CN110272057B - Method for preparing ordered mesoporous material Al-MCM-41 by utilizing rectorite - Google Patents
Method for preparing ordered mesoporous material Al-MCM-41 by utilizing rectorite Download PDFInfo
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Abstract
The invention belongs to the field of material preparation, and particularly discloses a method for preparing an ordered mesoporous material Al-MCM-41 by utilizing rectorite, namely rectoriteSoaking stone in acid liquor, performing solid-liquid separation, washing and drying to obtain acidified rectorite; performing alkaline leaching treatment on acidified rectorite, and then performing solid-liquid separation to obtain an alkaline leaching solution; mixing the alkaline leaching solution with strong acid type cation exchange resin, and then carrying out solid-liquid separation on the mixed solution to obtain filtrate containing silicon and aluminum sources; mixing the filtrate containing the silicon and aluminum source and a cationic surfactant, and then carrying out hydrothermal reaction to obtain a precursor; and calcining the precursor to obtain the ordered mesoporous material Al-MCM-41. The method takes cheap natural rectorite mineral as a raw material, and a silica-alumina source is not required to be additionally added, so that the ordered mesoporous material Al-MCM-41 is prepared; the prepared ordered mesoporous material Al-MCM-41 mesoporous channels are parallel to each other, the cross sections of the mesoporous material Al-MCM-41 mesoporous channels are in hexagonal arrangement, the ordered mesoporous material Al-MCM-41 mesoporous channels have a regular two-dimensional hexagonal structure, and the specific surface area can reach 1105m2The pore volume can reach 1.12cm3(g), the pore size distribution is concentrated, and the pore performance is good.
Description
Technical Field
The invention belongs to the field of inorganic non-metallic materials, and particularly relates to a method for preparing an ordered mesoporous material Al-MCM-41 by utilizing rectorite.
Background
The ordered mesoporous material is a novel material developed at the end of the 20 th century, and has a highly regular and ordered pore structure, adjustable pore size, higher specific surface area and larger adsorption capacity. In 1992, Mobil company used surfactant as template agent to prepare highly ordered M41S series silicon-based mesoporous material by hydrothermal synthesis, and the pore type included: hexagonal phase cylindrical pores (MCM-41) in directional arrangement, cubic phase polyhedral pores (MCM-48) in three-dimensional regular arrangement and lamellar pores (MCM-50) in parallel arrangement. Because of its unique structure and properties, the silicon-based ordered mesoporous material is widely used in the fields of separation, catalysis, environmental management, drug release and other biology, and especially after being modified by organic reagents, it has different biochemical, physical and chemical properties, thereby showing extraordinary application prospects and becoming a nano material with great development value.
At present, most silicon sources adopted for preparing silicon-based ordered mesoporous materials are chemical reagents, such as Tetraethoxysilane (TEOS), methyl orthosilicate (TMOS), sodium silicate and the like, raw materials are expensive, and environmental pollution is easily caused in the preparation process of the chemical reagents. The natural silicate mineral is rich in resources, low in price and rich in silicon and aluminum elements, and is an ideal raw material for preparing the silicon-based mesoporous material on a large scale. Chinese patent application (CN106145132A) of Guanyu et Al discloses a method for preparing ordered mesoporous material Al-MCM-41 by using attapulgite, and the specific surface area of the prepared ordered mesoporous material Al-MCM-41 can reach 998m2Per g, pore volume can reach 0.80cm3More than g, concentrated pore size distribution and good pore performance, and widens the application field of the attapulgite. The Chinese patent application (CN103861556A) of Van Jianwei et al discloses a method for preparing a mesoporous material by using fly ash, and the prepared fly ash-based SBA-15 has a regular two-dimensional hexagonal structure and a pore volume of 0.6-0.9 cm3Per g, specific surface area up to 800m2The pore diameter is 5-8 nm, and the application field of the fly ash is widened. Chinese patent application (CN101643217A) of Yanghuaning et al discloses a method for preparing ordered mesoporous material by using bentonite, and the specific surface area of the prepared ordered mesoporous material can be up to 1000m2More than g, the pore volume can reach 1.00cm3More than g, concentrated pore size distribution, and widened application field of bentonite. Chinese patent application (CN102992348B) of Zhouyuyu et Al discloses a method for preparing ordered composite mesoporous material Al-SBA-15 by using halloysite as a raw material, and widens the application field of halloysite. Wu Qi Sheng et al (CN102060301A) discloses a method for preparing mesoporous material with coal-series kaolin as raw material, and the specific surface area of the obtained mesoporous material is 800-1200 m2The method widens the application field of the coal-series kaolin. Chinese patent application (CN104016369A) of Duchufang, etc. discloses a method for synthesizing high-stability ordered mesoporous material Al-SBA-15 by using kaolin, the preparation process is simple, the raw materials are easy to obtain, the operation conditions are loose, the synthesized ordered mesoporous material has good hydrothermal stability and catalytic activity, and the application field of the kaolin is widened. In addition, it also relates to the use of bubblesThe research report of preparing ordered mesoporous material with stone, diatomite and talc as material. However, no research report on the development of rectorite to prepare the ordered mesoporous material Al-MCM-41 exists in various natural silicate minerals.
The rectorite crystal structure is different from clay minerals such as attapulgite, bentonite, halloysite, kaolin, sepiolite, diatomite, talc and the like, is a mineral with a special aluminosilicate crystal structure, and is formed by regularly and alternately stacking dioctahedral mica layers and dioctahedral montmorillonite layers according to a ratio of 1:1 under special natural conditions, but not simply combining the dioctahedral mica layers and the dioctahedral montmorillonite layers, so that the regular interlayer clay mineral is formed. The rectorite unit layers differ from the simple mathematical addition of the mica and montmorillonite layers by a qualitative difference. In the mica mineral structure layer, the tetrahedrons on two sides in the unit layer are high point load; in montmorillonite minerals, tetrahedrons on both sides of the unit layer are low-point charges, and the unique structural unit layer is quite rare. The discovery of rectorite has been for over one hundred years, and currently, researchers mainly concentrate on the fields of high-quality deep drilling mud, catalyst carriers, lubricating esters, ceramics, rubber, environment-friendly materials, filter materials, coating suspending agents and the like for developing and utilizing the rectorite. However, in the prior art, no report is available about how to prepare the ordered mesoporous material Al-MCM-41 by overcoming the problem of extracting a silica-alumina source by using rectorite as a raw material.
Disclosure of Invention
The invention aims to provide a method for preparing an ordered mesoporous material Al-MCM-41 by utilizing rectorite, and the method takes the rectorite as a raw material to prepare the Al-MCM-41.
A method for preparing ordered mesoporous material Al-MCM-41 by utilizing rectorite comprises the following steps:
step (1): soaking rectorite in acid solution, performing solid-liquid separation, washing and drying to obtain acidified rectorite;
step (2): performing alkaline leaching treatment on acidified rectorite, and then performing solid-liquid separation to obtain an alkaline leaching solution;
and (3): mixing the alkaline leaching solution with strong acid type cation exchange resin, and then carrying out solid-liquid separation on the mixed solution to obtain filtrate containing silicon and aluminum sources;
and (4): mixing the filtrate containing the silicon and aluminum source obtained in the step (3) with a cationic surfactant, and then carrying out hydrothermal reaction to obtain a precursor;
and (5): and calcining the precursor to obtain the ordered mesoporous material Al-MCM-41.
In the prior art, a silica-aluminum source is obtained by taking attapulgite, bentonite, halloysite, kaolin, sepiolite, diatomite, talc and other clay minerals as raw materials. Because rectorite has different structural properties from these clay minerals, the disclosed technology of extracting a silica-alumina source from clay minerals is not suitable for rectorite. In the invention, the rectorite is used as a raw material, an acid-base leaching method and a hydrothermal method are adopted, the unique crystal structure of the rectorite is hindered, and the ordered mesoporous material Al-MCM-41 is difficult to be successfully prepared; through a great deal of research, the inventor finds that the main reason of the failure in preparing the ordered mesoporous material Al-MCM-41 by using the rectorite is that when a silicon source is extracted by using the disclosed alkaline leaching technology, alkali is remained in the alkaline leaching process due to the unique crystal structure of the rectorite, however, the ordered mesoporous material Al-MCM-41 cannot be successfully prepared by neutralizing the alkali remained in the alkaline leaching solution by using inorganic acid in the earlier working period of the invention. Through further research, the invention discovers that the ordered mesoporous material Al-MCM-41 can be unexpectedly prepared by treating the rectorite alkaline leaching solution with strong acid type cation exchange resin.
According to the invention, rectorite is innovatively used as a raw material, the technical difficulty that mesoporous material Al-MCM-41 prepared by using the rectorite cannot be successfully prepared is overcome by the acid leaching-alkaline leaching-resin treatment technology, a suitable silica-alumina source is obtained, and then the ordered mesoporous material Al-MCM-41 with a regular and ordered pore channel structure, adjustable pore size and high specific surface area is prepared by using a cationic surfactant as a template and adopting a hydrothermal crystallization reaction method. The method provided by the invention does not need to add any pure silicon or pure aluminum chemical reagent, can expand the application field of the rectorite and realize the recycling of the rectorite.
Preferably, in the step (1), the acid solution is an aqueous solution of strong inorganic acid; preferably an aqueous hydrochloric acid solution.
Preferably, in the step (1), the acid solution H is+The concentration is 2-8 mol/L.
Preferably, in the step (1), the solid-to-liquid ratio of the rectorite to the acid solution is 1: 30-1: 100 g/mL.
Preferably, in the step (1), the temperature of the acid liquor soaking process is 60-140 ℃; the soaking time is 4-12 hours.
Soaking in acid solution, cooling to room temperature, performing solid-liquid separation (such as suction filtration), washing the obtained solid product with deionized water to neutrality (no chloride ion), drying, and grinding to obtain acidified rectorite powder.
Preferably, the alkali liquor adopted in the alkali leaching process is an aqueous solution of alkali metal hydroxide; the preferred alkali solution is sodium hydroxide solution.
Preferably, in alkaline solution, OH-The concentration of (b) is 2-6 mol/L.
Preferably, the solid-liquid ratio of the acidified rectorite to the alkali liquor is 1: 5-1: 20 g/mL.
Preferably, the temperature in the alkaline leaching process is 10-50 ℃; the time is 8-24 h.
The pH value of the alkali leaching solution obtained in the step (2) is 14.00-14.60; the alkali used in the alkali leaching process remains; the invention innovatively adds strong acid type cation exchange resin into the alkaline leaching solution obtained in the step (2) to neutralize residual alkali, and performs suction filtration on the mixed solution, and takes the filtrate as a silicon-aluminum source.
Preferably, in the step (3), the alkali remained in the alkali leaching solution is neutralized by using a strong acid type cation exchange resin until the pH value of the alkali leaching solution is 13.00-13.40. The innovation point in the process is that the strong acid type cation exchange resin releases H+With OH in the alkaline leach liquor-Reaction to form H2O, while adsorbing alkali-introduced cations (e.g. Na) from the alkali leach solution+) Compared with the conventional method of neutralizing by adopting acids such as HCl and the like, the method of the invention can unexpectedly and successfully prepare the solution without sodium hydroxide and the solution without a silicon-aluminum source (the pH value of the sodium silicate solution is 13.00-13.40, so that the pH value of the alkaline leaching solution is regulated to 13.00-13.40) by adopting the strong acid type cation exchange resinOrdered mesoporous material Al-MCM-41.
The strong acid cation exchange resin may be any type of strong acid cation exchange resin known to those skilled in the art.
And (3) mixing a cationic surfactant with the filtrate containing silicon and aluminum sources obtained in the step (3), regulating the pH value of the filtrate containing silicon and aluminum sources by using acid, then preserving heat in a high-pressure reaction kettle, carrying out hydrothermal reaction, and treating after the reaction is finished to obtain a precursor.
Preferably, the cationic surfactant is cetyl trimethyl ammonium bromide.
Preferably, the concentration of the cationic surfactant in the starting solution of the hydrothermal reaction is 0.1 to 0.5 mol/L.
Preferably, the pH value of the initial solution of the hydrothermal reaction is 8-12.
Preferably, the temperature of the hydrothermal reaction is 100-150 ℃; the hydrothermal reaction time is 24-72 h.
After the hydrothermal reaction is finished, cooling the reaction container to room temperature, washing the product with alcohol and deionized water until the supernatant does not contain a surfactant, drying and grinding to obtain the precursor.
And calcining the precursor, and removing the surfactant to obtain the ordered mesoporous material Al-MCM-41.
The calcination process may be carried out in existing conventional equipment, preferably in a muffle furnace.
Preferably, the atmosphere of the calcination treatment is an air atmosphere.
Preferably, the temperature of the calcination treatment is 500 to 600 ℃.
Preferably, the temperature rise rate in the calcining process is 1-3 ℃/min.
Preferably, the calcination time is 4-10 h.
The invention provides a more preferable method for preparing an ordered mesoporous material Al-MCM-41 by using rectorite, which comprises the following specific preparation steps:
(1) taking natural rectorite as a raw material, taking 2-8 mol/L hydrochloric acid aqueous solution as a leaching agent, mixing the rectorite and the hydrochloric acid aqueous solution according to the solid-liquid ratio of 1: 30-1: 100 (g: mL), magnetically stirring for 4-12 hours at the temperature of 60-140 ℃ to obtain turbid liquid, cooling the turbid liquid to room temperature, carrying out suction filtration, washing a solid product obtained by suction filtration to be neutral (without chloride ions) with deionized water, and drying and grinding at the temperature of 80 ℃ to obtain acidified rectorite powder;
(2) taking the acidified rectorite powder obtained in the step (1) as a raw material, taking 2-6 mol/L of sodium hydroxide aqueous solution as a leaching agent, mixing the acidified rectorite powder and the sodium hydroxide aqueous solution according to the solid-to-liquid ratio of 1: 5-1: 20 (g: mL), magnetically stirring at the temperature of 10-50 ℃ for 8-24 hours to obtain a turbid solution, cooling to room temperature, performing suction filtration, and reserving a filtrate (the pH value is 14.00-14.60) for later use;
(3) and (3) adding strong acid type cation exchange resin into the filtrate obtained in the step (2) to neutralize residual sodium hydroxide until the pH value of the alkaline leaching solution is 13.00-13.40, carrying out suction filtration on the mixed solution, and taking the filtrate as a silica-alumina source.
(4) Adding a cationic surfactant Cetyl Trimethyl Ammonium Bromide (CTAB) into the filtrate obtained in the step (3), regulating the pH value of the mixed solution to 8-12 by adopting 0.5-6 mol/L hydrochloric acid aqueous solution, magnetically stirring the mixed solution at the temperature of 60 ℃ for 2 hours, transferring the mixed solution into a high-pressure reaction kettle, carrying out hydrothermal crystallization reaction at the temperature of 100-150 ℃ for 24-72 hours, cooling the reaction kettle to room temperature, washing the product with alcohol and deionized water until the supernatant does not contain CTAB, and drying and grinding the product at the temperature of 80 ℃ to obtain a precursor.
(5) And (3) putting the precursor obtained in the step (4) into a muffle furnace, calcining at the temperature of 500-600 ℃ for 4-10 h (the heating rate is 1-3 ℃/min), and removing the surfactant to obtain the ordered mesoporous material Al-MCM-41.
Compared with the prior art, the invention has the characteristics and beneficial effects that:
(1) according to the method, the rectorite is used as a raw material, and the technical problem that alkali has residue when a silicon source is extracted by using an open alkali leaching technology due to the special structural property of the rectorite is solved through an acid leaching-alkali leaching-resin treatment technology to obtain a silica-alumina source, the silica-alumina source is not required to be additionally added in the process, and the ordered mesoporous material Al-MCM-41 is prepared through a chemical method, so that the application field of the rectorite is widened, and the method has the potential for producing a mineral-based composite material with high added value;
(2) the silicon source extraction technology can be realized at normal temperature, so that the energy consumption is saved, and the production cost is reduced;
(3) the invention utilizes strong acid type cation exchange resin to neutralize alkali remained in the alkali leaching solution, namely the strong acid type cation exchange resin releases H+With OH in the alkaline leach liquor-Reaction to form H2O, and simultaneously adsorbing Na in the alkali leaching solution+And obtaining the solution of the silica-alumina source without sodium hydroxide.
(4) The preparation process has little pollution to the environment, simple preparation process, large raw material storage amount and low price;
(5) the pore channels of the ordered mesoporous material Al-MCM-41 prepared by the method are parallel to each other, the cross section of the ordered mesoporous material Al-MCM-41 is in hexagonal arrangement, and the ordered mesoporous material Al-MCM-41 has a regular two-dimensional hexagonal structure;
(6) the specific surface area of the ordered mesoporous material Al-MCM-41 prepared by the invention can reach 1105m2The pore volume can reach 1.12cm3More than g, concentrated pore size distribution and good pore performance.
Description of the drawings:
FIG. 1 is an X-ray diffraction pattern of raw rectorite ore;
FIG. 2 is a small angle X-ray diffraction pattern of the ordered mesoporous material Al-MCM-41 prepared in examples 1-2 of the present invention and the white powder prepared in comparative examples 1-4;
FIG. 3 is a wide-angle X-ray diffraction pattern of the ordered mesoporous material Al-MCM-41 prepared in examples 1-2 of the present invention;
FIG. 4 shows N of the ordered mesoporous material Al-MCM-41 prepared in example 2 of the present invention2An adsorption-desorption isotherm (a) and a BJH pore size distribution curve (b);
FIG. 5 is a scanning electron micrograph of the ordered mesoporous material Al-MCM-41 prepared in example 2 of the present invention;
FIG. 6 is a transmission electron micrograph of the ordered mesoporous material Al-MCM-41 prepared in example 2 of the present invention.
Detailed Description
The invention provides a method for preparing ordered mesoporous material Al-MCM-41 by utilizing rectorite, which comprises the following specific preparation steps:
(1) taking natural rectorite as a raw material, taking 2-8 mol/L hydrochloric acid aqueous solution as a leaching agent, and mixing the raw material and the leaching agent according to a solid-liquid ratio of 1: mixing rectorite and a hydrochloric acid aqueous solution according to a ratio of 30-1: 100 (g: mL), magnetically stirring for 4-12 hours at a temperature of 60-140 ℃ to obtain a turbid liquid, cooling to room temperature, performing suction filtration, washing a solid product obtained by suction filtration to be neutral (free of chloride ions) by using deionized water, drying and grinding at a temperature of 80 ℃ to obtain acidified rectorite powder;
(2) taking the acidified rectorite powder obtained in the step (1) as a raw material, taking 2-6 mol/L of sodium hydroxide aqueous solution as a leaching agent, mixing the acidified rectorite powder and the sodium hydroxide aqueous solution according to the solid-to-liquid ratio of 1: 5-1: 20 (g: mL), magnetically stirring at the temperature of 10-50 ℃ for 8-24 hours to obtain a turbid solution, cooling to room temperature, performing suction filtration, and reserving a filtrate (the pH value is 14.00-14.60) for later use;
(3) and (3) adding strong acid type cation exchange resin into the filtrate obtained in the step (2) to neutralize residual sodium hydroxide until the pH value of the alkaline leaching solution is 13.00-13.40, carrying out suction filtration on the mixed solution, and taking the filtrate as a silica-alumina source.
(4) Adding a cationic surfactant Cetyl Trimethyl Ammonium Bromide (CTAB) into the filtrate obtained in the step (3), regulating the pH value of the mixed solution to 8-12 by adopting 0.5-6 mol/L hydrochloric acid aqueous solution, magnetically stirring the mixed solution at the temperature of 60 ℃ for 2 hours, transferring the mixed solution into a high-pressure reaction kettle, carrying out hydrothermal crystallization reaction at the temperature of 100-150 ℃ for 24-72 hours, cooling the reaction kettle to room temperature, washing the product with alcohol and deionized water until the supernatant does not contain CTAB, and drying and grinding the product at the temperature of 80 ℃ to obtain a precursor.
(5) And (3) putting the precursor obtained in the step (4) into a muffle furnace, calcining at the temperature of 500-600 ℃ for 4-10 h (the heating rate is 1-3 ℃/min), and removing the surfactant to obtain the ordered mesoporous material Al-MCM-41.
The present invention is further illustrated by the following examples.
In the present invention, the strong acid type cation exchange resin can be selected from those known in the art, and in the following examples, unless otherwise stated, they are selected from those of 001 × 7(732) type and those of Shanghai Hua membrance industries, Ltd.
Example 1
(1) Weighing 5g of natural rectorite, weighing 250ml of 6mol/L hydrochloric acid aqueous solution, mixing the rectorite and the hydrochloric acid aqueous solution, magnetically stirring at the temperature of 110 ℃ for 12 hours to obtain turbid liquid, cooling to room temperature, performing suction filtration, washing a solid product obtained by the suction filtration with deionized water to be neutral (without chloride ions), drying at the temperature of 80 ℃, and grinding to obtain acidified rectorite powder;
(2) weighing 3g of the acidified rectorite powder obtained in the step (1), weighing 30ml of a 4mol/L sodium hydroxide aqueous solution, mixing the acidified rectorite powder and the sodium hydroxide aqueous solution, magnetically stirring at the temperature of 30 ℃ for 20 hours to obtain a turbid solution, cooling to room temperature, performing suction filtration, and reserving a filtrate (the pH value is 14.00-14.60);
(3) and (3) adding strong acid type cation exchange resin into the filtrate obtained in the step (2) to regulate the pH value to 13.30 (neutralizing residual sodium hydroxide), carrying out suction filtration on the mixed solution, and supplementing deionized water into the filtrate to 50ml to serve as a silica-alumina source.
(4) Weighing 0.5g of Cetyl Trimethyl Ammonium Bromide (CTAB) into a 100mL beaker, adding 10mL of deionized water, stirring and dissolving to form a CTAB solution, adding the CTAB solution into 50mL of filtrate obtained in the step (3), regulating and controlling the pH value of the mixed solution to 9 by using 0.5-6 mol/L hydrochloric acid aqueous solution, magnetically stirring at 60 ℃ for 2 hours, transferring the mixed solution into a high-pressure reaction kettle, carrying out hydrothermal crystallization reaction at 110 ℃ for 24 hours, cooling the reaction kettle to room temperature, washing the product with alcohol and deionized water until the supernatant does not contain CTAB, and drying and grinding at 80 ℃ to obtain a precursor.
(5) Putting the precursor obtained in the step (4) into a muffle furnace (air atmosphere), calcining at 550 ℃ for 6h (the heating rate is 2 ℃/min), removing the surfactant to obtain the ordered mesoporous material Al-MCM-41 with the specific surface area of 968m2Per g, pore volume 0.83m3In terms of/g, the mean pore diameter is 3.4 nm.
Example 2
(1) Weighing 5g of natural rectorite, weighing 250ml of 6mol/L hydrochloric acid aqueous solution, mixing the rectorite and the hydrochloric acid aqueous solution, magnetically stirring at the temperature of 110 ℃ for 12 hours to obtain turbid liquid, cooling to room temperature, performing suction filtration, washing a solid product obtained by the suction filtration with deionized water to be neutral (without chloride ions), drying at the temperature of 80 ℃, and grinding to obtain acidified rectorite powder;
(2) weighing 3g of the acidified rectorite powder obtained in the step (1), weighing 30ml of a 4mol/L sodium hydroxide aqueous solution, mixing the acidified rectorite powder and the sodium hydroxide aqueous solution, magnetically stirring at the temperature of 30 ℃ for 20 hours to obtain a turbid solution, cooling to room temperature, performing suction filtration, and reserving a filtrate (the pH value is 14.00-14.60);
(3) and (3) adding strong acid type cation exchange resin into the filtrate obtained in the step (2) to regulate the pH value to 13.30 (neutralizing residual sodium hydroxide), carrying out suction filtration on the mixed solution, and supplementing deionized water into the filtrate to 50ml to serve as a silica-alumina source.
(4) Weighing 1g of Cetyl Trimethyl Ammonium Bromide (CTAB) into a 100mL beaker, adding 10mL of deionized water, stirring and dissolving to form a CTAB solution, adding the CTAB solution into 50mL of filtrate obtained in the step (3), regulating and controlling the pH value of the mixed solution to 9 by using 0.5-6 mol/L hydrochloric acid aqueous solution, magnetically stirring at 60 ℃ for 2 hours, transferring the mixed solution into a high-pressure reaction kettle, carrying out hydrothermal crystallization reaction at 110 ℃ for 24 hours, cooling the reaction kettle to room temperature, washing the product with alcohol and deionized water until the supernatant does not contain CTAB, and drying and grinding at 80 ℃ to obtain a precursor.
(5) Putting the precursor obtained in the step (4) into a muffle furnace (air atmosphere), calcining at 550 ℃ for 6h (the heating rate is 2 ℃/min), removing the surfactant to obtain the ordered mesoporous material Al-MCM-41 with the specific surface area of 1105m2Per g, pore volume 1.12m3In terms of/g, the mean pore diameter is 3.8 nm.
Comparative example 1
Compared with the example 2, the difference is that in the step (3), the alkaline leaching solution does not strengthen the acid type cation exchange resin, and the specific operation is as follows:
(1) weighing 5g of natural rectorite, weighing 250ml of 6mol/L hydrochloric acid aqueous solution, mixing the rectorite and the hydrochloric acid aqueous solution, magnetically stirring at the temperature of 110 ℃ for 12 hours to obtain turbid liquid, cooling to room temperature, performing suction filtration, washing a solid product obtained by the suction filtration with deionized water to be neutral (without chloride ions), drying at the temperature of 80 ℃, and grinding to obtain acidified rectorite powder;
(2) weighing 3g of the acidified rectorite powder obtained in the step (1), weighing 30ml of a sodium hydroxide aqueous solution of 4mol/L, mixing the acidified rectorite powder and the sodium hydroxide aqueous solution, magnetically stirring at the temperature of 30 ℃ for 20 hours to obtain a turbid solution, cooling to room temperature, performing suction filtration, and reserving a filtrate;
(3) and (3) adding deionized water to the filtrate obtained in the step (2) to 50ml as a silicon-aluminum source (the pH value is 14.20).
(4) Weighing 1g of Cetyl Trimethyl Ammonium Bromide (CTAB) into a 100mL beaker, adding 10mL of deionized water, stirring and dissolving to form a CTAB solution, adding the CTAB solution into 50mL of filtrate obtained in the step (3), regulating and controlling the pH value of the mixed solution to 9 by using 0.5-6 mol/L hydrochloric acid aqueous solution, magnetically stirring at 60 ℃ for 2 hours, transferring the mixed solution into a high-pressure reaction kettle, carrying out hydrothermal crystallization reaction at 110 ℃ for 24 hours, cooling the reaction kettle to room temperature, washing the product with alcohol and deionized water until the supernatant does not contain CTAB, and drying and grinding at 80 ℃ to obtain a precursor.
(5) And (3) putting the precursor obtained in the step (4) into a muffle furnace (air atmosphere), calcining at 550 ℃ for 6h (the heating rate is 2 ℃/min), removing the surfactant to obtain white powder, and failing to prepare the ordered mesoporous material Al-MCM-41.
Comparative example 2
Compared with the example 2, the difference is that in the step (3), HCl is used for replacing the strong acid type cation exchange resin, and the pH value of the solution is regulated to 13.30, and the specific operation is as follows:
(1) weighing 5g of natural rectorite, weighing 250ml of 6mol/L hydrochloric acid aqueous solution, mixing the rectorite and the hydrochloric acid aqueous solution, magnetically stirring at the temperature of 110 ℃ for 12 hours to obtain turbid liquid, cooling to room temperature, performing suction filtration, washing a solid product obtained by the suction filtration with deionized water to be neutral (without chloride ions), drying at the temperature of 80 ℃, and grinding to obtain acidified rectorite powder;
(2) weighing 3g of the acidified rectorite powder obtained in the step (1), weighing 30ml of a 4mol/L sodium hydroxide aqueous solution, mixing the acidified rectorite powder and the sodium hydroxide aqueous solution, magnetically stirring at the temperature of 30 ℃ for 20 hours to obtain a turbid solution, cooling to room temperature, performing suction filtration, and reserving a filtrate (the pH value is 14.00-14.60);
(3) and (3) adding 3mol/L hydrochloric acid aqueous solution into the filtrate obtained in the step (2) to regulate the pH value to 13.30 (neutralizing residual sodium hydroxide), carrying out suction filtration on the mixed solution, and supplementing deionized water into the filtrate to 50ml to be used as a silicon-aluminum source.
(4) Weighing 1g of Cetyl Trimethyl Ammonium Bromide (CTAB) into a 100mL beaker, adding 10mL of deionized water, stirring and dissolving to form a CTAB solution, adding the CTAB solution into 50mL of filtrate obtained in the step (3), regulating and controlling the pH value of the mixed solution to 9 by using 0.5-6 mol/L hydrochloric acid aqueous solution, magnetically stirring at 60 ℃ for 2 hours, transferring the mixed solution into a high-pressure reaction kettle, carrying out hydrothermal crystallization reaction at 110 ℃ for 24 hours, cooling the reaction kettle to room temperature, washing the product with alcohol and deionized water until the supernatant does not contain CTAB, and drying and grinding at 80 ℃ to obtain a precursor.
(5) And (3) putting the precursor obtained in the step (4) into a muffle furnace (air atmosphere), calcining at 550 ℃ for 6h (the heating rate is 2 ℃/min), removing the surfactant to obtain white powder, and failing to prepare the ordered mesoporous material Al-MCM-41.
Comparative example 3
Compared with the example 2, the difference is that in the step (3), the strong acid type cation exchange resin is adopted, the pH value of the solution is regulated to 9, and the specific operation is as follows:
(1) weighing 5g of natural rectorite, weighing 250ml of 6mol/L hydrochloric acid aqueous solution, mixing the rectorite and the hydrochloric acid aqueous solution, magnetically stirring at the temperature of 110 ℃ for 12 hours to obtain turbid liquid, cooling to room temperature, performing suction filtration, washing a solid product obtained by the suction filtration with deionized water to be neutral (without chloride ions), drying at the temperature of 80 ℃, and grinding to obtain acidified rectorite powder;
(2) weighing 3g of the acidified rectorite powder obtained in the step (1), weighing 30ml of a 4mol/L sodium hydroxide aqueous solution, mixing the acidified rectorite powder and the sodium hydroxide aqueous solution, magnetically stirring at the temperature of 30 ℃ for 20 hours to obtain a turbid solution, cooling to room temperature, performing suction filtration, and reserving a filtrate (the pH value is 14.00-14.60);
(3) and (3) adding strong acid type cation exchange resin into the filtrate obtained in the step (2) to regulate the pH value to 9, carrying out suction filtration on the mixed solution, and supplementing deionized water into the filtrate to 50ml to serve as a silica-alumina source.
(4) Weighing 1g of Cetyl Trimethyl Ammonium Bromide (CTAB) into a 100mL beaker, adding 10mL of deionized water, stirring and dissolving to form a CTAB solution, adding the CTAB solution into 50mL of filtrate obtained in the step (3), regulating and controlling the pH value of the mixed solution to 9 by using 0.5-6 mol/L hydrochloric acid aqueous solution, magnetically stirring at 60 ℃ for 2 hours, transferring the mixed solution into a high-pressure reaction kettle, carrying out hydrothermal crystallization reaction at 110 ℃ for 24 hours, cooling the reaction kettle to room temperature, washing the product with alcohol and deionized water until the supernatant does not contain CTAB, and drying and grinding at 80 ℃ to obtain a precursor.
(5) And (3) putting the precursor obtained in the step (4) into a muffle furnace (air atmosphere), calcining at 550 ℃ for 6h (the heating rate is 2 ℃/min), removing the surfactant to obtain white powder, and failing to prepare the ordered mesoporous material Al-MCM-41.
Example 3
(1) Weighing 5g of natural rectorite, weighing 250ml of 6mol/L hydrochloric acid aqueous solution, mixing the rectorite and the hydrochloric acid aqueous solution, magnetically stirring at the temperature of 110 ℃ for 12 hours to obtain turbid liquid, cooling to room temperature, performing suction filtration, washing a solid product obtained by the suction filtration with deionized water to be neutral (without chloride ions), drying at the temperature of 80 ℃, and grinding to obtain acidified rectorite powder;
(2) weighing 3g of the acidified rectorite powder obtained in the step (1), weighing 30ml of a 2mol/L sodium hydroxide aqueous solution, mixing the acidified rectorite powder and the sodium hydroxide aqueous solution, magnetically stirring at the temperature of 30 ℃ for 20 hours to obtain a turbid solution, cooling to room temperature, performing suction filtration, and reserving a filtrate (the pH value is 14.00-14.60);
(3) and (3) adding strong acid type cation exchange resin into the filtrate obtained in the step (2) to regulate the pH value to 13.30 (neutralizing residual sodium hydroxide), carrying out suction filtration on the mixed solution, and supplementing deionized water into the filtrate to 50ml to serve as a silica-alumina source.
(4) Weighing 0.5g of Cetyl Trimethyl Ammonium Bromide (CTAB) into a 100mL beaker, adding 10mL of deionized water, stirring and dissolving to form a CTAB solution, adding the CTAB solution into 50mL of filtrate obtained in the step (3), regulating and controlling the pH value of the mixed solution to 9 by using 0.5-6 mol/L hydrochloric acid aqueous solution, magnetically stirring at 60 ℃ for 2 hours, transferring the mixed solution into a high-pressure reaction kettle, carrying out hydrothermal crystallization reaction at 110 ℃ for 24 hours, cooling the reaction kettle to room temperature, washing the product with alcohol and deionized water until the supernatant does not contain CTAB, and drying and grinding at 80 ℃ to obtain a precursor.
(5) Putting the precursor obtained in the step (4) into a muffle furnace (air atmosphere), calcining at 550 ℃ for 6h (the heating rate is 2 ℃/min), removing the surfactant to obtain the ordered mesoporous material Al-MCM-41 with the specific surface area of 850m2Per g, pore volume 0.75m3In terms of/g, the mean pore diameter is 3.5 nm.
Example 4
(1) Weighing 5g of natural rectorite, weighing 150ml of 2mol/L hydrochloric acid aqueous solution, mixing the rectorite and the hydrochloric acid aqueous solution, magnetically stirring at 120 ℃ for 12 hours to obtain turbid liquid, cooling to room temperature, performing suction filtration, washing a solid product obtained by the suction filtration with deionized water to be neutral (without chloride ions), drying at 80 ℃, and grinding to obtain acidified rectorite powder;
(2) weighing 3g of the acidified rectorite powder obtained in the step (1), weighing 30ml of a 4mol/L sodium hydroxide aqueous solution, mixing the acidified rectorite powder and the sodium hydroxide aqueous solution, magnetically stirring at the temperature of 30 ℃ for 20 hours to obtain a turbid solution, cooling to room temperature, performing suction filtration, and reserving a filtrate (the pH value is 14.00-14.60);
(3) and (3) adding strong acid type cation exchange resin into the filtrate obtained in the step (2) to regulate the pH value to 13.30 (neutralizing residual sodium hydroxide), carrying out suction filtration on the mixed solution, and supplementing deionized water into the filtrate to 50ml to serve as a silica-alumina source.
(4) Weighing 0.5g of Cetyl Trimethyl Ammonium Bromide (CTAB) into a 100mL beaker, adding 10mL of deionized water, stirring and dissolving to form a CTAB solution, adding the CTAB solution into 50mL of filtrate obtained in the step (3), regulating and controlling the pH value of the mixed solution to 9 by using 0.5-6 mol/L hydrochloric acid aqueous solution, magnetically stirring at 60 ℃ for 2 hours, transferring the mixed solution into a high-pressure reaction kettle, carrying out hydrothermal crystallization reaction at 110 ℃ for 24 hours, cooling the reaction kettle to room temperature, washing the product with alcohol and deionized water until the supernatant does not contain CTAB, and drying and grinding at 80 ℃ to obtain a precursor.
(5) Putting the precursor obtained in the step (4) into a muffle furnace (air atmosphere), calcining at 550 ℃ for 6h (the heating rate is 2 ℃/min), removing the surfactant to obtain the ordered mesoporous material Al-MCM-41 with the specific surface area of 853m2Per g, pore volume 0.68m3In terms of/g, the mean pore diameter is 1.6 nm.
Example 5
(1) Weighing 5g of natural rectorite, weighing 250ml of 8mol/L hydrochloric acid aqueous solution, mixing the rectorite and the hydrochloric acid aqueous solution, magnetically stirring at the temperature of 80 ℃ for 12 hours to obtain turbid liquid, cooling to room temperature, performing suction filtration, washing a solid product obtained by the suction filtration with deionized water to be neutral (without chloride ions), drying at the temperature of 80 ℃, and grinding to obtain acidified rectorite powder;
(2) weighing 3g of the acidified rectorite powder obtained in the step (1), weighing 15ml of a 4mol/L sodium hydroxide aqueous solution, mixing the acidified rectorite powder and the sodium hydroxide aqueous solution, magnetically stirring at the temperature of 30 ℃ for 20 hours to obtain a turbid solution, cooling to room temperature, performing suction filtration, and reserving a filtrate (the pH value is 14.00-14.60);
(3) and (3) adding strong acid type cation exchange resin into the filtrate obtained in the step (2) to regulate the pH value to 13.30 (neutralizing residual sodium hydroxide), carrying out suction filtration on the mixed solution, and supplementing deionized water into the filtrate to 50ml to serve as a silica-alumina source.
(4) Weighing 0.5g of Cetyl Trimethyl Ammonium Bromide (CTAB) into a 100mL beaker, adding 10mL of deionized water, stirring and dissolving to form a CTAB solution, adding the CTAB solution into 50mL of filtrate obtained in the step (3), regulating and controlling the pH value of the mixed solution to 9 by using 0.5-6 mol/L hydrochloric acid aqueous solution, magnetically stirring at 60 ℃ for 2 hours, transferring the mixed solution into a high-pressure reaction kettle, carrying out hydrothermal crystallization reaction at 110 ℃ for 24 hours, cooling the reaction kettle to room temperature, washing the product with alcohol and deionized water until the supernatant does not contain CTAB, and drying and grinding at 80 ℃ to obtain a precursor.
(5) Putting the precursor obtained in the step (4) into a muffle furnace (air atmosphere), calcining at 550 ℃ for 6h (the heating rate is 2 ℃/min), removing the surfactant to obtain the ordered mesoporous material Al-MCM-41 with the specific surface area of 753m2Per g, pore volume 0.63m3In terms of/g, the mean pore diameter is 1.1 nm.
Example 6
(1) Weighing 5g of natural rectorite, weighing 500ml of 6mol/L hydrochloric acid aqueous solution, mixing the rectorite and the hydrochloric acid aqueous solution, magnetically stirring at 130 ℃ for 12 hours to obtain turbid liquid, cooling to room temperature, performing suction filtration, washing a solid product obtained by the suction filtration with deionized water to be neutral (without chloride ions), drying at 80 ℃, and grinding to obtain acidified rectorite powder;
(2) weighing 3g of the acidified rectorite powder obtained in the step (1), weighing 45ml of a 4mol/L sodium hydroxide aqueous solution, mixing the acidified rectorite powder and the sodium hydroxide aqueous solution, magnetically stirring at the temperature of 30 ℃ for 20 hours to obtain a turbid solution, cooling to room temperature, performing suction filtration, and reserving a filtrate (the pH value is 14.00-14.60);
(3) and (3) adding strong acid type cation exchange resin into the filtrate obtained in the step (2) to regulate the pH value to 13.30 (neutralizing residual sodium hydroxide), carrying out suction filtration on the mixed solution, and supplementing deionized water into the filtrate to 50ml to serve as a silica-alumina source.
(4) Weighing 0.5g of Cetyl Trimethyl Ammonium Bromide (CTAB) into a 100mL beaker, adding 10mL of deionized water, stirring and dissolving to form a CTAB solution, adding the CTAB solution into 50mL of filtrate obtained in the step (3), regulating and controlling the pH value of the mixed solution to 9 by using 0.5-6 mol/L hydrochloric acid aqueous solution, magnetically stirring at 60 ℃ for 2 hours, transferring the mixed solution into a high-pressure reaction kettle, carrying out hydrothermal crystallization reaction at 110 ℃ for 24 hours, cooling the reaction kettle to room temperature, washing the product with alcohol and deionized water until the supernatant does not contain CTAB, and drying and grinding at 80 ℃ to obtain a precursor.
(5) Putting the precursor obtained in the step (4) into a muffle furnace (air atmosphere), calcining at 550 ℃ for 6h (the heating rate is 2 ℃/min), removing the surfactant to obtain the ordered mesoporous material Al-MCM-41 with the specific surface area of 821m2Per g, pore volume 0.72m3In terms of/g, the mean pore diameter is 2.7 nm.
Example 7
(1) Weighing 5g of natural rectorite, weighing 250ml of 6mol/L hydrochloric acid aqueous solution, mixing the rectorite and the hydrochloric acid aqueous solution, magnetically stirring at the temperature of 110 ℃ for 12 hours to obtain turbid liquid, cooling to room temperature, performing suction filtration, washing a solid product obtained by the suction filtration with deionized water to be neutral (without chloride ions), drying at the temperature of 80 ℃, and grinding to obtain acidified rectorite powder;
(2) weighing 3g of the acidified rectorite powder obtained in the step (1), weighing 30ml of a 4mol/L sodium hydroxide aqueous solution, mixing the acidified rectorite powder and the sodium hydroxide aqueous solution, magnetically stirring at the temperature of 10 ℃ for 20 hours to obtain a turbid solution, cooling to room temperature, performing suction filtration, and reserving a filtrate (the pH value is 14.00-14.60);
(3) and (3) adding strong acid type cation exchange resin into the filtrate obtained in the step (2) to regulate the pH value to 13.30 (neutralizing residual sodium hydroxide), carrying out suction filtration on the mixed solution, and supplementing deionized water into the filtrate to 50ml to serve as a silica-alumina source.
(4) Weighing 0.5g of Cetyl Trimethyl Ammonium Bromide (CTAB) into a 100mL beaker, adding 10mL of deionized water, stirring and dissolving to form a CTAB solution, adding the CTAB solution into 50mL of filtrate obtained in the step (3), regulating and controlling the pH value of the mixed solution to 9 by using 0.5-6 mol/L hydrochloric acid aqueous solution, magnetically stirring at 60 ℃ for 2 hours, transferring the mixed solution into a high-pressure reaction kettle, carrying out hydrothermal crystallization reaction at 110 ℃ for 24 hours, cooling the reaction kettle to room temperature, washing the product with alcohol and deionized water until the supernatant does not contain CTAB, and drying and grinding at 80 ℃ to obtain a precursor.
(5) Putting the precursor obtained in the step (4) into a muffle furnace (air atmosphere), calcining at 550 ℃ for 6h (the heating rate is 2 ℃/min), removing the surfactant to obtain the ordered mesoporous material Al-MCM-41 with specific surface areaProduct of 786m2Per g, pore volume 0.69m3In terms of/g, the mean pore diameter is 1.9 nm.
Example 8
(1) Weighing 5g of natural rectorite, weighing 250ml of 6mol/L hydrochloric acid aqueous solution, mixing the rectorite and the hydrochloric acid aqueous solution, magnetically stirring at the temperature of 110 ℃ for 12 hours to obtain turbid liquid, cooling to room temperature, performing suction filtration, washing a solid product obtained by the suction filtration with deionized water to be neutral (without chloride ions), drying at the temperature of 80 ℃, and grinding to obtain acidified rectorite powder;
(2) weighing 3g of the acidified rectorite powder obtained in the step (1), weighing 30ml of a 4mol/L sodium hydroxide aqueous solution, mixing the acidified rectorite powder and the sodium hydroxide aqueous solution, magnetically stirring at 50 ℃ for 20 hours to obtain a turbid solution, cooling to room temperature, and performing suction filtration to obtain a filtrate (the pH value is 14.00-14.60) for later use;
(3) and (3) adding strong acid type cation exchange resin into the filtrate obtained in the step (2) to regulate the pH value to 13.30 (neutralizing residual sodium hydroxide), carrying out suction filtration on the mixed solution, and supplementing deionized water into the filtrate to 50ml to serve as a silica-alumina source.
(4) Weighing 0.5g of Cetyl Trimethyl Ammonium Bromide (CTAB) into a 100mL beaker, adding 10mL of deionized water, stirring and dissolving to form a CTAB solution, adding the CTAB solution into 50mL of filtrate obtained in the step (3), regulating and controlling the pH value of the mixed solution to 9 by using 0.5-6 mol/L hydrochloric acid aqueous solution, magnetically stirring at 60 ℃ for 2 hours, transferring the mixed solution into a high-pressure reaction kettle, carrying out hydrothermal crystallization reaction at 110 ℃ for 24 hours, cooling the reaction kettle to room temperature, washing the product with alcohol and deionized water until the supernatant does not contain CTAB, and drying and grinding at 80 ℃ to obtain a precursor.
(5) Putting the precursor obtained in the step (4) into a muffle furnace (air atmosphere), calcining at 550 ℃ for 6h (the heating rate is 2 ℃/min), removing the surfactant to obtain the ordered mesoporous material Al-MCM-41 with the specific surface area of 803m2Per g, pore volume 0.74m3In terms of/g, the mean pore diameter is 2.5 nm.
Comparative example 4
In this comparative example, the resin treatment was not performed on the alkaline leach solution as follows:
(1) weighing 5g of natural rectorite, weighing 50ml of 1mol/L hydrochloric acid aqueous solution, mixing the rectorite and the hydrochloric acid aqueous solution, magnetically stirring for 12 hours at room temperature to obtain turbid liquid, cooling to room temperature, performing suction filtration, washing a solid product obtained by suction filtration to be neutral (without chloride ions) by using deionized water, drying and grinding at the temperature of 80 ℃ to obtain acidified rectorite powder;
(2) weighing 3g of the acidified rectorite powder obtained in the step (1), weighing 10ml of a 1mol/L sodium hydroxide aqueous solution, mixing the acidified rectorite powder and the sodium hydroxide aqueous solution, magnetically stirring at room temperature for 20 hours to obtain a turbid solution, cooling to room temperature, performing suction filtration, and keeping a filtrate for later use;
(3) and (3) supplementing deionized water to 50ml of filtrate obtained in the step (2) as a silicon-aluminum source.
(4) Weighing 0.5g of Cetyl Trimethyl Ammonium Bromide (CTAB) into a 100mL beaker, adding 10mL of deionized water, stirring and dissolving to form a CTAB solution, adding the CTAB solution into 50mL of filtrate obtained in the step (3), regulating and controlling the pH value of the mixed solution to 9 by using 0.5-6 mol/L hydrochloric acid aqueous solution, magnetically stirring at 60 ℃ for 2 hours, transferring the mixed solution into a high-pressure reaction kettle, carrying out hydrothermal crystallization reaction at 110 ℃ for 24 hours, cooling the reaction kettle to room temperature, washing the product with alcohol and deionized water until the supernatant does not contain CTAB, and drying and grinding at 80 ℃ to obtain a precursor.
(5) And (3) putting the precursor obtained in the step (4) into a muffle furnace (air atmosphere), calcining at 550 ℃ for 6h (the heating rate is 2 ℃/min), removing the surfactant to obtain white powder, and failing to prepare the ordered mesoporous material Al-MCM-41.
Detection experiment:
1. the ordered mesoporous material Al-MCM-41 prepared in examples 1-2 and the white powder prepared in comparative examples 1-4 were subjected to small-angle X-ray diffraction analysis, and the results are shown in FIG. 2, wherein the ordered mesoporous material Al-MCM-41 prepared in examples 1-2 has three characteristic diffraction peaks of typical MCM-41: (100) diffraction peaks (110) and (200) show that the prepared ordered mesoporous material Al-MCM-41 has a typical hexagonal structure and higher order degree; the white powders prepared in comparative examples 1 to 4 did not exhibit three characteristic diffraction peaks typical of MCM-41: (100) diffraction peaks (110) and (200) indicate that the ordered mesoporous material Al-MCM-41 cannot be successfully prepared. The results of example 2 and example 3 show that the strong acid type cation exchange resin treatment of the alkaline leaching solution can overcome the technical problem that alkali remains when a silicon source is extracted, and the ordered mesoporous material Al-MCM-41 is successfully prepared by taking rectorite as a raw material.
2. The ordered mesoporous material Al-MCM-41 prepared in examples 1 to 2 was subjected to wide-angle X-ray diffraction analysis, and the results are shown in fig. 3, in which a diffraction peak package appeared in the range of 2 θ ═ 22 ° to 24 °, indicating that the prepared ordered mesoporous material Al-MCM-41 was composed of amorphous silica.
3. The ordered mesoporous material Al-MCM-41 prepared in example 2 was subjected to nitrogen adsorption and desorption analysis, and the result is shown in FIG. 4, where the prepared ordered mesoporous material Al-MCM-41 sample is a typical IV-type adsorption curve, and is characteristic of a mesoporous material, and the specific surface area of the sample is 1105m2The pore volume can reach 1.12cm3In terms of/g, the mean pore diameter is 3.8 nm.
4. Scanning electron microscope analysis is carried out on the ordered mesoporous material Al-MCM-41 prepared in the embodiment 2, the result is shown in figure 5, and it can be seen from the figure that the grain diameter of the prepared ordered mesoporous material Al-MCM-41 is relatively uniform, and the pore channel structure needs to be characterized by a transmission electron microscope.
5. The result of transmission electron microscope analysis of the ordered mesoporous material Al-MCM-41 prepared in example 2 is shown in fig. 6, which shows that the prepared ordered mesoporous material Al-MCM-41 has long-range order in the mesoporous channel in the direction perpendicular to the mesoporous channel, and the channel has a regular hexagonal structure along the channel direction, and is regular, uniform in size, and higher in order, which is consistent with the SAXRD analysis result.
Claims (4)
1. A method for preparing ordered mesoporous material Al-MCM-41 by utilizing rectorite is characterized by comprising the following steps:
step (1): soaking rectorite in acid solution, performing solid-liquid separation, washing and drying to obtain acidified rectorite; wherein the acid liquor isAqueous solution of strong inorganic acid, wherein H+The concentration is 2-8 mol/L; the solid-liquid ratio of the rectorite to the acid solution is 1: 30-1: 100 g/mL; the temperature of the acid liquor soaking process is 60-140 ℃; the soaking time is 4-12 hours;
step (2): performing alkaline leaching treatment on acidified rectorite, and then performing solid-liquid separation to obtain an alkaline leaching solution; the alkaline solution used in the alkaline leaching process is aqueous solution of alkali metal hydroxide, in which OH is contained-The concentration of (a) is 2-6 mol/L; the solid-liquid ratio of the acidified rectorite to the alkali liquor is 1: 5-1: 20 g/mL; the temperature in the alkaline leaching process is 10-50 ℃; the time is 8-24 h; the pH value of the obtained alkali leaching solution is 14.00-14.60;
and (3): mixing the alkali leaching solution with strong acid type cation exchange resin, neutralizing the alkali remained in the alkali leaching solution by using the strong acid type cation exchange resin until the pH value of the alkali leaching solution is 13.00-13.40, and then carrying out solid-liquid separation on the mixed solution to obtain filtrate containing silicon and aluminum sources;
and (4): mixing the filtrate containing the silicon and aluminum source obtained in the step (3) with a cationic surfactant, and then carrying out hydrothermal reaction to obtain a precursor;
and (5): and calcining the precursor to obtain the ordered mesoporous material Al-MCM-41.
2. The method for preparing ordered mesoporous material Al-MCM-41 with rectorite as claimed in claim 1, wherein the cationic surfactant is cetyl trimethyl ammonium bromide;
the concentration of the cationic surfactant in the initial solution of the hydrothermal reaction is 0.1-0.5 mol/L;
the pH value of the initial solution of the hydrothermal reaction is 8-12;
the temperature of the hydrothermal reaction is 100-150 ℃; the hydrothermal reaction time is 24-72 h.
3. The method for preparing ordered mesoporous material Al-MCM-41 using rectorite as claimed in claim 1, wherein the calcination treatment is performed in air atmosphere; the calcining temperature is 500-600 ℃;
the temperature rise rate in the calcining process is 1-3 ℃/min.
4. The method for preparing the ordered mesoporous material Al-MCM-41 with the rectorite as the claim 3, wherein the calcining time is 4-10 h.
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