al-MCM-41 using rectorite as claimed in claim 5, which is characterized in that
The pH value of alkali leaching liquor obtained by step (2) is 14.00~14.60.
7. the method as described in any one of claims 1 to 6 for preparing ordered mesoporous material Al-MCM-41 using rectorite,
It is characterized in that, in step (3), the alkali remained in alkali leaching liquor is neutralized using strongly acidic cation-exchange, until alkali leaches
Liquid pH value is 13.00~13.40.
8. the method for preparing ordered mesoporous material Al-MCM-41 using rectorite as described in claim 1, which is characterized in that
The cationic surfactant is cetyl trimethylammonium bromide；
The concentration of the cationic surfactant of the starting soln of hydro-thermal reaction is 0.1~0.5mol/L；
The pH value of the starting soln of hydro-thermal reaction is 8~12；
The temperature of hydro-thermal reaction is 100~150 DEG C；The hydro-thermal reaction time is 24~72h.
9. the method for preparing ordered mesoporous material Al-MCM-41 using rectorite as described in claim 1, which is characterized in that
Calcination processing carries out in air atmosphere；The temperature of calcining is 500~600 DEG C；
The heating rate of calcination process is 1~3 DEG C/min.
10. the method for preparing ordered mesoporous material Al-MCM-41 using rectorite as claimed in claim 9, which is characterized in that
Calcination time is 4~10h.
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| CN106745032A (en) * | 2016-11-29 | 2017-05-31 | 内蒙古师范大学 | The method that the mesopore molecular sieves of Al MCM 41 are directly synthesized by kaolin or Hanggin 2# soil |
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